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Reactivity and coordination chemistry of ruthenium(II) aminophosphine complexes with H2S,thiols,H2O and… Ma, Erin Shu Fen 1999

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REACTIVITY AND COORDINATION CHEMISTRY OF RUTHENIUM(II) AMINOPHOSPHINE COMPLEXES WITH H 2S, THIOLS, H 2 0 AND OTHER SMALL MOLECULES By ERIN SHU FEN MA B.Sc. (Hons.), University of British Columbia, 1994 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in THE FACULTY OF GRADUATE STUDIES (Department of Chemistry) We accept this thesis as conforming to the required standard THE UNIVERSITY OF BRITISH COLUMBIA August 1999 ©Erin Shu Fen Ma, 1999 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of The University of British Columbia Vancouver, Canada Date Qdtdbtr , (W DE-6 (2/88) Abstract The coordination of small molecules (H2S, RSH, H 20, ROH, H 2 , NH 3 , N 2 and N 20; R = alkyl) to the coordinatively unsaturated complexes RuX2(P-N)(PR3) (X = CL Br, I; P-N = [o-(7Y,A/-dimethylamino)phenyl]diphenylphosphine; R = Ph, /7-tolyl), themselves prepared from RuX2(PR3)3 and P-N, was investigated (see figure). The species containing the Ru(P-N) moiety were characterized spectroscopically, particularly by *H and 31P{1H} NMR and in some cases in conjunction with X-ray crystallography. I .',N L = H 2 S, RSH, H i N H 3 , N 2 , N 2 0 X — R U — L R3P' + L - L + L 1 • L ^ P — \ L = H 2 0 , ROH, N H 3 X — R u — X RsP*^ Os-RuX2(P-N)(PPh3)(L) species (X = CI, L = H2S, MeSH, EtSH; X = Br, L = H2S) were isolated from the reaction of RuX2(P-N)(PPh3) with excess L in acetone, and characterized crystallographically. The geometry of these complexes is pseudo-octahedral with the halogen atoms in mutual cis positions with the coordinated S-ligand cis to the P-atom of the P-N ligand and trans to a halogen atom; all H-atoms on the coordinated S-ligands were refined isotropically. The S-H bond lengths are of equal or shorter distances (1.20 - 1.34 A) than those of free gaseous ligands (1.33 - 1.40 A); in particular, the bond length of 1.03 A for the coordinated MeSH complex is the shortest S-H distance yet reported. Of interest, the ^ N M R spectrum of c/s-RuX2(P-N)(PPh3)(SH2) shows three-bond coupling of only one ii proton of the coordinated H2S to the P-atom of the P-N ligand (X = C1, 3JHP= 3.5 HZ; X = Br, 3JH P = 4.3 Hz) at -50°C, and this represents an extension of the Karplus relationship to vicinal coupling within a P-Ru-S-H system. The reaction of RuCl2(P-N)(PR3) with H 2 0 gave /raws-RuCl2(P-N)(PR3XOH2), which was crystallographically characterized. The geometry is pseudo-octahedral with mutually trans Cl-atoms; the H 2 0 ligand is trans to the P-atom of the P-N ligand. The orientation of incoming monodentate ligand L in either cis or trans positions (see figure) is affected by the mutual trans influence of L and of the apical phosphine of RuX2(P-N)(PR3). The thermodynamics for the reversible binding of H2S, thiols, H 2 and H 2 0 to RuCl2(P-N)(PPh3), in solution, were determined using UV-Vis and NMR spectroscopies. The low AH 0 values (-22 to -54 kJ/mol) imply relatively weak Ru-L bond energies and the negative AS° values (-32 to -140 J/mol K) are consistent with binding of a small molecule at a metal site. Differential scanning calorimetry on solid state samples also allowed for determination of AH° values, and estimation of enthalpy changes for a cis- to trans-rearrangement in solution. Cw-RuX2(P-N)(PPh3)(SH2) (X = CI, Br) reacted with NaSH or proton sponge (in the presence of added H2S) to give initially Ru(SH)Cl(P-N)(PPh3) and then Ru(SH)2(P-N)(PPh3). The mercapto species, however, are thermally unstable and were only observed by NMR spectroscopy at -78°C. Reaction of 1 atm NH 3 with RuX2(P-N)(PPh3) (X = CI, Br) in the solid state led to the formation of frans-RuX2(P-N)(PPh3)(NH3) which, when dissolved in solution, subsequently isomerized to cw-RuX2(P-N)(PPh3)(NH3). Evidence for bis- and tris-arnmine species, as well as for [RuX(P-N)(PPh3)(NH3)2—X] with a 'strongly associated' halide, is also presented. iii The formation of cfs-RuCl2(P-]S0(PPh3)(N2O) was observed by NMR spectroscopy at -40°C when RuCl2(P-N)(PPh3) was subjected to 6 atm N 2 0 in CD2C12. The coordination of N 2 0 is of particular interest because of the rarity of such a reaction and because of the potential of discovering an effective catalytic oxidation system using N 2 0 as an O-atom donor. In fact, c/5-RuCl2(P-N)(PPh3)(N20) appears to form c/s-RuCl2(P-]S0(PPh3)(V-N2) and 0 2 at T > -40°C. When the system was warmed to room temperature, 0=PPh3 and (u,-0)(n-Cl)2[RuCl(P-N)]2 were formed. The crystallographically characterized u>oxo complex was also formed when RuCl2(P-N)(PPh3) was reacted with 02. RuCl2(P-N)(PPh3) also reacted with HOCPh to give the crystallographically characterized cw-RuCl2{TJ-N)(PPh3)(=C=CHPh). The carbene complex reacted with H2S and H 2 0 to give c/j-RuCl2(P-N)(PPh3)(S=C(H)CH2Ph) and a mixture containing RuCl(P-N)(PPh3)(CH2Ph)(CO) and RuCl2(P-N)(PPh3)(CO), respectively. The formulations of the products were based on 31P{1H} NMR and IR spectroscopic data. The reactions of RuCl2(PR3)3 with aminophosphine ligands other than P-N were also explored: RuCl2(BPN)(PR3) (BPN = bis[o-(AyV*-dimethylammo)phenyl]phenylphosphine) and RuCl2(PAN)(PR3) (PAN = l-(A ,^A -^dimethylammo)-8-(diphenylphosphino)naphthalene) were isolated and characterized; RuCl2(AMPHOS)(PPh3) (AMPHOS = (#)-(+)-#, TV-dimethyl-l-[o-(dimethylphosphino)phenyl]ethylamine) was observed in situ, and an impure sample of RuCl2(ALAPHOS)2 (ALAPHOS = [(<S)-2-(dimethylamino)propyl]diphenylphosphine) was isolated. PTN (tris[o-(7Y,7V-dimethylamino)phenyl]phenylphosphine) did not react with RuCl2(PR3)3. iv Table of Contents Abstract ii Table of Contents v List of Figures xiii List of Tables xx List of Symbols and Abbreviations xxii Table of Compound Numbers xxvi Acknowledgements xxvii Chapter 1 Introduction 1 1.1 Natural and Industrial Occurrences Sulfur Compounds 2 1.1.1 The Natural Sulfur Cycle 2 1.1.2 Hydrodesulfurization (HDS) and the Claus Process 3 1.2 Coordination Chemistry of H2S and Thiols 5 1.2.1 Physical Properties of H2S and Thiols 5 1.2.2 Reactions of H2S and Thiols with Transition Metal Complexes 7 1.2.2.1 Mononuclear Mercapto and Thiolato Complexes 8 1.2.2.2 Bridging Mercapto and Thiolato Ligands 11 1.2.2.3 Recovery of H 2 from H2S using Pd2X2(u,2-dpm)2 17 1.3 The Chemistry of Transition Metal Aminophosphine Complexes 19 1.4 Overview of Thesis 22 1.5 References 23 Chapter 2 Experimental Procedures 29 2.1 Materials 29 2.1.1 Gases 29 2.1.2 Solvents 29 2.1.3 Compounds 30 2.2 Instrumentation 30 2.2.1 Nuclear Magnetic Resonance Spectroscopy 30 2.2.2 Infrared Spectroscopy 31 2.2.3 Ultraviolet Spectroscopy 31 2.2.4 Thermal Analysis 32 V 2.2.5 Microanalysis 32 2.2.6 X-ray Crystallography 32 2.2.7 Gas Chromatography 33 2.2.8 Magnetic Susceptibility Studies 33 2.2.9 Conductivity Measurements 33 2.3 Syntheses ofLigands 34 2.3.1 [o-(AyV-Dimethylaniino)phenyl]diphenylphosphine, P-N 35 2.3.2 Bis[o-(iV -^dimethylamino)phenyl]phenylphosphine, BPN 36 2.3.3 Tris[o-(iV -^dimethylamino)phenyl]phosphine, TPN 36 2.3.4 (i?)-(+)-A^A -^Dimethyl-l-[o-(diphenylphosphmo)phenyl]ethylarrune, AMPHOS ...37 2.3.5 l-(A -^Dimethylamino)-8-(diphenylphospliino)naphthalene, PAN 38 2.3.6 [(6 -^2-(pimethylamino)propyl]diphenylphosphine, ALAPHOS 39 2.3.7 o-Diphenylphosphineanisole, PO 41 2.4 Syntheses of Ruthenium Precursors 42 2.4.1 Dichlorotris(triphenylphosphine)ruthenium(II), RuCl2(PPh3)3 (1) 42 2.4.2 Dichlorotris(tri-/?-tolylphosphine)ruthenium(II), RuCl2(P(>-tolyl)3)3 (2) 43 2.4.3 Cw-dichlorotetrakis(dimethylsulfoxide)ruthenium(n), C/s-RuCl2(DMSO)4 (3) ...43 2.4.4 TricUorobis(triarylphospMne)(dimethylacetamide)mthemum(]TJ)-DMA solvate RuCl3(PPh3)2(DMA)(DMA) (4a) and RuCl2(P(p-tolyl)3)2(DMA)-(DMA) (4b)..43 2.5 Dichlorobis(o-diphenylphosphinoanisole)ruthenium(II), RuCl2(PO)2 (5) 44 2.6 Syntheses of Ruthenium(II) Aminophosphine Complexes 44 2.6.1 Dichloro{[o-(iV,iV-dimethylamino)phenyl](diphenylphospliine)}-(triphenylphosphine)ruthenium(II), RuCl2(P-N)(PPh3) (6a) 44 2.6.2 Dibromo{[o-(7Y -^dimethylamino)phenyl](diphenylphosphine)}-(triphenylphosphine) ruthenium(n), RuBr2(P-N)(PPh3) (6b) 45 2.6.3 Diiodo{[o-(A^A -^dimethylamino)phenyl](diphenylphosphine)}-(triphenylphosphine)ruthenium(n), RuI2(P-N)(PPh3) (6c) 45 2.6.4 DicWoro{[o-(A^A -^dimethylamino)phenyl](diphenylphosphine)}-(tri-/7-tolylphosphine)ruthenium(II), RuCl2(P-N)(P(>-tolyl)3) (7a) 46 2.6.5 Dibromo{[o-(iVVV-dimethylamino)phenyl](diphenylphosphine)}-(tri-/7-tolylphosphine)ruthenium(II), RuBr2{P-N)(P(p-tolyl)3) (7b) 46 vi 2.6.6 Duodo{ [o-(/V -^dimethylarmno)phenyl](diphenylpho (tri-/?-tolylphospMne)mthemum(II), RuI2(P-N)(P(>tolyl)3) (7c) 47 2.6.7 Dichlorobis { [o-(N, /V-dimethylamino)phenyl] (diphenylpho sphine) } -ruthenium(n),RuCl2(P-N)2 (8) 47 2.6.8 DicMoro[(l-(JV,N-dimethylaniin^ (triphenylphosphine) mthenium(II), RuCl2(PAN)(PPh3) (9) 48 2.6.9 DicMoro[(l-(AyV-dimethylam^ (tri-/7-tolylphosprune)mthemum(TI), RuCl2(PAN)(P(>tolyl)3) (10) 48 2.6.10 DicMoro{(i?)-AyV-dimet^ (triphenylphospMne)ruthenium(n), RuCl2(AMPHOS)(PPh3) (11) 48 2.6.11 Attempts to Prepare Dichlorobis{[(5)-2-(dimethylamino)propyl]-(diphenylphosphine)}ruthenium(n), RuCl2(ALAPHOS)2 (12) 49 2.6.12 Dichloro {bis[o-(7V,7V-dimethylamino)phenyl] (phenylphosphine) } -(triphenylphosphine)ruthenium(II), RuCl2(BPN)(PPh3) (13) 50 2.6.13 DicMoro{bis[o-(#,A -^d^methylamino)phenyl](phenylphosphine)}-(tri-/>-tolylphospttne) ruthenium(II), RuCl2(BPN)(P(p-tolyl)3) (14) 51 2.7 Syntheses of Ruthenium(III) Aminophosphine Complexes 51 2.7.1 TricUoro{[o-(A ,^iVLdimethylamino)phenyl](diphenylphosphine)}-(triphenylphosphine)ruthenium(III), RuCl3(P-N)(PPh3) (15a) 51 2.7.2 TricMoro{[o-(A /^V-dimethylamino)phenyl](diphenylphosphine)}-(tri-/?-tolylphosphine) ruthenium(m), RuCl3(P-N)(P(p-tolyl)3) (15b) 52 2.7.3 M?r-trichloro {bis[o-(A7, /V-dimethylamino)phenyl] (phenylphosphine)} -ruthenium(UI),MeA--RuCl3(BPN) (16) 52 2.7.4 Di- u.-chloro-u,-oxo-bis {chloro [o-(A^ALdimethylamino)phenyl] -(diphenylphosphine)ruthenium(m)}, (u.-0)(u-Cl)2[RuCl(P-N)]2 (17) 53 2.8 Syntheses of Ruthenium(II) Complexes Containing Coordinated H2S or Thiols: CVs-dichloro {[o-N,N-dimethylammo)phenyl](diphenylphosphine)} -(triarylphosphine)(ligand)ruthenium(II), C/s-RuX2(P-N)(PR3)(L) 53 2.8.1 a5-RuCl2(P-N)(PPh3)(SH2)-(acetone) (18a) 54 2.8.2 Cw-RuBr2(P-N)(PPh3)(SH2)-(acetone) (18b) 55 2.8.3 In situ Preparation of Gs-RuI2(P-N)(PPh3)(SH2) (18c) 55 2.8.4 Cw-RuCl2(P-N)(P(p-tolyl)3)(SH2)-(acetone) (19a) 56 vii 2.8.5 a5-RuBr2(P-N)(P(p-tolyl)3XSH2Hacetone) (19b) 56 2.8.6 In situ Preparation of Cis-RuI2(P-N)(P(p-tolyl)3)(SH2) (19c) 56 2.8.7 a5-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) 57 2.8.8 Cw-RuCl2(P-N)(PPh3)(TitSH)-(EtSH)-(acetone) (21) 57 2.8.9 In situ Preparation of C/5-RuCl2(P-N)(PPh3)(RSH), R - w-Pr, /-Pr, w-Pn, w-Hx, and Bz (Pr = propyl, Pn = pentyl, Hx = hexyl, Bz = benzyl) 58 2.9 In situ Preparation of Ru(L)X(P-N)(PPh 3) (L = SH, OH, H) and Ru(L) 2(P-N)(PPh 3) (X = CI, Br; L = SH, OH, H) 59 2.9.1 Ru(SH)Cl(P-N)(PPh 3) (27a) 59 2.9.2 Ru(SH)Br(P-N)(PPh 3) (27b) 60 2.9.3 Ru(OH)Cl(P-N)(PPh 3) (28a) 60 2.9.4 Ru(OH)Br(P-N)(PPh 3) (28b) 61 2.9.5 Ru(H)Cl(P-N)(PPh 3) (29) 61 2.9.6 Ru(SH) 2(P-N)(PPh 3) (30) 61 2.9.7 Ru(OH) 2(P-N)(PPh 3) (31) 62 2.9.8 Ru(H) 2(P-N)(PPh 3) (32) 62 2.10 Syntheses of Ruthenium(II) Complexes Containing Coordinated H 2 0 , MeOH, or EtOH 62 2.10.1 7>a«5-RuCl2(P-N)(PPh3)(OH2) (33a) 62 2.10.2 7>a»5-RuCl2(P-N)(P(p-tolyl)3)(OH2) (33b) 63 2.10.3 rrawj-RuCl2(P-N)(PPh3)(MeOH) (34) 63 2.10.4 rra«s-RuCl2(P-N)(PPh3)(EtOH) (35) 64 2.11 Syntheses of Ruthenium(II) Complexes with Other Coordinated Gases 65 2.11.1 a5-RuCl 2(P-N)(PPh 3Xri 2-H2) (36) 65 2.11.2 Reactions with NH 3 66 2.11.3 Cw-RuCl2(P-N)(PPh3)(V-N2) (43) 69 2.11.4 C«-RuCl 2(P-N)(PPh 3)(N 20) (44) 70 2.12 Synthesis and Reactions of Ruthenium(TI) Carbene Complexes 70 2.12.1 C/5-RuCl2(P-N)(PPh3)(=C=CHPh) (45) 70 2.12.2 Cw-RuCl2(P-N)(P(p-tolyl)3)(=C=CHPh) (46) 71 2.12.3 Cw-RuCl 2(P-N)(PPh 3)(=C=CHPhCH 3) (47) 71 vi i i 2.12.4 Cw-RuCl 2(P-N)(PPh 3)(SCHCH 2Ph) (48) 72 2.12.5 Reaction of Cw-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) with H 2 0 72 2.13 References 74 Chapter 3 Synthesis and Reactivity of Ruthenium Aminophosphine Precursors. .76 3.1 Introduction 76 3.2 Preparation ofRuCl 2(P-N)(PR 3) (R = Ph (6a), R= p-tolyl (7a)) 76 3.2.1 Decomposition of RuCl 2(P-N)(PPh 3) (6a) to (|>0)(u-Cl)2[RuCl(P-N)]2 (17) 79 3.3 Metathesis Reactions 85 3.3.1 Synthesis and Characterization of RuBr 2(P-N)(PR 3) (6b) and RuI 2(P-N)(PR 3) (6c) 86 3.3.2 In situ Formation of Ru(OH)X(P-N)(PPh 3) (X = CI (28a), Br (28b)) and Ru(OH) 2(P-N)(PPh 3) (31) 88 3.3.3 In situ Reactions of 6a or 6b with NaSHxH 20 91 3.3.4 In situ Formation of Ru(H) 2(P-N)(PPh 3) (32) 92 3.4 Synthesis of RuCl 2(BPN)(PR 3) (R = Ph(13),p-tolyl (14)) 93 3.5 Synthesis of Mer-RuCl 3(BPN) (16) 96 3.6 The Reactions of TPN withRu(II) and (III) 99 3.7 Characterization and Reactivity ofRuCl 2(PAN)(PR 3) (R = Ph (9),/?-tolyl (10)) 100 3.8 Attempted Synthesis and Reactivity ofRuCl 2(AMPHOS)(PPh 3) (11) 101 3.9 Attempted Preparations ofRuCl 2(ALAPHOS) 2 (12) 104 3.10 Miscellaneous: Reactivity of 7ra«s-RuCl 2(PO) 2 (5) withH 2S 104 3.11 Summary 105 3.12 References 107 Chapter 4 Transition Metal H2S AND Thiol Complexes: Synthesis and Characterization of Cis-RuX(P-N)(PR)(L); L = H2S, Thiols 110 4.1 Introduction 110 4.1.1 Transition Metal H 2S Complexes 110 4.1.2 Transition Metal Thiol Complexes 115 4.2 Synthesis and Characterization of Cw-RuX2(P-N)(PPh3)(SH2), X = CI, Br, 1 119 4.2.1 Cw-RuCl 2(P-N)(PPh 3)(SH 2) (18a) 120 4.2.2 Cw-RuBr 2(P-N)(PPh 3)(SH 2) (18b) 131 ix 4.2.3 In situ Preparation of C/s-RuI2(P-N)(PPh3)(SH2) (18c) and a5-RuI2(P-N)(P(p-tolyl)3XSH2) (19c) 135 4.3 The Synthesis and Characterization of C/s-RuCl2(P-N)(PPh3)(RSH) Species (R = alkyl) 1 3 6 4.3.1 Cw-RuCl2(P-N)(PPh3)(MeSH) (20) 136 4.3.2 C/s-RuCl2(P-N)(PPh3)(EtSH) (21) 140 4.3.3 In situ Preparation of C/s-RuCl2(P-N)(PPh3)(RSH) Species, R = w-Pr, /-Pr, n-Pn, H-HX, Bz 145 4.4 Comparison of Coordinated S-H Vibrational Frequencies for 18a, 18b, 19a, 20 and 21 148 4.5 The UV-Vis Spectra of RuX2(PN)(PR3) (X = halogen; PN = P-N, PAN or AMPHOS; R = Ph OR/7-tolyl) and Cw-RuX2(P-N)(PPh3)(L) (L = H2S, MeSH orEtSH) Species 149 4.6 Solution Thermodynamics for Reversible Formation ofH2S and Thiol Complexes.... 152 4.7 The Ru-S Bond Strengths in the Solid State: DSC Experiments 156 4.8 The Acidity of RuCl2(P-N)(PPh3)(H2S): Proton Abstraction with Proton Sponge.... 158 4.9 Reaction ofRuCl2(P-N)(PPh3) with S0 2 166 4.10 Decompositon ofCw-RuCl2(P-N)(PPh3)(SH2) 167 4.11 Summary 168 4.12 References 169 Chapter 5 Coordination of H 2 0 and Alcohols to RuCl2(P-N)(PPh3) 173 5.1 Preparation of rra«s-RuCl2(P-N)(PR3)(OH2) 173 5.2 X-Ray Crystal Structures of rra«s-RuCl2(P-N)(PPh3)(OH2) (33a) 175 5.3 NMR Spectra 7>am-RuCl2(P-N)(PPh3)(OH2) (33a) 181 5.4 Trans Influence of Ligands and its Effect on 3 1P NMR Chemical Shifts 186 5.5 UV-Vis Spectral Studies of the RuCl2(P-N)(PPh3)/H20 System 191 5.6 The Preparation of rran5-RuCl2(P-N)(PPh3)(L) (L = MeOH (34) and EtOH(35)) 195 5.7 DSC Data for Complexes Containing O-Donor ligands 198 5.8 Summary 201 5.9 References 202 Chapter 6 Reactions of RuCl2(P-N)(PPh3) with Dihydrogen, Ammonia, Nitrous Oxide, Alkynes, and Hydrogen Chloride 205 6.1 The Structure and Reactivity of C/s-RuCl2(P-N)(PPh3)(ri2-H2) (36) 205 6.1.1 The Crystal Structure Cw-RuCl2(P-N)(PPh3)(Ti2-H2) (36) 206 6.1.2 Thermodynamic Studies of C«-RuCl2(P-N)(PPh3)(ri2-H2) (36) in Solution and in the Solid State 208 6.1.3 The pKa of C/5-RuCl2(P-N)(PPh3)(ri2-H2) (36) 211 6.2 Reactions of RuX2(P-N)(PPh3) (X = CI Br) withNH3 214 6.2.1 Isolation of [RuX(P-N)(PPh3)(NH3)2-X] (37) in the Presence of Excess NH 3... 214 6.2.2 The Solution Chemistry of [RuX(P-N)(PPh3)(NH3)2-X] (37) 216 6.2.3 The Solid State Reaction of RuX2(P-N)(PPh3) with NH 3 219 6.2.4 The Preparation of [RuCl(P-N)(PPh3)(NH3)2]PF6 (41) 220 6.3 The Coordination Chemistry of N 2 0 225 6.3.1 N 2 0 as a Potential Oxidant 225 6.3.2 The Reaction of RuCl2(P-N)(PPh3) with N 2 0 229 6.4 Ruthenium Carbene Complexes: The Synthesis and Reactivity of C/5-RuCl2(P-N)(PR3)(=C=C(H)R') (R, R' = Ph,p-tolyl) 235 6.4.1 Characterization of C/5-RuCl2(?-N)(PR3)(=C=C(H)R) 23 5 6.4.2 The Reactivity of Cz5-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) 240 6.5 The Reaction of RuCl2(P-N)(PPh3) (6a) with HC1 243 6.6 The Catalytic Hydrogenation of PhC(H)=NPh Using Complexes Containing the Ru(P-N) Moiety 244 6.7 Summary 246 6.8 References 248 Chapter 7 General Conclusions and Recommendations for Future Research 253 7.1 References 256 Appendices....... 257 Appendix I X-Ray Crystallographic Analysis of Bis[o-N,N-dimethylamino)phenyl]phenylphosphine, BPN 258 Appendix II X-Ray Crystallographic Analysis of M?r-RuCl3(BPN) (16) 261 xi Appendix IH X-Ray Crystallographic Analysis of (fA-0)(u-Q)2[RuCl(P-N)]2 (17) 266 Appendix IV X-Ray Crystallographic Analysis of Cw-RuCl2(P-N)(PPh3)(SH2Hacetone) (18a) 271 Appendix V X-Ray Crystallographic Analysis of C/5-RuBr2(P-N)(PPh3XSH2Hbenzene) (18b) 276 Appendix VI X-Ray Crystallographic Analysis of C;5-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) 279 Appendix VII X-Ray Crystallographic Analysis of C/5-RuCl2(P-N)(PPh3)(EtSH)-(1.5C6D6) (21) 284 Appendix VIII X-Ray Crystallographic Analysis of rra«5-RuCl2(P-N)fPPh3)(OH2)-(2C6H6) (33a, T) and 7>a/75-RuCl2(P-N)(PPh3)(OH2)-(1.5C6H6) (33a, II) 287 Appendix IX X-Ray Crystallographic Analysis of Cw-RuCl2(P-N)(PPh3)(ri2-H2) (36) 295 Appendix X X-Ray Crystallographic Analysis of Gs-RuCl2(P-N)(PPh3X=C=CHPh) (45) 298 Appendix XI Thermodynamic Calculations and Data for the Reversible Formation of C/5-RuCl2(P-N)(PPh3)(L) (X = CI, Br; R - Ph, ^ p-tolyl; L = H2S, MeSH, EtSH) 302 Appendix XTJ Thermodynamic Calculations and Data for the Reversible Formation of rra«5-RuCl2(P-N)(PPh3)(OH2) (33a) 308 Appendix XIII Thermodynamic Calculations and Data for the Reversible Formation of C/5-RuCl2(P-N)(PPh3)(r|2-H2) (36) 316 xii List of Figures Figure 1.1 The sulfur cycle in nature 2 Figure 1.2 The most widely utilized methods for the synthesis of thiols 6 Figure 1.3 Some common coordination modes of SR" (R = H or alkyl) and S2" ligands to transition metal centres (M) 7 Figure 1.4 Formation of hydrido mercapto and bis(mercapto) Ru(II) phosphine complexes...9 Figure 1.5 Formation of/raw5-IrCl(H)(SH)(CO)(PPh3)2 9 Figure 1.6 Reactions of /ra/M-Mo(N2)2(dppe)2 with thiols 10 Figure 1.7 Formation of five-coordinate, trigonal bipyramidal mercapto and thiolato complexes 11 Figure 1.8 Reactions of H2S with monomeric complexes to form di- and tri-u.2-SH dinuclear complexes 12 Figure 1.9 Reaction of [Ir(H)2(MeCO)2(PPh3)2][BF4] with H2S 13 Figure 1.10 Formation of dinuclear mercapto and thiolato-bridged complexes containing arene co-ligands 14 Figure 1.11 Clusters containing u.2- and u,3-SR bridged ligands 15 Figure 1.12 Formation of |x2-S and u.2-SMe dinuclear complexes 16 Figure 1.13 S-H bond activation in H2S and thiols by (a) RhRe(CO)4(u,-dpm)2 and (b) [Pt 3(^ 3-CO)(Mpm) 3] 2 + 17 Figure 1.14 Structure of intermediate formed during the reaction of Pd2X2(u.-dpm)2 With H2S en route to Pd2X2(n2-S)(u.-dpm)2 and H 2 18 Figure 1.15 Homogeneous catalytic cycle for the recovery of H 2 from H2S 19 Figure 1.16 Proposed transition state for the reconversion of Pd2X2(u.-dpm)2 from Pd 2X 2(u. 2-S)(Mpm)2 19 Figure 1.17 [o-(i\^ -dimethylamino)phenyl]diphenylphosphine] (P-N) 19 Figure 1.18 Reaction of RuCl2(P-N)(PR3) with small molecules L 21 Figure 2.1 Ligands studied in this thesis work 34 xiii Figure 3.1 The preparation of RuCl2(P-N)(PR3) (R = Ph (6a), R = p-tolyl (7a)) 76 Figure 3.2 The ORTEP plot of RuCl2(P-lSQ(P(p-tolyl)3) (7a) 78 Figure 3.3 The ORTEP plot of (n-0)(n-Cl)2[RuCl(P-N)]2 (17) 80 Figure 3.4 Antiferromagnetic coupling between two Ru centres through an O 2' ligand 83 Figure 3.5 UV-Vis spectrum of (u-0)(|i-Cl)2[RuCl(P-N)]2 (17) in DMSO at 25°C 84 Figure 3.6 The catalytic oxidation of PPh3 to 0=PPh3 by 6a in the presence of 0 2 85 Figure 3.7 Synthesis of RuBr2(P-N)(PPh3) (6b) and RuI2(P-N)(PPh3) (6c) 86 Figure 3.8 ^ Pf/H} NMR spectra (81.0 MHz, C 6 D 6 , 20°C) for (a) RuCl2(P-N)(PPh3) (6a), (b) RuBr2(P-N)(PPh3) (6b) and (c) RuI2(P-N)(PPh3) (6c) 87 Figure 3.9 31?{lH.} NMR spectra (121.4 MHz) for the reaction of RuCl2(P-N)(PPh3) (6a) with NaOH in d6-acetone after (a) 2 h and (b) 20 h at 25°C 89 Figure 3.10 The subsitution of CI" ligands by OH" ligands 90 Figure 3.11 High field l H NMR spectrum (300 MHz) for the reaction of 6a with NaH in de-acetone at 25°C 93 Figure 3.12 The ORTEP plot of BPN 94 Figure 3.13 Possible structures of RuCl2(BPN)(PR3) 95 Figure 3.14 The ORTEP plot of /wer-RuCl3(BPN)-CHCl3 (16) 97 Figure 3.15 The ORTEP plot of TPN 99 Figure 3.16 Possible structures for RuCl2(PAN)(PR3) 100 Figure 3.17 Synthesis of RuCl2(AMPHOS)(PPh3) (11) 102 Figure 3.18 Synthesis of [(PPh3)2(ri2-H2)Ru(^-H)(^-Cl)2Ru(H)(PPh3)2] 102 Figure 3.19 Synthesis of Ru(H)Cl(PPh3)3 using AMPHOS as the base 103 Figure 3.20 Structure of RuCl2(ALAPHOS)2 (12) (proposed) and RuCl2[K2(7 J^0-Ph2PCH2CH2NMe2]2 104 Figure 3.21 Reactions of RuCl2(PO)2 (5) with H2S 105 Figure 4.1 The (a) preparation, (b) structure and (c) oxidation of [Ru(SH2)(PPh3)('S4')]... I l l xiv Figure 4.2 Formation of [Pt(PPh 3)2(SH 2)] 112 Figure 4.3 Formation of W(CO) 5(SH 2) 113 Figure 4.4 Formation of metal carbonyl H 2S salts 114 Figure 4.5 Formation of [(ThiCp)Ru(PPh 3) 2][OTfJ 114 Figure 4.6 Preparation of thiol complexes containing the electron rich CpM (M = Ru, Fe) moieties 116 Figure 4.7 Formation of [Ru(r] 3:ri 3-CioHi 6)Cl 2(HSR)] 117 Figure 4.8 Preparation of [IrH(SCH 2CH 2PPh 2)(HSCH 2CH 2PPh 2)(CO)]Cl 118 Figure 4.9 In situ formation of [MH(CO)(N-SH)(PPh 3) 2][BF 4] 119 Figure 4.10 The ORTEP plot of czs-RuCl2(P-N)(PPh3)(SH2) (18a) ... 121 Figure 4.11 Bond distances between H-atom and C-atom of phenyl ring to indicate SH/TX interactions in (PhMe 2P) 3Ru(|>SH) 3Ru(SH)(PMe 2Ph) 2 123 Figure 4.12 3 1P{ 1H} NMR spectra (202.47 MHz) of c/5-RuCl2(P-N)(PPh3)(SH2) (18a) in CD 2C1 2 at various temperatures 125 Figure 4.13 *H NMR spectra (121.4 MHz) of cw-RuCl2(P-N)(PPh3)(SH2)-(acetone) (18a) in CeDs 126 Figure 4.14 V T *H NMR spectra (500 MHz) of czs-RuCl2(P-N)(PPh3)(SH2) (18a) in CD 2C1 2 (under 1 atm H 2S) for the region 8 0.0 to 5 4.0 127 Figure 4.15 JH and ^{"P} NMR spectra (500 MHz) of cw-RuCl 2(P-N)(PPh 3)(SH 2) (18a) in CD 2C1 2 (under 1 atm H 2S) at -50°C for the region 8 0.2 to 1.6 128 Figure 4.16 *H NMR (500 MHz) signal at 5 1.49 for czs-RuCl2(P-N)(PPh3)(SH2) (18a) with decoupler transmitter centred at 202.4685838 MHz with increasing 3 1P decoupler power 129 Figure 4.17 The vicinal Karplus correlation. Relationship between dihedral angle ((()) and 3J '. 130 Figure 4.18 End-on schematic view of the solid state structure of 18a 131 Figure 4.19 The ORTEP plot of Czs-RuBr2(P-N)(PPh3)(SH2) (18b) 133 Figure 4.20 End-on view schematic view of the solid state structure of 18b 135 XV Figure 4.21 The ORTEP plot of c/s-RuCl2(P-N)(PPh3)(MeSH) (20) 137 Figure 4.22 *H NMR spectra of c/5-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) in CD2C12 (a) 20°C andb) -50°C 139 Figure 4.23 The ORTEP plot of cw-RuCl2(P-N)(PPh3)(EtSH) (21) 141 Figure 4.24 *H NMR spectrum (500 MHz) of 21 in CD2C12 at 20°C 143 Figure 4.25 *H NMR spectra of 21 (500 MHz, CD2C12): (a) simulated spectrum; (b) expanded regions 144 Figure 4.26 *H NMR resonance of Ru-S-tL. in c/5-RuCl2(P-N)(PPh3)(EtSH) (21): (a) *H NMR spectrum; (b) 1H{31P}NMR spectrum (500 MHz, 20°C, CD2C12) 145 Figure 4.27 31P{1H} NMR (300 MHz) spectra of in situ reactions of 6a with (a) z'-PrSH and (b) w-PnSH in CeDe at 20°C..; 147 Figure 4.28 The vibrational modes for H2S (or any bent triatomic molecules) 148 Figure 4.29 UV-Vis spectra for RuCl2(P-N)(PPh3) (6a) and c/s-RuCl2(P-N)(PPh3)(SH2) (18a) in CH2C12 151 Figure 4.30 Van't Hoff plots for the K equilibria (see p. 42) for (a) 18a, (b) 18b, (c) 19a, (d) 20 and (e) 21 in C 6 D 6 153 Figure 4.31 *H NMR spectra in the region 8 -0.5 to 4.5 (300 Mhz, C 6D 6) for the equilibrium between 18a, 6a and H2S at (a) 20°C, (b) 36°C and (c) 50°C 154 Figure 4.32 DSC curves for czs-RuCl2(P-N)(PPh3)(L) complexes 157 Figure 4.33 Proposed reaction scheme for the loss of L from c/s-RuCl2(P-N)(PPh3)(L) 158 Figure 4.34 Structure of a typical proton sponge 158 Figure 4.35 (a), (b) Dihydrogen activation by Ru(II) complexes in the presence of added base, and (c) abstraction of proton from RuCl2(P-N)(PPh3)(SH2) 159 Figure 4.36 31P{1H} NMR (300 MHz, CD2C12) spectra for various Ru(II) complexes containing sulfur ligands: (a) RuCl2(P-N)(PPh3)(SH2) at 20°C; RuCl2(P-N)(PPh3) + 3PS + 1 atm H2S at (b) 20°C, (c) -25°C, (d) -60°C and (e) -70°C 161 Figure 4.37 *H NMR spectra (200 MHz, CDC13, r.t.) of (a) PS and (b) PSlfCl" 162 xvi Figure 4.38 (a) Equilibrium for formation of RuCl2(P-N)(PPh3)(SH2) (18a); (b), (c), (d) are subsequent equilibria en route to the formation of Ru(SH)2(P-N)(PPh3) (30) in the presence of added PS 163 Figure 5.1 TGA spectrum of 33a 174 Figure 5.2 PLUTO plots of 33a (/ra/75-RuCl2(P-N)(PPh3)(OH2)-2C6H6(r) and /ram-RuCl^-^PhsXOH^-l.SCsHe (II)) 176 Figure 5.3 The ORTEP plot of RuCl2(P-N)(PPh3)(OH2)-1.5C6H6 (33a (IT)) 177 Figure 5.4 Rapid equilibrium between 6a and 33a 182 Figure 5.5 "P^H} NMR spectra of rra«5-RuCl2(P-N)(PPh3)(OH2) (33a) in CD2C12 at various temperatures.. 183 Figure 5.6 "p^H} NMR spectra (20°C) of RuCl2(P-N)(PPh3) (6a) in de-acetone with various H 2 0 concentrations 184 Figure 5.7 X H NMR spectra of /ra«s-RuCl2(T-N)(PPh3)(0H2) (33a) in CD2C12 at various temperatures 186 Figure 5.8 The relationship between Ru-PA bond length (A) and 8 P A (in CDC13) for the complexes containing the Ru(P-N) moiety 188 Figure 5.9 Proposed mechanism for the formation of czs-RuCl2(P-N)(PPh3)(SH2) (18a).... 190 Figure 5.10 Species in equilibrium when 6a is dissolved in a coordinating solvent in the presence of H 2 0 191 Figure 5.11 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) in CH2C12 192 Figure 5.12 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) in CeHe 192 Figure 5.13 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) in acetone 193 Figure 5.14 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) inTHF 193 Figure 5.15 Solving K for the addition of H 2 0 to 6a at 25°C 194 Figure 5.16 *H NMR spectrum of /ra/w-RuCl2(P-N)(PPh3)(>leOH) (34) in CD2C12 196 Figure 5.17 J H NMR spectrum of *ram-RuCl2(P-N)(PPh3)(EtOH) (35) in CD2C12 197 xvii Figure 5.18 DSC curves for /raws-RuCl2(?-N)(PPh3)(L) 199 Figure 5.19 DSC curves for *rans-RuCl2(P-N)(PPh3)(OH2) (33a) and />-aw5-RuCl2(P-N)(P(p-tolyl)3)(OH2) (33b) 200 Figure 6.1 The ORTEP plot of czs-RuCl2(P-N)(PPh3)(r|2-H2) (36) 207 Figure 6.2 "P^H} NMR spectrum (81.0 MHz) of 36 in equilibrium with 6a in C6D 6 at20°C 210 Figure 6.3 *HNMR spectrum (200 MHz) of 36 in equilibrium with 6a in C6D6 at 20°C.... 210 Figure 6.4 DSC curve for c/s-RuCl2(P-N)(PPh3)(r|2-H2) (36) 211 Figure 6.5 31V{lK) NMR (121.4 MHz, 20°C, CD2C12) spectrum of the in situ reaction of RuCl2(P-N)(PPh3) (6a) with 1.5 equiv PS under 1 atm H 2 213 Figure 6.6 *H NMR (121.4 MHz, 20°C, CD2C12) spectrum in the region 5 2.0 to 4.0 of the in situ reaction of RuCl2(P-N)(PPh3) (6a) with 1.5 equiv PS under 1 atm H 2 213 Figure 6.7 Proposed structure of [RuX(P-N)(PPh3)(NH3)2-X] (37) 215 Figure 6.8 *H NMR spectrum (CDC13, 300 MHz) of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) under 1 atm NH 3 at 20°C 215 Figure 6.9 31P{1H} spectra (121.4 MHz, 20°C, CDC13) for [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a): (a) with 1 atm NH 3 and (b) absence of excess NH 3 217 Figure 6.10 Reversible conversion of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) to cw-RuCl2(P-N)(PPh3)(NH3) (39a) 218 Figure 6.11 NMR spectrum (121.4 MHz) of /raws-RuCl2(P-N)(PPh3)(NH3) (38a) after 5 min of being dissolved in CDC13 at 20°C 220 Figure 6.12 *H NMR spectrum (300 MHz) of rra«s-RuCl2(P-N)(PPh3)(NH3) (38a) (after 5 min of being dissolved in CDC13 at 20°C) in the region 8 0.0 to 4.0 220 Figure 6.13 31P{1H} NMR spectra of (a) [RuCl(P-N)(PPh3)(NH3)2][PF6] (41) and (b) [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) 222 Figure 6.14 31P{1H} NMR spectrum for the in situ formation of [Ru(P-N)(PPh3)(NH3)3-Cl][PF6] (40a) 222 Figure 6.15 Reaction scheme for the preparation of NH 3 complexes containing PF6" ions.. 223 xviii Figure 6.16 *H NMR spectrum of rRuCl(P-N)(PPh3)(NH3)2][PF6] (41) 224 Figure 6.17 Potential catalytic cycle for the oxidation of organic substrates using N 2 0 226 Figure 6.18 Stoichiometric formation of PhCH2C(0)Ph utilizing N 2 0 227 Figure 6.19 Transfer of th O-atom of N 2 0 into Ni-C bond 228 Figure 6.20 Formation to Ru-OH complexes by O-atom insertion from N 2 0 228 Figure 6.21 Possible coordination modes of N 2 0 to (dmpe)2Ru(H)2 229 Figure 6.22 "P^H} NMR spectrum (121.4 MHz, CD2C12) of (a) 6a, and the reaction of 6a with 6 atm N 2 0 at (b) 20°C, (c) -40°C, (d) -90°C and (e) 20°C after reaction time of 2 days 231 Figure 6.23 "P^H} NMR spectra (121.4 MHz, CD2C12) for the reaction of 6a with (a) 6 atm N 2 at 20°C and (b) 6 atm N 2 0 at -40°C 232 Figure 6.24 Proposed reaction scheme for the formation of 17 and 0=PPh3 if N 2 0 is initially coordinated to 6a via the terminal N atom 233 Figure 6.25 The catalytic oxidation of PPh3 by N 2 0 234 Figure 6.26 Formation of a vinylidene complex from a 1-alkyne ligand 236 Figure 6.27 The ORTEP plot of c/s-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) 237 Figure 6.28 "P^H} NMR spectrum (81.0 MHz, 20°C) of cw-RuCl^-^tTP^X^CtT^Ph) (45) in CDC13 239 Figure 6.29 *H NMR spectrum (200 MHz, 20°C) of cw-RuCl2(P-N)(PPh3)(=C„-Cp(H)Ph) (45) in CDC13 240 Figure 6.30 Proposed mechanism for the formation of cz'5-RuCl2(P-N)(PPh3)(S=C(H)-CH2Ph) (48) from 45 and H2S 241 Figure 6.31 The reaction of c/5-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) with H 2 0 at 80°C in THF 243 Figure 6.32 Reaction of RuCl2(P-N)(PPh3) (6a) with HC1: formation of RuCl3(P-N)(PPh3) (15a) 244 Figure 6.33 "P^H} NMR spectra for the reaction of RuCl2(P-N)(PPh3) (6a) with (a) 1 equiv HC1 and (b) 5 equiv HC1 in CeD6 244 Figure 7.1 Examples for the modification of P-N 255 xix List of Tables Table 1.1 Some physical properties of H2S and thiols 6 Table 3.1 Selected bond lengths (A) for (u-0)(^-Cl)2[RuCl(P-N)]2 (17) 81 Table 3.2 Selected bond angles (°) for (u^O)(u-Cl)2[RuCl(P-N)]2 (17) 81 Table 3.3 31P{'H} NMR data for the in situ reactions of RuX2(P-N)(PPh3) (X = CI, Br) with NaOH in d6-acetone 91 Table 3.4 ! H NMR data for the in situ reactions of RuX2(P-N)(PPh3) (X = CI, Br) with NaOH in d6-acetone 91 Table 3.5 31P{1H) NMR spectroscopic data for RuCl2(BPN)(PR3) in CDC13 95 Table 3.6 *H NMR chemical shifts for RuCl2(BPN)(PR3) in CDC13 95 Table 3.7 Selected bond lengths (A) for /wer-RuCl3(BPN) (16) 98 Table 3.8 Selected bond angles (°) for mer-RuCl3(BPN) (16) 98 Table 4.1 Selected bond lengths (A) for e/-s-RuCl2(P-N)(PPh3)(SH2) (18a) and c/5-RuCl2(P-N)(P(p-tolyl)3)(SH2) (19a) 122 Table 4.2 Selected bond angles (°) for czs-RuCl2(P-N)(PPh3)(SH2) (18a) and c/s-RuCl2(P-N)(P(p-tolyl)3)(SH2) (19a) 122 Table 4.3 Selected bond lengths (A) for c/s-RuBr2(P-N)(PPh3)(SH2) (18b) 134 Table 4.4 Selected bond angles (°) for c/\s-RuBr2(P-N)(PPh3)(SH2) (18b) 134 Table 4.5 Selected bond lengths (A) for c/s-RuCl2(P-N)(PPh3)(MeSH) (20) 138 Table 4.6 Selected bond angles (°) for c/5-RuCl2(P-N)(PPh3)(MeSH) (20) 138 Table 4.7 Selected bond lengths (A) for cw-RuCl2(P-N)(PPh3)(EtSH) (21) 142 Table 4.8 Selected bond angles (°) for czs-RuCl2(P-N)(PPh3)(EtSH) (21) 142 Table 4.9 31P{1H} NMR chemical shifts (121.4 MHz) for cw-RuCl2(P-N)(PPh3)(RSH) in the presence of added RSH 146 Table 4.10 V S - H (cm'1) frequencies (vi and v3 bands) for H2S and thiols, in the free gaseous state and upon coordination to Ru 149 Table 4.11 Xi and X2 UV-Vis bands for RuX2(PN)(PPh3)(L) in CD2C12 150 XX Table 4.12 Thermodynamic parameters for the formation of c/£-RuX2(P-N)(PR3)(L) inCeDs 155 Table 4.13 3 1P{ 1H) NMR chemicals shifts of Ru(II) mercapto complexes in d6-acetone.... 165 Table 5.1 Selected bond lengths (A) for /ra/w-RuCl2(P-N)(PPh3)(OH2)-2C6H6 (I), /raw5-RuCl2(P-N)(PPh3)(OH2)-1 SCeth (II) and /ran5-RuCl2(P-N)(P(>-tolyl)3(OH2) (33b) 179 Table 5.2 Selected bond angles (°) for rra^-RuCl2(P-N)(PPh3)(OH2)-2C6H6 (I), /raw£-RuCl2(P-N)(PPh3)(OH2)-1.5C6H6 (TS) and /row5-RuCl2(P-N)(P(p-tolyl)3(OH2) (33b) 180 Table 5.3 P A and P x chemical shifts for RuCl 2(P-N)(PPh 3) (6a) and rraAM-RuCl2(P-N)(PPh3)(OH2) (33a) 182 Table 5.4 Comparison of "P^H} NMR chemical shifts and Ru-P bond lengths 187 Table 5.5 Ru-Cl bond lengths (A) for /raw5-RuCl2(P-N)(PR3)(L) 189 Table 5.6 Ru-Cl bond lengths (A) for c/s-RuCl2(P-N)(PR3)(L) 190 Table 6.1 Selected bond lengths (A) for cw-RuCl 2(P-N)(?Ph 3)(ri 2-H 2) (36) 208 Table 6.2 Selected bond angles (°) for cw-RuCl2(P-N)(PPh3)(r|2-H2) (36) 208 Table 6.3 "P^H} NMR data for Ru(H) ammonia complexes in CDC1 3 217 Table 6.4 *H NMR data for Ru(IT) ammonia complexes in CDC1 3 218 Table 6.5 Selected bond lengths (A) for cw-RuCl2(P-N)(PPh3)(<:=C(H)Ph) (45) 238 Table 6.6 Selected bond angles (°) for c/5-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) 238 Table 6.7 Hydrogenation of PhC(H)=NPh using ruthenium aminophosphine complexes.... 246 xxi List of Symbols and Abbreviations 5 chemical shift (parts per million) u, descriptor for bridging s extinction coeffiecient or molar absortivity ( M 1 cm"1) K kappa, coordination of different atoms of ligand X wavelength (nm) v frequency (cm"1) AM molar conductivity (ohm"1 mol"1 cm2) rj" hapticity of degree n (R)- absolute configuration (Latin: rectus; right) (S)- absolute configuration (Latin: sinister; left) ° degrees * chiral centre * transition state [ ] molar concentration 1 3C {1H} carbon-13 -observed proton-decoupled (NMR) ^{^P} proton-observed phosphorus-31 -decoupled (NMR) 3 JP {'H} phosphorus-31 -observed proton-decoupled (NMR) A angstrom, 10"10m ALAPHOS [(6^-2-(dimethylamino)proplyl]diphenylphosphine AMPHOS (i?)-(+)-iV,7Y-dimethyl-l-[o-(dimethylphospMno)phenyl]ethylamine anal. analysis atm atmosphere(s) b.p. boiling point bdpp (2S, 467)-2,4-bis(diphenylphosphino)pentane binap (R)- or (5)-2,2'-bis(diphenylphosphino)-l,r-binaphthyl BPN bis[o-(A^,iV-dimethylamino)phenyl]phenylphosphine br broad bu butyl bz benzyl calcd calculated xxii cct cis, cis, trans chiraphos 2,3-bis(diphenylphosphino)butane Cp cyclopentadienyl Cp* pentamethylcyclopentadienyl Cy cyclohexyl d doublet dd doublet of doublets ddd doublet of doublet of doublets diop 4,5-bis[(diphenylphospMno)methyl)-2,2-dimethyl-1,3-dioxolane] dippe 1,2-bis(diisopropylphosphine)ethane DMA /Yj/Y-dimethylacetamide dmpe l,2-bis(dimethylphosphino)ethane DMSO dimethylsulfoxide dpm, dppm 1,1 -bis(diphenylphosphino)methane dppb 1,4-bis(diphenylphosphino)butane dppe 1,2-bis(diphenylphosphino)ethane dppn l,5-bis(diphenylphosphino)pentane dppp 1,3 -bis(diphenylphosphino)propane dq doublet of quartets DSC differential scanning calorimetry e.e. enantiomeric excess equiv equivalent(s) Et ethyl h hour(s) HDS hydrodesulfurization hx hexyl Hz Hertz, cycles per second /' iso IR infrared (spectroscopy) isn isonicotinamide isoPFA 1 -[a-A ,^A -^cUmethylaminoethyl]-2-(diphenylphosphino)ferrocene J coupling constant (Hz) xxiii K equilibrium constant L litre m multiplet (NMR), medium (IR), milli-, meter M molarity (mol/L), mega-m meta m.p. melting point Me methyl min minute(s) MNAA 2-(6'-methoxynaphth-2'-yl)acrylate anion n normal N-S pyridine-2-thiolate or quinoline-8-thiolate NMR nuclear magnetic resonance (spectroscopy) NP3 tris(2-diphenylphosphinoethyl)amine o ortho OTf triflate OTs /7-toluenesulfonate p para P-N [o-(AyV-dimethylamino)phenyl]diphenylphoshine PAN 1 -(7V",A/-dimethylamino)-8-(diphenylphoshino)naphthalene Ph phenyl PN aminophosphine ligand pn pentyl PNP 1 -A ,^A'-bis[(diphenylphosphino)ethyl]propylamine PO o-diphenylphosphineanisole PP3 tris(2-diphenylphosphinoethyl)phosphine PPFA 1 -[7Y,7Y-a-dimethylaminoethyl]-2-diphenylphosphinoferrocene ppm parts per million Pr propyl PS proton sponge or l,8-bis(dimethylamino)naphthalene psi pounds per square inch q quartet qn quintet xxiv r.t. room temperature s singlet, second(s), strong (IR) t tertiary t triplet T i longitudinal relaxation time (NMR) T G A thermogravimetric analysis THF tetrahydrofuran ThiCp 2-(thienylmethyl)cyclopentadienyl TPN tris[o-(vV,^dimethylamino)phenyl]phenylphosphine TPP tetraphenylporphyrin triphos 1,1,1 -tris(diphenylphosphinoethyl)ethane trpy 2,2'2"-terpyridine UV-Vis ultraviolet-visible (spectroscopy) V T variable temperature w weak XXV Table of Compound Numbers Number Compound 1 RuCl 2 (PPh 3 ) 3 2 RuCl2(P(p-tolyl)3)3 3 c/s-RuCl 2(DMSO) 4 4a RuCl 3(PPh 3) 2(DMA)-(DMA) 4b RuCl 3(P(p-tolyl) 3) 2(DMA)-(DMA) 5 RuCl 2 (PO) 2 6a RuCl 2(P-N)(PPh 3) 6b RuBr2(P-N)(PPh3) 6c RuI2(P-N)(PPh3) 7a RuCl2(P-N)(P(p-tolyl)3) 7b RuBr2(P-N)(P(p-tolyl)3) 7c RuI2(P-N)(P(p-tolyl)3) 8 RuCl 2 (P-N) 2 9 RuCl 2(PAN)(PPh 3) 10 RuCl2(PAN)(P(p-tolyl)3) 11 RuCl 2(AMPHOS)(PPh 3) 12 RuCl 2 (ALAPHOS) 2 13 RuCl 2(BPN)(PPh 3) 14 RuCl2(BPN)(P(p-tolyl)3) 15a RuCl 3(P-N)(PPh 3) 15b RuCl3(P-N)(P(p-tolyl)3) 16 »jer-RuCl 3 (BPN) 17 (H-0)(u-Cl)[RuCl(P-N)]2 18a c;s-RuCl2(P-N)(PPh3)(SH2) 18b cw-RuBr2(P-N)(PPh3)(SH2) 18c czs-RuI2(P-N)(PPh3)(SH2) 19a cw-RuCl2(P-N)(P(p-tolyl)3)(SH2) 19b c/5-RuBr2(P-N)(P(p-tolyl)3)(SH2) 19c cis-RuI2(P-N)(P(p-tolyl)3)(SH2) 20 c/s-RuCl2(P-N)(PPh3)(MeSH) 21 c/>RuCl2(P-N)(PPh3)(EtSH) 22 cw-RuCl2(P-N)(PPh3)(n-PrSH) 23 c/s-RuCl2(P-N)(PPh3)(/-PrSH) 24 c/5-RuCl2(P-N)(PPh3)(7j-PnSH) Number Compound 25 c /s -RuCl 2 (P-N)(PPh 3 ) («-HxSH) 26 c/\s-RuCl2(P-N)(PPh3)(BzSH) 27a Ru(SH)Cl(P-N)(PPh3) 27b Ru(SH)Br(P-N)(PPh3) 28a Ru(OH)Cl(P-N)(PPh3) 28b Ru(OH)Br(P-N)(PPh3) 29 Ru(H)Cl(P-N)(PPh3) 30 Ru(SH)2(P-N)(PPh3) 31 Ru(OH)2(P-N)(PPh3) 32 Ru(H)2(P-N)(PPh3) 33a /7-a«s-RuCl 2 (P-N)(PPh 3 )(OH 2 ) 33b r?-anj-RuCl2(P-N)(P(p-tolyl)3)(OH2) 34 fra«j-RuCl 2 (P-N)(PPh 3 )(MeOH) 35 /ra«j-RuCl 2 (P-N)(PPh 3 )(EtOH) 36 cw-RuCl 2(P-N)(PPh 3)(Ti 2-H 2) 37a [RuCl(P-N)(PPh 3)(NH 3) 2-Cl] 37b [RuBr(P-N)(PPh 3)(NH 3) 2-Br] 38a /ra>w-RuCl2(P-N)(PPh3)(NH3) 38b /ran5-RuBr2(P-N)(PPh3)(NH3) 39a c/5-RuCl2(P-N)(PPh3)(NH3) 39b /ranj-RuBr2(P-N)(PPh3)(NH3) 40a [Ru(P-N)(PPh 3)(NH 3) 3-Cl] [PF6] 40b [Ru(P-N)(PPh3)(NH3)3][PF6]2 41 rRuCl(P-N)(PPh3)(NH3)2]rPF6] 42 [RuCl(P-N)(PPh3)(NH3)] [PF6] 43 c;>RuCl2(P-N)(PPh3)(V -N 2) 44 c;\s-RuCl2(P-N)(PPh3)(N20) 45 cis-RuCl2(P-N)(PPh3)(=C=CHPh) 46 c/>RuCl2(P-N)(P(p-tolyl)3)(=C=CHPh) 47 m-RuCl 2(P-N)(PPh 3)(=C=CHPhCH 3) 48 c/s-RuCl 2(P-N)(PPh 3)(SCHCH 2Ph) 49 RuCl(P-N)(PPh 3)(CH 2Ph)(CO) 50 RuCl 2(P-N)(PPh 3)(CO) xxvi Acknowledgements I offer my most sincere gratitude to my supervisor, Prof. Brian R. James for his expert guidance and support throughout this thesis work. The opportunity to work in his laboratory has provided me with invaluable experience for my career as a scientist. I would like to thank the past and present members of the James group, in particular Ian Baird, Terrance Wong, Graham Cairns, Patric Meessen, Nathan Jones, Craig Pamplin, Paul Cyr, Matt LePage, and Elizabeth Cheu for their friendship, encouragement and useful discussions. Thanks for your support and proofreading parts of this thesis. I would also like to thank the departmental services, especially Dr. Nick Burlinson, Lianne Darge, and Marietta Austria from the NMR labs; the late Dr. Steve Rettig from the X-ray crystallography lab; Peter Borda from the microanalysis lab and Steve Rak from the glassblowing lab for their indispensable assistance. I am also gratfttl to Jim Sawada for assistance with the TGA/DSC instruments. Finally, I would like to thank my parents and sisters for their support, encouragement and understanding over the years. Many thanks to Susan Ong, thanks for listening. xxvii Chapter 1 Introduction The reactions of H 2S with transition metal complexes have been one of the main focuses in this laboratory.1 One aspect of such research emphasizes the development of homogeneous catalytic systems for the recovery of H 2 from H2S.2"7 From another perspective, we are interested in studying the mechanisms of simple models in homogeneous systems and correlating these findings to those of heterogeneous catalytic systems.8'13 One such system is the catalytic hydrodesulfurization (HDS) of S-containing hydrocarbons in fuel (see below). This thesis work was largely initiated by the synthesis and characterization of the stable coordinated H2S complex, c/s-RuCl2(P-N)(P(/?-tolyl)3)(SH2) (P-N = [o-(N,N-dimethylamino)phenyl]diphenylphosphine.14 The discovery of this complex provided a rare opportunity to investigate the properties, including thermodynamic and kinetic aspects, resulting from the binding of H2S to a transition metal (Ru(II)) centre. The precursor, five-coordinate complex RuCl2(P-N)(PR3) (R = Ph or /?-tolyl), is also fascinating as a range of small molecules including H 2 , N 2 , H 20, MeOH, CO and S0 2 can also be coordinated to the vacant sixth site.15'16 Thus, it was also the objective of this thesis to investigate further the reactivity of RuCl2(P-N)(PPh3) with these molecules and other small, neutral molecules, as well as with reagents such as salts and bases. In this Chapter, the natural and industrial occurrences and implications of H2S chemistry are briefly reviewed, some structural types of transition metal complexes containing S-moieties are presented, and the general chemistry associated with ruthenium aminophosphine complexes is discussed. 1 References on page 23 Chapter 1 1.1 Natural and Industrial Occurrences of Sulfur Compounds 1.1.1 The Natural Sulfur Cycle Sulfur is essential for life as it plays key roles in growth and metabolism of all organisms. Assirnilatory actions of plants and animals (via plants) convert sulfur compounds to amino acids (e.g. L-methionine and L-cysteine), proteins and vitamins (e.g. thiamine and biotin) while dissimilatory processes, mediated by bacteria, involve metabolic reduction and oxidation of sulfur compounds.17 Upon death of an organism, a large portion of organic sulfur is reduced to H2S during decomposition.18 The above biological conversions constitute the biogeochemical sulfur cycle (see Figure 1.1).18 Bacterial oxidation Sulfur Bacterial oxidation Bacterial reduction Hydrogen Sulfide Action of heterotrophic bacteria Bacterial oxidation Bacterial reduction Oxidation by animals and micro-organisms Organic Sulfur Compounds Sulfate Plant and microbial synthesis Figure 1.1 The sulfur cycle in nature (adapted from ref. 18). H2S, Sg and S-containing organics, which originate from the degradation of biological matter, are found in coal, natural gas, oil, volcanoes, soil, sulfur springs, undersea vents, swamps, marshes, and stagnant bodies of water. The natural biogenic sources account for up 2 References on page 23 Chapter 1 to 50% o f sulfur in the atmosphere. 1 9 In many industrial process such as H D S o f petroleum 2 0" 2 5 (see Section 1.1.2) and the Kraft process 2 6 for chemical wood pulping, H 2 S is formed as a by-product. In the Kraft process, Na 2S is added to the alkaline (NaOH) pulping liquor to strengthen wood pulp; as a result, H 2 S is given off during the recovery o f spent chemicals. 1.1.2 Hydrodesulfurization (HDS) and the Claus Process The presence o f S-containing hydrocarbons in petroleum causes environmental concerns because during the combustion o f fuel, S 0 2, a major source o f anthropogenic emission, is produced. In the atmosphere, S 0 2 is oxidized to S 0 3 that subsequently reacts with H 2 0 to form H2SC«4 which causes acid rain, smog and corrosion o f materials. Acy c l i c and cyclic sulfides (including highly stable aromatic types such as benzothiophenes) are the major components o f sulfur compounds in petroleum feedstocks. Besides environmental issues, desulfurization o f oil stocks is implemented for several other reasons. Removal o f sulfur in naphtha-reforming (conversion o f gasoline range hydrocarbons into high-octane-number gasoline) is economically favourable as this prevents poisoning o f precious metal catalysts. A t high temperatures and pressures, sulfur compounds cause corrosion o f burner heating equipment. Further, it is also desirable to remove offensive odours caused by volatile sulfide species. H D S is the industrial process in which sulfur is removed from organosulfur compounds found in natural gas and petroleum. This process, based on the reaction CxHyS + 2 H 2 — • C xH y+ 2 + H 2S, is catalyzed by Co- or Ni-doped M o S 2 or W S 2 catalysts supported on A l 2 0 3 at high temperatures (400 - 825°F) with H 2 pressures o f 150-3000 p s i . 2 1 * 2 3 , 2 4 Sulfides o f Ru, Os, Ir 3 References on page 23 Chapter 1 and Rh have been shown to be much better catalysts than those of Co or Ni, 2 7 but are not used commercially because of their high costs. Despite the importance of HDS, details about the catalyst structures and the mechanism of the HDS reaction remain obscure. Thiophene is chosen as the model substrate in many studies because it has the simplest structure of thiophenes, which are most difficult class of compounds to desulfurize. The products of thiophene HDS are H2S and a mixture of w-butane, w-butenes and butadiene. Continuing debate on the mechanism is centred on the bonding mode of thiophene, on the way the C-S bond is cleaved, and whether desulfiirization occurs before or after hydrogenation of the .L- i • „ 20,22,23,25,28 thiophene ring. The majority of the H 2S generated by HDS is converted to H 2S0 4 , the largest volume inorganic substance industrially produced (43 billion kg in the US in 1995).29 H 2 S0 4 is used in the synthesis of fertilizers, organic sulfuric acids, plastics, explosives, batteries and refining of petroleum. For ease of transport and storage, elemental sulfur is recovered from H2S by the Claus process:30'31 2 H2S + 3 0 2 • 2 S0 2 + 2 H 2 0 catalysts , 2H 2S + S0 2 — • 3 / 8 S 8 + 2H 2 0 The Claus reaction, catalyzed by alumina, combines H2S and S0 2 to give Sg and H 2 0. The interactions of H2S and S0 2 on alumina, however, are not well understood. Three models for the surface-catalyzed process have been proposed: (1) adsorbed SO2 is attacked by H2S, (2) adsorbed H2S is attacked by SO2, and (3) both gases are adsorbed on alumina before reaction.32 It is clear that both important industrial processes, HDS and the Claus reaction, involve the interactions of H2S with catalyst surfaces. However, the nature of these 4 References on page 23 Chapter 1 interactions are uncertain. Thus, it is advantageous to study the reactions of H2S and S-containing organic compounds with metal complexes in homogeneous systems and correlate these findings to those of heterogeneous systems. 1.2 Coordination Chemistry of H 2S and Thiols 1.2.1 Physical Properties of H ;S and Thiols Perhaps the most distinguishable physical characteristic of H2S and thiols is their unpleasant odour. H2S, in particular, has an odour that resembles rotten eggs. Some physical properties of H2S and thiols used in this thesis work are shown in Table 1.1. Thiols are more acidic than their corresponding alcohols by 5 to 6 pKj units. Notably, H2S and thiophenol are more acidic than alkanethiols. For H2S, the greater acidity has been attributed to formation of a symmetrical solvation shell around the SH" ion upon deprotonation, this effect being greatly reduced when the H-atom is replace by an alkyl group. For thiophenol, the negative charge on the S-atom of the conjugate base is stabilized by the resonance effect of the aromatic ring, and thus the acidity is increased. H 2S and thiols are extremely toxic. Exposure to 1400 mg/m3 H2S for a few minutes results in human deaths; inhalation of thiol fumes may lead to failure of the olfactory senses, headaches, nausea, and loss of consciousness. Alkanethiols are generally prepared by acid-catalyzed (sulfuric or phosphoric acid) reactions of alcohols (Figure 12(a)) or alkenes (Figure 12(b)) with H2S. Halide displacement is most effective in the preparation of oc-toluenethiol (Figure 12(c)). Arenethiols such as benzenethiol are synthesized by reduction of the arene sulfonyl chloride (Figure 12(d)). The principal applications of thiols are in the production of synthetic rubber, agricultural chemicals and other organosulfur compounds. 5 References on page 23 Chapter 1 Table 1.1 Some physical properties of H2S and thiols. Compou Common Name(s) nd Structure Melting Point (°C)a Boiling Point (°C)a AH° formation (kJ/mol)a AG° formation (kJ/mol)a pK. (aqueous media)b hydrogen sulfide H2S -85.5 -60.3 -20.6 -33.6 7.0 14.9C methanethiol; methyl mercaptan CH 3SH -123.0 6.0 -22.9 -9.80 10.3 ethanethiol; ethyl mercaptan CH 3CH 2SH -147.9 35.0 -46.3 -4.81 10.5 1-propanethiol; w-propyl mercaptan CH3(CH2)2SH -113.2 67.7 -67.5 2.58 10.7 2-propanethiol; isopropyl mercaptan (CH3)2CHSH -130.5 52.6 -75.9 2.18 10.9 1-pentanethiol; n-pentyl mercaptan CH3(CH2)4SH -75.7 126.6 -110 18.0 d 1-hexanethiol; w-hexyl mercaptan CH3(CH2)5SH -80.5 152.7 -129 27.6 d a-toluenethiol; benzyl mercaptan C6H5 CH 2 SH -29.2 198.9 93.3 163 9.4 benzenethiol; thiophenol CfrHsSH -14.9 169.1 112 148 6.5 a(ref. 33), AH° and AG 0 values are for formation of gaseous product; b(ref. 34), pKa values were measured at 25°C ; csecond dissociation constant; dthiol is essentially insoluble in water. (a) CH3OH + H 2S c a ^ s t » CH3SH + H 2 0 (b) CH 3CH=CH 2 + H2S e a t a l y s t> (CH3)2CHSH (c) C6H5CH2C1 + NaSH »• C6H5CH2SH + NaCl (d) CsHsSC^Cl + H 2 »• C6H5SH + 2H 20 + HC1 Figure 1.2 The most widely utilized methods for the synthesis of thiols. 6 References on page 23 Chapter 1 1.2.2 Reactions of H 2S and Thiols with Transition Metal Complexes There are comparatively few examples of transition metal complexes containing H2S or thiols (RSH; R = H, alkyl) as ligands owing to the acidic and therefore ionic nature of the ligands.1 A summary of the complexes reported is presented in Sections 4.1.1 and 4.1.2 (p. 110). Although coordination of RSH to transition metal centres (M) has been demonstrated, it is more often proposed as an intermediate step in reactions of RSH with M that usually result in cleavage of S-H bonds and formation of mercapto or thiolato (SR") complexes. The S-H bond strengths of H2S, PhSH and alkanethiols (an average value) are 381, 314 and 362 ± 6 kJ/mol, respectively.35 Structural chemistry of transition metal sulfur complexes is diverse because of the versatility of sulfur ligands to act as two-, four- or six-electron donors (Figure 1.3). R / S R R s^ M—SR M ^ * ^ M ^ S R Wf ^ M S R (a) (b) (c) (d) R < S R > M ^ p M M - S - M M T M R (e) © (g) (h) Figure 1.3 Some common coordination modes of SR' (R = H or alkyl) and S2' ligands to transition metal centres (M) (adapted from ref. 36). Literature dealing with metal mercapto and thiolato complexes is plentiful, partly because of their utilization in model studies for HDS catalysts (Section 1.1.2) and their 7 References on page 23 Chapter 1 occurrence in metalloenzymes such as nitrogenase and ferredoxins.37 While no effort is given to describe comprehensively the metal complexes containing the SR" and S2" ligands in the literature, examples of complexes with structures shown in Figure 1.3 are presented in this Chapter to display the intriguing and versatile coordination modes of SR". In particular, focus is given to work done in this laboratory regarding the reactions of transition metal complexes with H 2S and thiols. 1.2.2.1 Mononuclear Mercapto and Thiolato Complexes In many cases, cleavage of the S-H bonds leads to the oxidative addition of RSH to metal complexes. James et al. showed that the reactions of Ru(CO)2(PPh3)3 or cc^Ru(H)2(CO)2(PPh3)2 (cct = cis, cis, trans) with H2S in solution give (with the liberation of H2) ccf-Ru(H)(SH)(CO)2(PPh3)2 at -35°C and the structurally characterized ccf-Ru(SH)2(CO)2(PPh3)2 at ambient conditions (Figure 1.4(a)).8'10,11 A similar reaction of a mixture of cis- and rra«s-Ru(H)2(dpm)2 (dpm = bis(diphenylphosphino)methane) with H2S gives initially jra«s^Ru(H)(SH)(dpm)2, which subsequently reacts with further H2S to produce a mixture cis- and rran5-Ru(SH)2(dpm)2 and H 2 (Figure 1.4(b)).11'12 A range of thiols RSH (R - Me, Et, Ph, CH2Ph, o-, m- and p-tolyl) also oxidatively add to Ru(CO)2(PPh3)3 or ccf-Ru(H)2(CO)2(PPh3)2 to generate solely cc/-Ru(H)(SR)(CO)2(PPh3)2 at 20°C with no tendency to form the bis(thiolato) species.8'10 The reaction of cis- and /raw5-Ru(H)2(dpm)2 with thiols generate cis- and ?raws-Ru(H)(SR)(dpm)2.12 Kinetic studies showed that the rate-determining step for the reaction of cc?-Ru(H)2(CO)2(PPh3)2 with RSH is the loss of H 2 , while an initial protonation of dpm precursor to give [Ru(H)(r|2-H2)(dpm)2]+ followed by dissociation of H 2 is proposed for the dpm system; the difference in mechanism is attributed to the higher basicity of the hydride ligands in cis-/trans-Ru(H)2(dpm)2.12 8 References on page 23 Chapter 1 CO PhsP... ^Ru —PPh3 CO (a) PPh3 O C , I . .H ^ R ^ PPh3 O C H 2 S H 2 S PPhs PPhs i ! PPhs OC... H 2 H 2 S PPh3 O C , I . .SH R < ^ + H 2 O C ^ I "*SH ' Ph3 H Ph2 P. PrcP^ I ^ P ^ (b) Phz Pre .P.. . P . Pha ^ Phz H 2 S - H 2 Ph2 i Ph2 H 2 S - H 2 SH HS, Ph2 P. tP^  ^ 1 \ PPhj1 Ph2 fH Pre .P.. ..P. Ph. ^ P h 2 Figure 1.4 Formation o f hydrido mercapto and bis(mercapto) Ru(U) phosphine complexes. Pignolet's group has shown that H 2 S also oxidatively adds to /ra«£-IrCl(CO)(PPh 3) 2 forming the crystallographically characterized IrCl(H)(SH)(CO)(PPh 3) 2 (Figure 1.5).3 38 PPh, OC. ,PPh 3 X Ph 3P*^ ^ C l H,S H, HS 1 ..CO ' ^ C l PPh, Figure 1.5 Formation of /raw5-IrCl(H)(SH)(CO)(PPh 3) 2 9 References on page 23 Chapter 1 Reaction of /ra«5-Mo(N2)2(dppe)2 (dppe = bis(diphenylphosphino)ethane) with RSH (R = alkyl or aryl) generates the intermediate species c/s-Mo(H)(SR)(dppe)2 en route to fraws-Mo(SR)2(dppe)2.39 However, the intermediate species can be stabilized and isolated by using a 1.1 ratio of RSH and Mo, or a bulky RSH (R = Pr', Bu', 2,4,6-Me3C6H2, 2,4,6-Pr'3C6H2, 4,2,6-BrPr'2C6H2) (Figure 1.6).40 The mechanism is proposed as follows: dissociation of one N 2 ligand results in an equilibrium between the six-coordinate precursor and a five-coordinate species; RSH oxidatively adds to the five-coordinate species forming the hydrido thiolato species; a second N 2 ligand then dissociates, and a second RSH oxidatively adds; H2 is finally eliminated to form the bis(thiolato) species. Figure 1.6 Reactions of *rans-Mo(N2)2(dppe)2 with thiols. Stabilization of unsaturated five-coordinate complexes can be achieved by using bulky [MCl(dippe)2][BPh4] (M = Ru, Os) with PhSH results in [M(SPh)(dippe)2][BPh4] (Figure [M(SR)L][BPh4] (M = Fe, Co, Ni; L = tris(2-diphenylphosphinoethyl)phosphine (PP3), tris(2-diphenylphosphinoethyl)amine (NP3)) further indicates that the stability of monomelic metal-sulfur complexes is influenced by sterically demanding and electron rich ligands (Figure 1.7(b)); the X-ray structures of [Fe(SH)(PP3)][BPh4], [Co(MeS)(NP3)][BPh4], and [Ni(SH)(PP3)][BPh4] were reported.42 ligands such as l,2-bis(diisopropylphosphine)ethane (dippe). Reaction of 1.7(a)), and the Ru analogue is structurally characterized. 41 The formation of 10 References on page 23 Chapter 1 (a) r ?(Pr )2 ( P r V - M CI + + PhSH -HC1 M = Ru, Os ^ P ( P 4 ^ P M — S P h ( P r ) 2 P ^ P C P r ^ (b) f M ( H 2 0 ) L ] + R S H + L M = Fe, Co, N i R = H , M e L = X P 3 ; X = P,N (7 X ;M SR + + H L Figure 1.7 Formation o f five-coordinate, trigonal bipyramidal mercapto and thiolato complexes. 1.2.2.2 Bridging Mercapto and Thiolato Ligands The monomelic mercapto or thiolato complexes discussed above are relatively rare compared to dinuclear complexes because sulfur ligands have a tendency to utilize their lone pairs o f electrons to bridge two or more metal centres. 4 3 D i - and tri-jj, 2-SR dinuclear complexes are often formed by initial oxidative addition o f R S H to a monomelic metal complex followed by dimerization. H 2 S reacts with R h C l ( P P h 3 ) 3 3 8 and RhCl(triphos)(C 2H4) (triphos = M e C C Q L i P P h ^ ) 4 4 in CH 2 C 1 2 solutions to form the structurally characterized, SIT-bridged, dinuclear complexes [RhCl(H)(u 2-SH)PPh 3) 2] 2 (Figure 1.8(a)) and [Rh(triphos)(H)(u, 2-SH)] 2 2 + (Figure 1.8(b)), respectively. Interestingly, the reversible elimination o f 2 moi H 2 from [Rh(triphos)(H)(u, 2-SH)]2 2 + to form [Rh(triphos)(u, 2-S)]2 2 + was also observed. Similar reactions o f H 2 S with R u ( H ) 2 ( P M e 2 P h ) 4 and [Ir(H) 2(MeCO) 2(PPh 3) 2][BF 4] lead to the formation o f the 11 References on page 23 Chapter 1 structurally characterized (PhMe2P)2(SH)Ru(^2-SH)3Ru(PhMe2P)3 (Figure 1.8(c))45 and [(PPh3)2(H)Ir(u.2-H)(u.2-SH)2lr(H)(PPh3)3][BF4] (Figure 1.9),46 respectively; generation of H 2 was observed for both reactions. In the latter reaction, a minor product containing three different bridging ligands, [(PPh3)2(Ti)Ir(u2-H)(u.2-SH)(^ was also formed. Figure 1.8 Reactions of H2S with monomeric complexes to form di- and tri-u.2-SH dinuclear complexes. 12 References on page 23 Chapter 1 Me Me P3F4] minor product prfHfeOVlezCO^Phj^lBFJ + H phjP""/^ Nr'" ^ ' P P ^ [BF 4] major product H Figure 1.9 Reaction of [Ir(H)2(MeCO)2(PPh3)2][BF4] with H2S. In addition to phosphine ligands, arene ligands have also been utilized to stabilize complexes containing bridging mercapto and thiolato ligands as shown in Figure 1.10. Dinuclear molybdenum complexes [(ri7-C7H7)Mo(|i-SR)3Mo(ri7-C7H7))][BF4] are formed by treatment of [Mo(ri6-C6H5Me)(Ti7-C7H7)][BF4] with RSH (Figure 1.10(a)).47 Formation of di-u2-SR or tri-u.2-SR Ir(JJI) dinuclear complexes is dependent on the nature of the substituent R (Figure 1.10(b)). When the precursor [Cp*IrCl(u2-Cl)]2 (Cp* = Ti 2-C 5Me 5) is treated with RSH, [Cp*Ir(n2-SEt)3IrCp*]Cl is formed when R = Et, and [Cp*IrCl(^i2-SR)2ClIrCp*] is formed when R = Pr', Cy (cyclohexyl) or CH 2Ph. 4 8 Reaction of the Ir(UI) precursor complex with excess H2S afforded first the doubly-bridged u,2-SH complex [Cp*IrCl((i2-SH)2CUrCp*] which subsequently consumes more H2S to form the triply-bridged n2-SH complex [Cp*Ir(u,2-SH)3IrCp*]Cl.49 As the R groups become more bulky, formation of the triply-bridged species is disfavoured, for example, when R = Bu'SH.48 13 References on page 23 Chapter 1 Figure 1.10 Formation of dinuclear mercapto and thiolato-bridged complexes containing arene co-ligands. Sulfur ligands constitute the fundamental building blocks of the metal clusters found in enzymatic and industrial catalytic processes.50'51 Bridging thiolate ligands are used to connect metal centres in the clusters shown in Figure 1.11: (a) reaction of Co(N0 3 )2-6H 20 with PhSH 14 References on page 23 Chapter 1 in the presence of E t 3 N and Me^Cl affords [ M e ^ t ^ S P h M p ^ - S P h ^ ] ; 5 0 (b) reaction of Co(0 2CMe) 2-4H 20 with RSH (R = Me, Et) in the presence of PEt 3 and NaBPlu or TIPF 6 yields [Co 3(^ 2-SR) 6(PEt 3) 3]X (X = BPh,, PF 6); 5 2 and (c) reaction of ZnMe 2 with Pr'SH gives octameric [Me3Zn((x3-SPr')]8.53 SPh (a) r M e 4 N ] 2 P h ^ c C o ^ P h S i P h S - C o ^ s J - C o : -SPh P h / SPh Ph (c) (b) Et3P. 1 I PEt 3 ,S: | .c^1 A S - R PEt 3 R = Me, Et X = BPh4",PF6" Zn= Zn-Me S = S-Pr" Figure 1.11 Clusters containing u,2- and u.3-SR bridged ligands. Both H-atoms of H 2S can be cleaved from the S-atom upon reaction with metal complexes resulting in formation of species containing a bridging S2" ligand. Examples include [(P 3)Ni(u. 2-S)Ni(P 3)] 2 + (Ps = l,l,l-tris(diphenylphosphinomethyl)ethane; see Figure 1.12(a))54 and Pd2X2(u.2-S)(u-dpm)2 (X = CI, Br, I; see Figure 1.12(b) and Section 1.2.2.3)2 produced as shown. Cleavage of the S-C bond of alkanethiols, however, is not favoured as shown by the formation of [Pt 2(H) 2(^ 2-SMe)(^-dpm) 2] + from the reaction of [Pt 2(H)(CO)(|i-dpm) 2] + and 15 References on page 23 Chapter 1 MeSH (Figure 1.12(c)).55 Further evidence to display the different reactivities of H 2S and thiols are shown in Figure 1.13. When RhRe(CO)4(^-dpm)2 is treated with H 2S, PxhRe(CO)4(fX2-S)(u-dpm)2 and H 2 are generated quantitatively, while the analogous reaction with RSH (R = Et, Ph) yields RhRe(CO)3(ii2-H)(^2-SR)(^-dpm)2 (Figure 1.13(a)).56 Similarly, reaction of an equal molar quantity of RSH with |Tn3(u3-CO)3(u-dpm)3][PF6]2 gives [Pt3(H)(n3-S)(n-dpm)3][PF6] when R = H, Bu', and [Pt3(H)(n3-SR)(n-dpm)3][PF6]2 when R = Me, Et, CH2Ph, CH 2C0 2Et, Ph or p-tolyl (Figure 1.13(b)).57 The formation of the U3-S complex when Bu'SH was used is attributed to the loss of the relatively good leaving group Bu^ during the reaction.57b (a) 2[Ni(H 20) 6] 2+ + 4P3 + H2S 2P3H 6H 20 PPh. MeC ''-p .Ni S-V PPb,/ PPh2 PPh2 P- 2 _ N l / p ^ C M e \ P h 2 P P-PPh2 Ph,P' Ph, -PPh, (b) X Pd Pd X PPh, + H,S -H 2 X = CLBr,I Ph,P- •PPh, Ph, 1 A 1 p ' d P d , j. PPh, Ph,P-P h -*PPh, + (c) H Pt Pt CO PPh, MeSH CO Ph,P- Me ..Ss •PPh, + H1 Ph, • . i ' r ''ii • Pt! P t . N H PPh, Figure 1.12 Formation of u.2-S and ^ 2-SMe dinuclear complexes. 16 References on page 23 Chapter 1 P h 2 P - ^ ^ P P h 2 OC,, (a) O C — R h - — ^ R e — C O .ocr Ph2P-^PPh2 OC. I OC. I ,CO + H 2 S • H 2 CO ProP^ -PPra -PPfe \ + R S H ( R = Et,Ph^ CO P h z P - ^ ^ P P t e H . CO P h 2 P \ ^ p p h 2 PPh2 2+ Pte - P ' Ph2 + RSH(R = H , B u ) - H + , - C O H -+RSH, - CO (R = Me,Et ,CH 2 Ph, CHsCOiB, Ph, p-tolyl) H " Ph 2 Ph2P^ ^ P P h 2 Pte PhaP-I ^ p p f c Pte 2 + PPte Ph2 Pre Figure 1.13 S-H bond activation in H2S and thiols by (a) RhRe(CO)4(u-dpm)2 and (b) [Pt3(^-CO)(|i-dpm)3]z . 1.2.2.3 Recovery ofH 2 from H2S using Pd2X2(n-dpm)2 Study of H2S interactions with transition metal complexes is of great interest in this laboratory because of their potential utilization in H 2 recovery.1"7 The reaction of Pd2X2(u,-dpm)2 with H2S to give Pd2X2(u.2-S)(u,-dpm)2 and H 2 (Figure 1.12(b)) was the first homogeneous system demonstrating a 1:1 H 2S:H 2 stoichiometry at a metal centre.2 Kinetic 17 References on page 23 Chapter 1 and mechanistic studies showed first-order behaviour in both Pd2X2(u,-dpm)2 and H2S. The reaction proceeds via oxidative addition of H 2S to the Pd2 dimer which results in formation of the hydrido mercapto dinuclear intermediate Pd2X2(H)(SH)(u.-dpm)2 (Figure 1.14); which was detected at -78°C by *H and "Pf/H} NMR spectroscopy.3,4 P h 2 P " ' ^ P P h : ph 2 p .H P d P d ,.SH X ^ 'Ph2 Figure 1.14 Structure of intermediate formed during the reaction of Pd2X2(u-dpm)2 with H2S en route to Pd2X2(u,2-S)(u.-dpm)2 and H 2 . Pursuance of a catalytic cycle for the conversion of H 2 from H2S revealed that the bridged S-atom of Pd2X2(u.2-S)(u-dpm)2 can be effectively abstracted by dpm with formation of dpm(S) and quantitative reconversion of Pd2X2(u,-dpm)2 from Pd2X2(u.2-S)(u-dpm)2 (Figure 1.15).5 This is the first reported homogeneous catalytic process that generates H 2 from ffeS.1 Solution kinetic and mechanistic studies showed that this reaction is first-order in both Pd2X2(|x2-S)(u,-dpm)2 and dpm.5 Further, this process is thought to proceed via a transition state where a five-membered ring is formed by binding one end of the added dpm to one Pd centre and another end to u,2-S of Pd2X2(M,2-S)(u,-dpm)2 as shown in Figure 1.16.5 18 References on page 23 Chapter 1 H 2S H 2 X—pjd —Pjd - X Ph^-^PPte A ,s.„ Id' "ftL PteP^^PPrri dpm(S) dpm X = CI, Br, I dpm(S) = bis(diphenylphosphino)methane monosulnde Figure 1.15 Homogeneous catalytic cycle for the recovery of H 2 from H2S. Ph,P: Ph,P^ ^PPh2 --^y^pph 2 / PPh, PhzP-Figure 1.16 Proposed transition state for the reconversion of Pd2X2(Mpm)2 fr°m Pd2X2(n2-S)(u-dpm)2. 1.3 The Chemistry of Transition Metal Aminophosphine Complexes PPh, NMej Figure 1.17 [o-(AT -^dimethylamino)phenyl]diphenylphosphine] (P-N). 19 References on page 23 Chapter 1 The reactivity of [o-(/Y -^dimethylaimno)phenyl]diphenylphosphine (P-N, Figure 1.17) toward transition metals has been investigated since the ligand was reported in 1965.58 The coordination chemistry of this ligand and other aminophosphine ligands to many metal centres including Ag, 5 9' 6 0 Co, 6 1' 6 2 Cr, 6 3 ' 6 4 Cu , 6 0 , 6 5 lr,66"70 Mo, 6 3 , 6 4 Ni, 6 1' 7 1" 7 3 Pd, 5 8' 6 1' 6 2 , 7 0' 7 3" 7 6 P t w « 7 7 Re,7 8 Rh 6 1' 6 2- 7 0' 7 9- 8 0 and RU14>15'61-62.81-83 ls representative of P-N type system. Aminophosphine ligands are appealing for the synthesis of complexes utilized for catalysis (e.g. hydrogen transfer reduction,68'69 hydrosilylation,70 hydrogenation80) and for inorganic medicinal studies (e.g. binding of DNA). 8 4 Ligands containing a tertiary phosphine group and an amine group satisfy the following desirable qualities required for effective homogeneous catalysts: (1) strong coordination of the phosphine entity stabilizes low oxidation state metal complexes; (2) the relative ease of dissociation of the metal-amine bond may generate a vacant site for which a substrate may enter the coordination sphere of the metal ion; (3) a high nucleophilicity is conferred on the metal ion through nitrogen coordination (a-donation).66'79b The original interest of ruthenium aminophosphine complexes in this department was to evaluate the catalytic activity of RuCl2(PPFA)(PPh3) (PPFA = \-[N, JV-a-dimethylaminoethyl]-2-diphenylphosphinoferrocene)81a with respect to that of the well-known complex RuCl2(PPh3)3.85 The former complex was found to be an efficient catalyst for the hydrogenation of 1-hexene under mild conditions (30-60°C, < 1 atm H 2 ). 8 1 a To further develop this chemistry, studies were extended to other ruthenium aminophosphine complexes, and this led to the discovery of the very reactive, five-coordinate, square pyramidal complexes RuCl2(P-N)(PR3) (R = Ph, p-tolyl).14'16 With the availability of a vacant sixth-coordination site, a range of small molecules (L = H 2 0, MeOH, H 2S, EtSH, H 2 , N 2 , 20 References on page 23 Chapter 1 S02) were found to coordinate to yield either trans- or cz's-RuCl2(P-N)(PR3)(L) (Figure 1.18).14"16 + L + L trans isomer R = Ph, />-tolyl cis isomer L = H20,MeOH L = H2S, EtSH, H 2, N 2, S02* Figure 1.18 Reaction of RuCl2(P-N)(PR3) with small molecules L; *the formation of the S0 2 complex is not measureably reversible. 31P{1H} NMR and ! H NMR spectroscopic techniques are invaluable for the characterization of RuCl2(P-N)(PR3)(L) in solution. The presence of an AX coupling pattern in the 31P{1H} NMR spectra are characteristic of complexes containing two distinctively different phosphorus environments. Upon addition of L to RuCl2(P-N)(PPh3), the positions of the P A and Px doublets shift with respect to those of the precursor if coordination of L takes place. In general, P A is shifted by a greater magnitude for the trans isomer than the cis isomer because of the strong trans influence exerted by L on PA; the positions of Px are relatively unaffected for both isomers because the PR3 groups are always trans to a NMe2 group. Furthermore, the average 2 JPP coupling constants14'16 are 3 6 and 2 9 Hz for the trans and cis isomers, respectively; both values are consistent with coupling of cis-phosphines.86 The NMe groups are equivalent and only one singlet is observed in the X H NMR spectra; thus, in solution, the five-coordinate structures have C s symmetry. The cis isomers, however, have C i symmetry with nonequivalent NMe groups and two singlets are observed in the ^ N M R spectra. In some cases, the trans and cis structural assignments are supported by X-ray 2 1 References on page 23 crystallographic data (e.g. c/5-RuCl2(P-N)(P(p-tolyl)3)(H2S)).14 Chapter 1 zra«5-RuCl2(P-N)(P(p-tolyl)3)(H20)16 and 1.4 Overview of Thesis In this thesis work, the coordination chemistry of RuCl2(P-N)(PR3) and other ruthenium aminophosphine systems are further investigated. General experimental details are presented in Chapter 2, while the synthesis, characterization and reactivity of ruthenium aminophosphines complexes are discussed in Chapter 3. The solution and solid structural properties of C75-RuCl2(P-N)(PPh3)(L) (L = H2S, RSH) and rra/M-RuCl2(P-N)(PPh3)(L) (H20, ROH) are presented and compared in Chapters 4 and 5, respectively. In Chapter 6, the binding of various small molecules other than S- or O- containing species (e.g. those have N-donor ligands) to RuCl2(P-N)(PPh3) are explored. Finally a summary of results and some recommendations for future work are given in Chapter 7. 22 References on page 23 Chapter J 1.5 References 1. James, B. R. Pure Appl. Chem. 1997, 69, 2213. 2. Lee, C.-L.; Besenyei, G ; James, B. R.; Nelson, D. A.; Lilga, M. A. J. Chem. Soc, Chem. Commun. 1985, 1175. 3. Besenyei, G ; Lee, C.-L.; Gulinski, J.; James, B. R.; Nelson, D. A.; Lilga, M. A. Inorg. Chem. 1987, 26, 3622. 4. Barnabas, A. F.; Sallin, D.; James, B. R. Can. J. 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Ed Engl. 1997, 36, 1185. 85. James, B. R. In Comprehensive Organometallic Chemistry, Vol. 8; Wilkinson, G., Stone, F. G. A.; Abel, E. W., Eds.; Pergamon Press: Oxford, 1982, Chapter 51. 86. (a) Krassowski, D. W.; Nelson, J. H ; Brower, K. R; Hauenstein, D.; Jacobson, R. A. Inorg. Chem. 1988, 27, 4294. (b) Joshi, A. M.; Thorburn, I. S.; Rettig, S. J.; James, B. R. Inorg. Chim. Acta 1992, 198-200, 283. 28 Chapter 2 Experimental Procedures General Procedures Unless otherwise stated all manipulations were performed under an oxygen-free Ar or N 2 atmosphere at r.t. using standard Schlenk techniques. All solvents were dried and purged free of oxygen prior to use. 2.1 Materials 2.1.1 Gases Purified Ar (H.P.), N 2 (U.S.P.), H 2 (Research, extra dry) and 0 2 (U.S.P.) were obtained from Union Carbide Canada Ltd., anhydrous H2S, HC1 and NH3 from Matheson Gas Co., and N 2 0 from Praxiar. All gases except Ar, N 2 and H 2 were used without further purification. Ar and N 2 were dried by passing through columns of CaS04. H 2 was passed through an Engelhard Deoxo catalytic hydrogen purifier to remove traces of 0 2. 2.1.2 Solvents All spectral or analytical grade solvents were obtained from Fisher, Eastman, Aldrich, Mallinckrodt Chemical Co., BDH, or MCB, and were refluxed and distilled over appropriate drying agents1 under N 2 prior to use. CH2C12 was dried over CaH2; CeH6, hexanes, and Et 20 over Na^enzophenone; acetone over K2C03; MeOH and EtOH over Mg/I2; isopropanol over CaO; and THF over K/Na alloy. All solvents used in reactions involving Ru complexes were purged with Ar or N 2 (for at least 10 min) to remove traces of 0 2 before 29 References on page 74 Chapter 2 being transferred into their reaction flasks via cannula. All deuterated solvents (CD2CI2, CDCI3, C6D6, C 7 D 8 , (CD3)2CO, DMSO-de and D20) were obtained from Cambridge Isotope Laboratories (CJJL), MSD Isotopes, or Isotec Inc., and stored over activated molecular sieves (Fisher, type 4 A, 4 - 8 mesh), with the exception of D20. For the preparation of 02-sensitive samples, the deuterated solvents were de-oxygenated (via the freeze-pump-thaw method), dried over drying agents (CD2C12, CDCI3 and (CD3)2CO using activated molecular sieves; CeD6 and C7D8 using Na/benzophenone), and stored under vacuum or Ar atmosphere. 2.1.3 Compounds All commerically available compounds were supplied by Aldrich, Anachemia, BDH, Eastman, Fisher, Mallinckrodt or MCB. These materials were used as received unless otherwise specified. Proton sponge (l,8-bis(dimethylamino)naphthalene), obtained from Aldrich, was purified by passing a solution of the amine in w-pentane through a column of alumina, and evaporating the eluant to yield a white solid.2 Anal. Calcd. Ci4Hi gN 2: C, 78.46; H, 8.47; N, 13.07. Found: C, 78.48; H, 8.37; N, 12.78. *H NMR (CD2C12): 8 6.9 - 7.4 (6H, m, Ph), 2.80 (6H, s, N(C#3)2). The NMR data correspond with literature data.3 2.2 Instrumentation 2.2.1 Nuclear Magnetic Resonance Spectroscopy NMR spectra were recorded on a Bruker AC200 (200.1 MHz for *H and 81.0 MHz for 31P), a Varian XL300 (300.0 MHz for 'H, 121.4 MHZ for 31P{XH} and 75.0 MHz for "Cl/H} NMR), a Bruker WH400 (400.0 MHz for XH) or a Bruker AMX500 (500.0 MHz for 'H and 202.5 MHz for 31P) FT-NMR spectrometer. Residual protonated species in the 30 References on page 74 Chapter 2 deuterated solvents were used as internal references (8 5.32 for CD2CI2, 8 7.15 for C6D6, 8 7.24 for CDC13, and 8 2.20 for (CD 3)2CO; all are reported relative to the external standard of tetramethylsilane (TMS) at 8 0.00) for *H NMR NMR chemical shifts. The 31P{XH} NMR chemical shifts are reported relative to 85 % H3PO4 (external reference) with the downfield shifts taken as positive. For the 31P{1H} NMR spectra recorded on the Varian XL300, the chemicals shifts reported were externally referenced to trimethylphosphite, P(OMe)3 at 8141.04 (relative to 85% H3P04). Unless otherwise specified, all variable-temperature NMR spectra were performed on the Varian XL300 or the Bruker AMX500 spectrometers. Samples were prepared in 5 mm NMR tubes with poly(propylene) caps or rubber septa. For C -^sensitive samples, NMR tubes with poly(tetrafluoroethylene), J. Young valves (Aldrich) were used. Solid samples were initially place in the NMR tubes, which were then evacuated, and deuterated solvents were subsequently vacuum transferred into the tubes maintained at liquid N2 temperature. These samples were carefully warmed to room temperature (r.t.) and the tubes placed under 1 atm of Ar or another gas as required by the specific experiment. 2.2.2 Infrared Spectroscopy An ATLI Mattson Genesis Series FTIR spectrophotometer was used to record all infrared spectra (range: 500 to 4000 cm'1). Samples for analysis were made into KBr pellets; data are reported in cm'1. 2.2.3 Ultraviolet Spectroscopy UV-Vis spectra were recorded on a Hewlett Packard 8452A diode-array spectrophotometer (range: 190 to 820 nm) equipped with a thermostatted cell compartment 31 References on page 74 Chapter 2 using 1 cm quartz cells. For (^ -sensitive compounds or in situ reactions, an anaerobic cell5 equipped with a side-arm flask for mixing of solutions was used. Data are reported as in nm (e in units of M^cm'1). 2.2.4 Thermal Analysis Thermogravimetric analyses (TGA) were performed using a TA Instruments TGA 51 Thermogravimetric Analyzer. Solid samples were weighed accurately (10 - 15 mg) into an inert Pt pan. The samples were then heated in a N 2 atmosphere (flow rate =100 cc/min) at a rate of 10°C/min to a maximum of 500°C. Differential Scanning Calorimetery (DSC) data were collected on a TA Instruments 910S Differential Scanning Calorimeter. Solid samples were weighed accurately (2-5 mg) into disposable aluminum pans. The samples were then heated in a N 2 atmosphere (flow rate = 40 cc/min) at a rate of 5°C per min to a maximum of 500°C. 2.2.5 Microanalysis Microanalyses (%C, H, N, and/or CI, S) were performed by Mr. P. Borda of this department. A Carlo Erba Model 1106 Elemental Analyzer or a Fisons (Erba) Instruments EA 1108 CHN-0 Elemental Analyzer was used and the results have an absolute accuracy within ±0.3 %. 2.2.6 X-ray Crystallography All single crystal X-ray, diffraction studies with the exception of data for c/.s-RuCl2(P-N)(PPh3)(r|2-H2) 36 (P-N = [o-(Ar,/Y-dimethylaniino)phenyl](diphenylphosphine)), were performed by the late Dr. S. J. Rettig of this department on a Rigaku/ADSC CCD area 32 References on page 74 Chapter 2 detector or a Rigaku AFC6S diffractometer (both with graphite monochromated Cu-Ka radiation). The single crystal X-ray diffraction study of 36, was performed by Dr. V. G. Young, Jr. of the X-Ray Crystallographic Laboratory at the University of Minnesota, using a Siemens SMART Platform CCD system (with Mo-Ka radiation). 2.2.7 Gas Chromatography Gas chromatographic analyses were performed on a temperature-programmable Hewlett Packard 5890A instrument equipped with a thermal conductivity detector, using He as the carrier gas. 2.2.8 Magnetic Susceptibility Studies The Johnson-Matthey Magnetic Susceptibility Balance was (Gouy method) used to measure the magnetism of samples. The mass susceptbility per gram of sample, %e, was calculated according to the equation below. Diamagnetic contributions from Ru(III) and ligands were obtained and calculated from Pascal's constants.6 _ CBSI I (R~ R-o) X g 109 m where: C B a i = balance calibration constant I = sample length (cm) R = reading for tube plus sample Ro = reading for empty tube m = sample mass (g) 2.2.9 Conductivity Measurements A Serfass Conductance Bridge Model RCM15B1 (Arthur H. Thomas Co. Ltd.) connected to a 3403 cell from the Yellow Springs Instrument Company was used for conductivity measurements. The cell was thermostatted at 25°C in a water-bath. The cell 33 References on page 74 Chapter 2 constant, a = 0.001413 ohm'1 cm"1, was determined by measuring the resistance of a 0.0100 M aqueous solution of KCI. Solutions with concentrations of ~10'3 M were used for conductance measurements. All solutions were prepared using dried and (Vfree solvents; the most extensive set of data was obtained during studies of some reactions of complexes with NH 3 (Section 6.2). 2.3 Syntheses of Ligands The ligands synthesized in this thesis work are shown in Figure 2.1. M e 2 N Me2N P - N (ref. 7) BPN(ref. 7) TPN(ref. 7) P A N (ref. 14) ( f l ) - A M P H O S (ref. 12) ( S ) - A L A P H O S ( r e f . 15) PO(ref.9) Figure 2.1 Ligands studied in this thesis work. 34 References on page 74 Chapter 2 2.3.1 [o-(/V^V-Dimethylamino)phenyl]diphenylphosphine, P-N7 2.3.1.1 o-Bromo-AyV-dimethylaniline8 The aniline was prepared by the method described by Gilman and Banner.8 One equiv. of dimethylsulfate (14 mL, 0.148 moi) was added to a stirring solution of o-bromoaniline (25 g, 0.145 moi) in water (30 mL), and the mixture was stirred for 1 h to achieve homogeneity. While cooling in an ice-bath, this solution was neutralized with 5.0 M KOH. Addition of dimethylsulfate (14 mL, 0.148 moi) and neutralization with KOH were repeated twice. After the mixture was stirred for 3 h, the organic layer was extracted with Et 20 (3 x 20 mL). The combined etheral extracts were washed with water (3 x 20 mL) and dried over K 2 C0 3 . Product distillation gave a clear, colourless oil (21 g, yield: 72 %), bp 96°C (15 mmHg). X H NMR (CDC13): 5 2.80 (6H, s, N(C#3)2), [6.88 (IH, t), 7.12 (1H, d), 7.27 (IH, t), 7.59 (IH, d), Ph]. The NMR data were not determined in the original reference.8 2.3.1.2 [0-(AyV-Dimethylamino)phenyl]diphenylpnosphine, P-N7 P-N was prepared following the method of Fritz et al.7 A solution of o-bromo-A^TV-dimethylaniline (3.5 g, 0.0175 moi) in Et 20 (7mL) was added dropwise to a 1.6 M solution of "BuLi in hexane (11 mL, 0.0175 moi) which had been cooled to -20°C. The mixture was warmed to r.t. and stirred for 1 h during which time a white precipitate, o-Li(C6H4)NMe2, formed. This mixture was cooled to -40°C and a solution of Ph2PCl (3.2 mL, 0.0175 moi) in Et 20 (3.5 mL) was added dropwise. Again, the mixture was warm to r.t. and stirred for 1 h, when water (20 mL) was added to the turbid pale-yellow mixture. The product was extracted with Et 20 (4 x 15 mL). The combined ethereal extracts were dried over anhydrous MgS04. The white residue which remained after removal of the Et 20 was recrystallized from hot EtOH to give clear, colourless crystals. Yield: 3.2 g, 60%. 35 References on page 74 Chapter 2 Mp 122 - 123°C. Anal. Calcd. C2oH2oNP: C, 78.67; H, 6.60; N, 4.59. Found: C, 78.80; EL 6.47; N, 4.59. 31P{1H} NMR (C6D6): 5 -14.4 (s). lH NMR (C6D6): 5 6.8 - 7.3 (14H, m, Ph), 2.60 (6H, s, N(C#3)2). The NMR data agree with the literature data.7'9'10 2.3.2 Bis [0-(AyV-dimethylamino)phenyl] phenylphosphine, BPN7 BPN was prepared in the same manner as described for P-N but using PhPCl2 (1.2 mL, 8.75 mmol). Yield: 3.0 g, 50 %. Mp 85 - 86°C. Anal. Calcd. C 2 2H 2 5N 2P: C, 75.84; H, 7.23; N, 8.04. Found: C, 75.84; H, 7.26; N, 7.99. 31P{1H) NMR (CDC13): 8 -22.8 (s). J H NMR (CDC13): 6 6.6 - 7.3 (13H, m, Ph), 2.56 (12H, s, N(C#3)2). X-ray quality crystals were recrystallized from EtOH at 0°C. The ORTEP plot, selected bond lengths and angles of the crystal structure are shown and discussed in Section 3.5, while full experimental parameters and details are presented in Appendix I. 2.3.3 Tris[o-(/y^V-dimethylamino)phenyl]phosphine, TPN 7 TPN was prepared by Dr. P. Meessen of this laboratory in the same manner as described for P-N but using PC13 (0.5 mL, 5.83 mmol). X-ray quality crystals were recrystallized from EtOH and the structure was determined.11 Yield: 0.9 g, 40%. Mp 108 - 109°C. Anal. Calcd. C 2 4H 3 0N 3P: C, 73.63; H, 7.72; N, 10.73. Found: C, 73.49; H, 7.81; N, 10.53. 31P{1H} NMR (CDC13): 8 -28.9 (s). XHNMR (CDC13): 8 6 5 - 7.4 (12H, m, Ph), 2.6 (18H, s, N(C#3)2). The data given here were determined by Dr. P. Meessen.11 36 References on page 74 Chapter 2 2.3.4 (i?)-(+)-7Y^V-Dimethyl-l-[o-(diphenylphosphino)phenyl]ethylamine, AMPHOS 1 2 2.3.4.1 (/?)-(+)-/V^V-Dimethyl-l-phenylethylamine13 The title amine was prepared by the method described by Pine and Sanchez.13 A flask charged with (i?)-(+)-l-phenylethylamine (30 g, 0.25 moi) was cooled to 0°C. Formic acid (90%, 35 mL, 0.8 moi) and then formaldehyde (37%, 56 mL, 0.75 moi) were added dropwise, and the yellow mixture was refluxed at 80°C for 24 h. It was then acidified with 6 M HC1 (50 mL) while being cooled in an ice-bath. Nonbasic material was extracted from the mixture using E t 2 0 (3 x 50 mL) and discarded. The aqueous layer was made basic by adding 50 % NaOH and then extracted with E t 2 0 (2 x 50 mL). The combined ethereal extracts were washed with water (20 mL) and dried over anhydrous MgS04. Removal of the Et 20 resulted in a yellow liquid, the distillation of which gave a clear, colourless liquid (32°C, -ImmHg). Yield: 20 g, 54%. J H NMR (CDC13): 8 7.2 (4H, m, Ph), 3.1 (1H, q, C#CH3), 2.1 (6H, s, N(C#3)2), 1.3 (3H, d, CHC#3). The NMR data were not given in the original reference.13 2.3.4.2 AMPHOS-HCl-(acetone)12 The AMPHOS ligand was prepared by the method described by Payne and Stephan.12 An 1.6 M solution of "BuLi in hexane (84 mL, 0.134 moi) was added dropwise to a solution of (R)-(+)-TV, TV-dimethyl- 1-phenylethylamine (20 g, 0.134 moi) and Et 20 (100 mL). The yellow mixture was stirred for 24 h, and cooled in an ice-bath, before Ph2PCl (24 mL, 0.134 moi) was added slowly. The reaction mixture was stirred for 2 h, and water (100 mL) was then added to the resultant orange solution. The organic layer was extracted with E t 2 0 (3 x 50 mL), and the combined organic layers were dried over anhydrous MgS04. HC1 gas was passed through the filtered E t 2 0 solution for 10 min, before removal of the E t 2 0 resulted 37 References on page 74 Chapter 2 in an orange oil. A minimum of acetone was added to dissolve the oil and Et20 was slowly added to precipitate a white solid. NMR analysis of this white powder indicate a mixture of starting amine (30%) and AMPHOS-HCl-(acetone) (70%). The NMR data for AMPHOS-HCl-(acetone) are: "Pf/H} NMR (CDC13): 6 -17.2 (s). X H NMR (CDC13): 8 12.4 (1H, br s, -NHC1), 6.9-8.1 (14H, m, Ph), 5.04 (1H, hx, CH3C#), 2.89, 2.45 (6H, d, N(C#3)2), 8 1.6 (3H, d, C773CH), 8 2.1 (6H, s, acetone). The NMR data correspond to those in the literature.12 2.3.4.3 Purification of AMPHOS 1 2 Crude AMPHOS-HC1-(acetone) (3.8 g) was recrystallized from hot acetone to obtain a white powder. This was redissolved in hot EtOH and was neutralized to pH ~8 with 1 M KOH ethanolic solution. After removal of EtOH, Et 20 was added, and the mixture was filtered. An oily residue remained after the removal of the Et 20 from the filtrate. MeOH was then added to redissolve the residue. At 0°C, a white precipitate that formed was filtered off and washed with cold MeOH (2 x 10 mL). Clear, colourless crystals formed after recrystallization from hot MeOH once again. Yield: 1.0 g, 20 %. Mp 80-81°C. Anal. Calcd. C 2 2H 2 4NP: C, 79.25; H, 7.26; N, 4.20. Found: C, 79.18; H, 7.33; N, 4.22. "Pf/H} NMR (CDC13): 8-17.2 (s). X H NMR (CDC13): 8 6.9-7.5 (14H, m, Ph), 4.12 (1H, qn, CH3C#), 2.00 (6H, s, N(C#3)2), 8 1.20 (3H, d, Cff3CH). The above characterization data are consistent with literature data.12 2.3.5 l-(JV^V-Dimethylamino)-8-(diphenylphosphino)naphthalene, PAN 1 4 PAN was prepared by the method described by Horner and Simons with minor modifications.14 Tetramethylethylenediamine (TMEDA) was used to assist the lithiation of 38 References on page 74 Chapter 2 l-(dimethylamino)naphthalene with «-BuLi. To a cooled solution (-20°C) of "BuLi (1.6 M in hexane, 9.1 mL, 0.0146 mol), a solution of l-(dimethylamino)naphthalene (2.5 g, 0.0146 mol) in hexanes (15 mL) was added dropwise. The yellow mixture was stirred for 10 min, after which TMEDA (2.2 mL, 0.0146 mol) was added. The mixture was slowly warmed to r.t. and stirred for 16 h during which time a white precipitate, l-(dimethylamino)-8-lithionaphthalene, formed. A solution of PI12PCI (2.6 mL, 0.0146 mol) in E t 2 0 was added dropwise to the cooled (-40°C) reaction mixture. This was then warmed to r.t., stirred for 1 h, and made basic with 6 M KOH. The organic layer was extracted with E t 2 0 (3 x 20 mL) and the combined ethereal extracts were washed with water (20 mL) and dried over anhydrous MgSCv Removal of E t 2 0 resulted in a yellow-orange residue. Recrystallization of this solid from C H 2 C I 2 at 0°C resulted in yellow crystals. Yield: 2.6 g, 50 %. Mp 170 - 171°C. Anal. Calcd. C24H22NP: C, 81.10, H, 6.24; N, 3.94. Found: C, 80.83; H, 6.18; N, 3.93. "P^H} NMR (CDCI3): 5 -2.86 (s). lH NMR (CDC13): 8 6.8 - 7.9 (16H, m, Ph), 2.57 (6H, s, N(C#3)2). The physical and spectroscopic data agree with those reported.14 2.3.6 [(5)-2-(Dimethylamino)propyl]diphenylphosphine, A L A P H O S 1 5 2.3.6.1 (6)-2-(Dimethylamino)propanoic acid16 The methylation of (,S)-2-aminopropanoic acid (alanine) was carried out according to the method described by Bowman and Stroud.16 Formaldehyde (37 %, 30 mL) was added to a stirring suspension of (5)-alanine (15.0 g, 0.168 mol) and Pd/C (10%, 1.5 g) in water (400 mL, and H 2 gas was passed through the mixture for 24 h. After removal of the H 2 source, the mixture was refluxed for 15 min and was immediately filtered into a Buchner funnel containing Celite. Such filtration through Celite was repeated three times to remove any Pd/C. Removal of water resulted in a hygroscopic, white solid. Yield: 17.9 g, 90%. J H 39 References on page 74 Chapter 2 NMR (D20): 5 4.77 (1H, s, COH), 3.66 (IH, q, (H3C)C#, 3 J H H = 7.0HZ), 2.79 (6H, d, N(C#3)2, 3 J H H = 20.7 Hz), 1.42 (3H, d, (#3C)CH, 3 J H H = 7.0 Hz). The NMR data were not given in the original reference.16 2.3.6.2 (5)-2-(DimethyIamino)-l-propanol15 The title alcohol was prepared by the method described by Hayashi et al.15 (5)-2-(Dimethylamino)propanoic acid (17.9 g, 0.153 moi) in 1 g portions was added over a period of 30 min to a stirring suspension of UAIH4 (12.4g, 0.327 moi) in THF (400 mL). The mixture was refluxed for 4 h, cooled, and stirred under N 2 for 16 h. The white precipitate that formed after the successive addtion of water (25 mL), 15 % NaOH (25 mL) and water (75 mL) was removed by filtration and washed with THF (2 x 20 mL). The combined THF filtrates were dried over anhydrous NaS04. Removal of THF resulted in a yellow oil whose product distillation gave a clear, colourless oil, bp 60°C (15 mmHg). Yield: 7 g, 45 %. J H NMR (CDC13): 8 3.50 (IH, br s, H2CO#), 3.22 (2H, m, #2COH), 2.61 (1H, m, (H3C)C//), 2.10 (6H, s, N(C#3)2), 0.79 (3H, d, (#3C)CH). The NMR data correspond to the literature data.15 2.3.6.3 (iS)-2-(DimethyIamino)propylchloride hydrochloride15 A solution of (6>2-(dimethylamino)-l-propanol (7.0 g, 0.068 moi) in EtOH (10 mL) was cooled in an ice-bath and acidified with 12 M HC1 (20 mL). Evaporation of the EtOH gave the H Q salt as a clear colourless oil. CHC13 (20 mL) was then added to form two immisible layers. This mixture was cooled to 0°C and SOCl2 (15 mL, 0.206 moi) was added over a period of 30 min. The resultant homogeneous, clear solution was refluxed for 2 h; removal of the solvent from the cooled solution gave an orange oil. Recrystallization of the oil from EtOH (3 times) gave clear, colourless, hygroscopic crystals. Yield: 6.7 g, 62 %. J H 40 References on page 74 Chapter 2 NMR (CDCI3): 5 12.76 (IH, br s, HN*(CK3)2), 3.96 (2H, m, H2CCl), 3.62 (1H, m, (H3C)C#), 2.83 (6H, s, HN+(C/f3)2), 150 (3H, d, (#3C)CH). The NMR data were not given in the original reference.15 2.3.6.4 [(.S>2-(Dimethylamino)propyl|diphenylphosphine, ALAPHOS 1 5 To a 3-neck, 200 mL flask charged with t-BuOK (1.8 g, 16.0 mmol) and THF (30 mL) was added Ph2PH (l.lOmL, 6.3 mmol). A bright orange solution formed immediately. (S)-2-(pimethylamino)propylcMoride hydrochloride (1.0 g, 6.3 mmol) was added and the mixture was refluxed for 2 h. The mixture turned colourless and a white precipitate (KC1) formed. The solvent was removed and 3 M HC1 (150 mL) was added to the residue. This cloudy mixture was extracted with CeFL; (50 mL). The aqueous layer was made basic by adding 15 % NaOH (50 mL) and extracted with CeHe (2 x 80 mL). The combined C.6H6 extracts were washed with a saturated NaCl solution (100 mL) and dried over anhydrous NaSOj. A yellow oily residue remained after the removal of C&H6. Et 20 was added to dissolve the residue and the solution was passed through a neutral alumina column to remove any phosphine oxide. Evaporation of Et 20 gave a clear, colourless oil. Yield: 1.25 g, 73 %. 3lV{lH} NMR(CDC13): 8 -19.11 (s). 'HNMR (CDC13): 6 7.2 - 7.7 (10H, m, Ph), 3.07 (1H, m, (H3C)Cfl), 2.87 (IH, br. d, C/faHbPPh,), 2.56 (6H, s, N(C#3)2), 2.00 (IH, t of d, CHa#bPPh2), 1.43 (3H, d, (#3C)CH). The NMR data agree with the literature data.15 2.3.7 0-Diphenylphosphineanisole, PO 9 The preparation of o-diphenylphosphineanisole was initiated by a Grignard reaction described by Roundhill and co-workers.9 A 3-neck flask, equipped with an addition funnel and a condenser, was charged with Mg turnings (3.25 mg, 0.134 moi) and Et 20 (100 mL) under a flow of N 2 . o-Bromoanisole (25 g, 0.134 moi) was then slowly added, and the 41 References on page 74 Chapter 2 mixture was allowed to react for 2 h. The grey-green mixture that resulted was cooled in an ice-bath and a solution of Ph2PCl (25 mL, 0.139mol) in Et 20 (20 mL) was added. The rnixture was stirred for 20 h at 20°C during which time a white precipitate formed. Water (50 mL) was added and the product was extracted with Et 20 (2 x 50 mL). The combined etheral extracts were washed with H 2 0 (2 x 20 mL) and dried over K2C03. Removal of Et 20 resulted in a white residue, whose recrystallization from hot EtOH (2 times) gave clear, colourless, crystalline needles. Yield: 15 g, 38%. Melting point: 123-124°C. Anal. Calcd. Ci 9H 1 7OP: C, 78.07; H, 5.86. Found: C, 78.11; H, 5.76. 31P{1H} NMR (CDCI3): 8-15.34 (s). *H NMR (CDCI3): 8 6.6 - 7.8 (14H, m, Ph), 3.76 (3H, s, O-CH3). The physical and spectroscopic data are consistent with the literature data.9 2.4 Syntheses of Ruthenium Precursors The ruthenium as RuCl3 3H20 (41.5 - 43.96% Ru) was obtained on loan from Johnson Matthey Ltd. and Colonial Metals Inc. 2.4.1 Dichlorotris(triphenylphosphine)ruthenium(n), RuCl2(PPh3)3 (l) 1 7 The title complex was prepared following a literature method17 with slight modifications. A solution of RuCl3 3H20 (2.11 g, 8.5 mmol) in MeOH (250 mL) was refluxed for 5 min, and then cooled to r.t., when PPI13 (14.0 g, 53.4 mmol) was added. The mixture was refluxed for 3 h during which time a dark brown suspension formed. The mixture was filtered while still hot and the brown solid was washed with hot MeOH (6 x 20 mL), Et 20 (2 x 20 mL) and hexanes (2 X 20 mL) to remove excess PPh3. Yield: 8.0 g, 97 %. Anal. Calcd. C54H45Cl2P3Ru: C, 67.64; H, 4.73. Found: C, 67.50; H, 4.69. 42 References on page 74 Chapter 2 2.4.2 Dichlorotris(tri-/7-tolylphosphine)ruthenium(II), RuCI2(P(p-tolyI)3)3 (2)18 The title complex was prepared following a literature method.18 A solution of RuCl3 3H20 (1.0 g, 3.8 mmol) in MeOH (100 mL) was refluxed for 5 min, and then cooled to r.t., when P(/?-tolyl3)3 (5.0 g, 16.4 mmol) was added. The mixture was then refluxed for 24 h to give a dark purple solid which was filtered off and washed with MeOH (7x10 mL) and Et 20 (3 x 10 mL). Yield: 4.15 g, 74 %. Anal. Calcd. C63H63Cl2P3Ru: C, 69.74; H, 5.85. Found: C, 69.66; H, 5.83. 2.4.3 Cis-Dichlorotetrakis(dimethylsuIfoxide)ruthenium(IT), Cis-RuCl2(DMSO)4 (3)19 A solution of RuCl3 3H20 (1.18 g, 4.5 mmol) and excess DMSO (12 mL) was refluxed for 30 min. The volume of the resulting deep red solution was reduced to 2 mL and acetone (5 mL) was added to precipitate a yellow solid, that was filtered off and washed with acetone (5mL) and Et 20 (5 mL). Yield: 1.36 g, 62%. Anal. Calcd. C63H63Cl2P3Ru: C, 19.88; H,4.97. Found: C, 20.02; H, 5.11. 2.4.4 Trichlorobis(triarylphosphine)(dimethylacetamide)ruthenium(ni)-DMA solvate RuCl3(PPh3)2(DMA)(DMA) (4a) and RuCl3(P(p-tolyl)3)2(DMA)(DMA) (4b)20 The title complexes were prepared by Dr. D. E. Fogg, previously of this laboratory. Solid PPh3 (4.34 g, 16.6 mmol) or P(p-tolyl)3 (5.05 mg, 16.6 mmol) was added to a dark brown solution of RuCl33H20 (2.0 g, 8.3 mmol) in DMA (60 mL), and the reaction mixture was stirred at r.t. for 24 h. The resulting green precipitate was filtered off, washed with DMA (2x5 mL) and hexanes (3x5 mL), and dried under vacuum. For 4a: yield: 5.2 g, 69 %. Anal. Calcd. C44H48N202Cl3P2Ru: C, 58.32; H, 5.34; N, 3.09. Found: C, 58.22; H, 5.23; N, 3.01. For 6b: yield: 5.5 g, 67 %. Anal. Calcd. CsoHsoNzOzClsPjRu: C, 60.64; H, 6.11; N, 2.83. Found: C, 60.32; H, 6.11; N, 2.80. 43 References on page 74 Chapter 2 2.5 Dichlorobis(o-diphenylphosphinoanisole)ruthenium(II), RuCl2(PO)2 (5)9 The title complex was prepared by the method described by RoundhilFs group9 with modifications. To a suspension of RuCl2(PPh3)3 (104 mg, 0.109 mmol) in acetone (5 mL) was added a solution of PO (70 mg, 0.239 mmol) in acetone (5 mL). The mixture was heated at 50°C for 3 h during which time a burgundy solid formed. This was filtered off and washed with Et 20 (2X5 mL). Yield: 66 mg, 80 %. Anal. Calcd. C^HwOzCkPzRu: C, 60.32; H, 4.53. Found: C, 60.12; H, 4.34.31P{XH> NMR (CDC13): 5 64.20 (s). J H NMR (CDC13): 8 6.8 - 7.6 (28H, m, Ph), 4.57 (6H, s, 0-CH3). The NMR data agree with the literature data.9 2.6 Syntheses of Ruthenium(II) Aminophosphine Complexes 2.6.1 Dichloro{[o-(/V^V-dimethylamino)phenyl](diphenylphosphine)} (triphenylphosphine)riithenium(II), RuCl2(P-N)(PPh3) (6a)2'21 Method l 2 1 To a solution of RuCl2(PPh3)3 (0.30 g. 0.31 mmol) in CH2C12 (50 mL) was added P-N (0.096 g, 0.31 mmol). The dark brown solution turned dark green immediately and was stirred for 2h. After the solvent was removed in vacuo, 5 mL CH2C12 was added to redissolve the dark green residue. Hexanes (30 mL) was added to the solution to precipitate a dark green solid. The product was reprecipitated in CFkCl^exanes twice more to remove excess PPh3 and OPPh3. Yield: 127 mg, 55 %. Anal. Calcd. C 3 8H 3 5NCl 2P 2Ru: C, 61.71; H, 4.77; N, 1.89. Found: C, 61.51; H, 4.84; N, 1.85. 31P{1H} NMR (C6D6): 8 83.69 (d, P-N), 48.87 (d, PPh3); 2 J P P = 36.54 Hz. J H NMR (C6D6): 8 7.0-7.9 (29H, m, Ph), 3.07 (6H, s, N(C#3)2). The NMR data correspond to those reported.2,21 UV-Vis (CH2C12): 454 (1100), 678 (480). 44 References on page 74 Chapter 2 Method 2 A sample of /rara-RuCl2(P-N)(PPh3)(OH2) (33a) (Section 2.10.1) was placed in vacuo and heated to 80°C for 16 h. With the removal of H 20, the pink solid turned green (yield: 100 %). 2.6.2 Dibromo{[o-(Ar»A'-dimethylamino)phenyl](diphenylphosphine)} (triphenylphosphine)ruthenium(II), RuBr2(P-N)(PPh3) (6b) A solution of P-N (135.9 mg, 0.44 mmol) in acetone (10 mL) was added to a suspension of RuCl2(PPh3)3 (420.8 mg, 0.44 mmol) in acetone (10 mL), and the mixture was stirred at 50°C for 30 min. Excess NaBr (1.14 g, 11.09 mmol) was added to the resulting dark green solution. The mixture, containing a suspension of NaBr and NaCl, was stirred at r.t. for 24 h. The salts were filtered off through Celite and the volume of the filtrate was removed in vacuo. CH2C12 (10 mL) was then added to redissolve the dark green residue and this solution was filtered through Celite once more. The volume of the filtrate was reduced to ~5 mL before hexanes was added to precipitate a green-brown solid. This was filtered off and washed with hexanes (2x lOmL). Yield: 185 mg, 51 %. Anal. Calcd. C38H35NBr2P2Ru: C, 55.09; H, 4.26; N, 1.69. Found: C, 54.57; H, 4.23; N, 1.64. 31P{1H) NMR (C6D6): 8 85.47 (d, P-N), 50.08 (d, PPh3); 2 J P P = 36.30 Hz. J H NMR (C<>D6): 8 6.7-7.8 (29H, m, Ph), 3.17 (6H, s, N(C#3)2). UV-Vis (CH2C12): 472 (1170), 706 (615). 2.6.3 Diiodo{[o-(iVyV-dimethylamino)phenyl](diphenylphosphine)} (triphenylphosphine)ruthenium(II), RuI2(P-N)(PPh3) (6c) The title complex was prepared following the same procedure used the Br analogue (Section 2.6.2) but using excess Nal (1.64 g, 10.97 mmol). A dark red solid was isolated from the acetone solution. Yield: 348 mg, 86 %. Anal. Calcd. C3gH35NI2P2Ru: C, 49.47; 45 References on page 74 Chapter 2 H, 3.82; N, 1.52. Found: C, 49.21; H, 3.78; N, 1.58. "Pf/H} NMR (CDC13): 6 89.18 (d, P-N), 8 53.62 (d, PPh3); 2 J P P = 35.56 Hz. *H NMR (CDC13): 8 6.9-7.8 (29H, m, Ph), 3.48 (6H, s, N(C#3)2). UV-Vis (CH2C12): 510 (900), 774 (510). 2.6.4 Dichloro{[0-(7VVV-dimethyIainino)phenyl](diphenylphosphine)} (tri-/>-tolylphosphine)ruthenium(n),RuCl2(P-N)(POE>-tolyI)3) (7a)2,21 The title complex was prepared in the same manner as described for the PPh3 analogue (Section 2.6.1), but using RuCl2(P(p-tolyl)3)3 (335 mg, 0.31 mmol, method 1) or RuCl2(P(p-tolyl)3)3(OH2) (method 2). The product is a dark green solid which in the solid state is much more sensitive to 0 2 than that of its PPh3 analogue. Yield: method 1, 130 mg, 55 %; method 2, 100%. Anal. Calcd. C4iH4iNCl2P2Ru: C, 63.00; H, 5.29; N, 1.79. Found: C, 63.03; H,5.26; N, 1.86. ^Pf^ H} NMR (CsDfi): 8 81.46 (d, P-N), 47.64 (d, PPh3); 2 J P P = 37.15 Hz. *H NMR (C6D6): 8 6.6-8.0 (26H, m, Ph), 3.11 (6H, s, N(C#3)2), 2.00 (9H, s, p-iCaRdCHi). The NMR data are consistent with those reported.2,21 UV-Vis (CH2C12): 452(1155), 672 (555). 2.6.5 Dibromo{[0-(iV^V-dimethyIamino)phenyI](diphenyIphosphine)} (tri-p-tolylphosphine)ruthenium(n), RuBr2(P-N)(P07-tolyl)3) (7b) The title complex was prepared in the same manner as the PPh3 analogue (Section 2.6.2) but using RuCl2(P(p-tolyl)3)3 (476.0 mg, 0.44 mmol). A light orange solid was isolated. Yield: 202 mg, 53 %. Anal. Calcd. C4iH4iNBr2P2Ru: C, 56.56; H, 4.75; N, 1.61. Found: C, 57.09; H, 4.86; N, 1.75. 31V{lH) NMR (CDC13): 8 84.56 (d, P-N), 47.48 (d, PPh3); 2 J P P = 35.51 Hz. lH NMR (CDC13): 8 6.6-8.0 (26H, m, Ph), 3.12 (6H, s, N(C/7r3)2),2.30(9H,s,jp-(C6H4)C/Y3). UV-Vis: 474 (1150), 700 (560). 46 References on page 74 Chapter 2 2.6.6 Diiodo{[o-(iV^V-dimethylamino)phenyl](diphenylphosphine)} (tri-p-to!ylphosphine)ruthenium(II), RuI2(P-N)(P(p-tolyl)3) (7c) The title complex was prepared in the same manner as the Br analogue (Section 2.6.5) but using excess Nal (25 equiv). The solid is dark red. Yield: 300 mg, 72 %. Anal. Calcd. C41H41NI2P2RU: C, 51.05; H, 4.28; N, 1.45. Found: C, 51.05; H, 4.25; N, 1.48. 31V{lH) NMR (CDCI3): 5 89.27 (d, P-N), 51.27 (d, PPh3); 2 J P P = 35.82 Hz. J H NMR (CDC13): 5 6.7-7.8 (26H, m, Ph), 3.46 (6H, s, N(C#3)2), 2.30 (9H, s, p-iCeH^CH^). UV-Vis: 512 (780), 780 (435). 2.6.7 Dichlorobis{[o-(iNyV-dimethylamino)phenyI](diphenylphosphine)}ruthenium(II), RuCl2(P-N)2 (8)9 The title complex was prepared using the method described by Shen et al. for the synthesis of RuCl2[K2(P^V)-Ph2PCH2CH2NMe2]2.22 Zn powder (66 mg, 1.00 mmol) was added to a THF (15 mL) solution containing P-N (360 mg, 1.18 mmol) and RuCl3-3H20 (100 mg, 0.38 mmol). The dark brown suspension was refluxed for 4 h. After the removal of the heat source, the mixture was stirred for 24 h during which time a deep red solution formed. Insoluble materials were filtered off through Celite and the volume of the filtrate was reduced to 5 mL before hexanes was added to precipitate a dark red solid. The product was filtered off and washed with hexanes (2x10 mL). Yield: 160 mg, 54 %. Anal. Calcd. C4oH4oN2Cl2P2Ru-1/2(CH2Cl2): C, 58.95; H, 5.01, N, 3.39. Found: C, 59.19; H, 5.04; N, 3.29. 31PCH} NMR (CDC13): 8 58.9 (s, P-N). *H NMR (CDC13): 8 6.9-7.8 (28H, m, Ph), 5.32 (1H, s, CH2C12) 3.25 (12H, s, N(Cr73)2). The NMR data agree with the literature data.9 47 References on page 74 Chapter 2 2.6.8 Dichloro[(l-(Ar^-dimethylamino)-8-(diphenylphosphino)naphthalene](triphenyl phosphine)ruthenium(II), RuCl2(PAN)(PPh3) (9) A solution of PAN (51 mg, 0.143 mmol) in CH2CI2 (5 mL) was transferred to a stirring solution of RuCl2(PPh3)3 (137 mg, 0.143 mmol) in CH2CI2 (5 mL) via a cannula. A dark green solution was formed within 10 min. The solution was stirred for 4 h and its volume was then reduced to 2 mL. Hexanes (15 mL) was added slowly to precipitate a green solid that was filtered off and washed with hexanes (3x15 mL). Yield: 55 mg, 50 %. Anal. Calcd. C42H37NCl2P2Ru: C, 63.88; H, 4.72; N, 1.77. Found: C, 64.19; H, 4.84; N, 1.59. ^Pl/H} NMR (CDC13): 8 97.10 (d, P-N), 41.39 (d, PPh3); 2 J P P = 32.05 Hz. *H NMR (CDC13): 5 6.6-8.3 (31H, m, Ph), 3.68 (3H, s, N(C#3)), 2.96 (3H, s, N(C#3)). UV-Vis: 450 (1210), 622 (490). 2.6.9 Dichloro[(l-(A^V-dimethylamino)-8-(diphenylphosphino)naphthalene](tri-/;-tolyl phosphine)ruthenium(II), RuCl2(PAN)(P(p-tolyl)3) (10)2 The title complex, a dark green solid, was prepared in the same manner as described for 9 (Section 2.6.8) but using RuCl2(P0?-tolyl)i)3 (155 mg, 0.143 mmol). Yield: 58 mg, 45 %. Anal. Calcd. C45H43NCl2P2Ru: C, 64.98; H, 5.21; N, 1.68. Found: C, 64.98; H, 5.25; N, 1.66. 31P{lH} NMR (C6D6): 8 97.71 (d, P-N), 39.57 (d, PPh3); 2 J P P = 33.39 Hz. *H NMR (CsDs): 8 6.4-8.0 (28H, m, Ph), 3.50 (3H, s, N(C#3)), 2.90 (3H, s, N(C#3)), 2.00 (9H, s, ^-(CeH^Ctfj). The NMR data agree with those reported.2 UV-Vis: 450 (1280), 622 (520). 2.6.10 Dichloro{(/?)-/V^V-dimethyl-1- [o-(diphenylphosphino)phenyl] ethylamine} (triphenylphosphine)ruthenium(II), RuCl2(AMPHOS)(PPh3) (l l ) 2 The title complex was prepared in situ by dissolving RuCl2(PPh3)3 (12 mg, 0.013 mmol) and excess AMPHOS (5.0 mg, 0.015 mmol) in C 6 D 6 (0.8 mL). The ^PI^ H} 48 References on page 74 Chapter 2 NMR spectrum of the dark green solution indicates 100 % formation of 11 with 2 equiv. of PPh3 liberated. "Pf/H} NMR (C6D6): 8 84.56 (d, P-N), 40.32 (d, PPh3); 2 J P P = 37.03 Hz. *H NMR (CsDg): 8 6.6-8.2 (29H, m, Ph), 6.17 (1H, m, CH3C/7), 2.86 (3H, s, N(C#3)), 2.33 (3H, s, N(C#3)), 1.01 (3H, d, C#3CH). The NMR data agree with those reported.2 UV-Vis (in situ): 460 (1050), 636 (570). Repeated attempts to isolate an analytically pure product were unsuccessful. A solution of AMPHOS (35 mg, 0.105 mmol; or 70 mg, 0.210 mmol) in acetone (5 mL) was added to a solution of RuCl2(PPh3)3 (100 mg, 0.104 mmol) in acetone (15 mL), and the mixture was stirred for 16 h. The volume of the resulting dark green solution was reduced to 5 mL and hexanes was added to precipitate a dark green/brown solid. This was filtered off and washed with hexanes (2x5 mL). Yield: 45 mg, 56 %. Anal. Calcd. C4oH39NP2Cl2Ru: C, 62.58; H, 5.12; N, 1.82. Found: C, 59.99; H, 4.70; N, 1.36. 31P{1H} NMR spectrum (in CDC13) indicate the presence of 11, RuCl2(PPh3)3 (br, 8 42.5), OPPh3 (s, 8 30.5) and PPh3 (s, 8-4.0). 2.6.11 Attempts to Prepare Dichlorobis{[(*S)-2-(dimethylamino)propyl] (diphenylphosphine)}ruthenium(Il), RuCI2(ALAPHOS)2 (12) 2.6.11.1 Reaction of ALAPHOS with RuCl2(PPh3)3 A solution of (5)-Alaphos (30 mg, 0.110 mmol) in CH2C12 (2 mL) was added to a solution of RuCl2(PPh3)3 (50 mg, 0.052 mmol) in CH2C12 (5 mL). The pink solution which formed immediately was stirred for 16 h. Then the volume of the solvent was reduced to 2 mL, and hexanes (10 mL) was slowly added to precipitate a pink solid (15 mg), that was filtered off and washed with hexanes (2 x 10 mL). NMR spectroscopic analysis indicates the presence of at least two Ru complexes. Reprecipitation of this solid using CH^Vhexanes gave a similar, impure solid. The *H NMR spectrum is complex and peaks could not be 49 References on page 74 Chapter 2 assigned. 31P{lH} NMR (CDC13): 5 55.60 (s) is assigned to fra«s-RuCl2(ALAPHOS)2 (cf. 8 57.4 (s) is due to rraw5-RuCl2(Ph2PCH2CH2NMe2)2);22 49.7 and 43.1 (broad peaks) due to a minor product. 2.6.11.2 Reaction of ALAPHOS with ds-RuCl2(DMSO)2 A solution of (iS)-Alaphos (30 mg, 0.110 mmol) in CH2C12 (2 mL) was added to a solution of cw-RuCl2(DMSO)2 (26 mg, 0.053 mmol) in CH2C12 (5 mL). The initial yellow suspension, after being stirred for 2 h, slowly turned to a pink, homogeneous solution. After 24 h the solution volume was reduced to 2 mL. Et 20 (15 mL) was added to precipitate a pale pink solid that was isolated by filtration and washed with Et 20 (2x10 mL). NMR spectroscopic analysis gave similar results to those given in Section 2.6.11.1, indicating a mixture of products. 2.6.12 DichIoro{bis[o-(Ar»A7-dimethylamino)phenyl](phenylphosphine)} (triphenylphosphine)ruthenium(II), RuCl2(BPN)(PPh3) (13) A solution of BPN (34.8 mg, 0.100 mmol) in CH2C12 (3 mL) was added to a solution of RuCl2(PPh3)3 (80.5 mg, 0.084 mmol) in CH2C12 (5 mL). A dark orange solution formed after the mixture was stirred for 24 h. The volume of CH2C12 was then reduced to ~3 mL and hexanes (10 mL) was added to precipitate a dark orange solid. The filtered product was reprecipitated using CH^Cyhexanes (2 times), washed with hexanes (2x10 mL) and dried in vacuo at 80°C. Yield: 25 mg, 38%. Anal. Calcd. C4sH46N2Cl2P2Ru: C, 61.38; H, 5.15; N, 3.58. Found: C, 60.95; H, 4.87; N, 3.39.31P{1H} NMR (CDCI3): 8 56.00 (d, BPN), 33.67 (d, PPh3); 2 J P P = 32.05 Hz. TTNMR (CDC13): 8 6.6-7.8 (28H, m, Ph), 3.63 (3H, s, N(C#3)), 3.15 (3H, s, N(Cff3)), 2.60 (3H, s, N(C#3)), 2.20 (3H, s, N(C#3)). 50 References on page 74 Chapter 2 2.6.13 Dichloro{bis[0-(7A^V-dimethylainino)phenyI](phenylphosphine)} (tri-/Molylphosphine)ruthenium(II), RuCl2(BPN)(P(j>-tolyl)3) (14) The title complex was prepared using the same method as described for the PPh3 analogue 13 (Section 2.6.12), but using RuCl2(P(/?-tolyl)3)3 (33.4 mg, 0.031 mmol) and BPN (12.3 mg, 0.035 mmol) Yield: llmg, 43%. Anal. Calcd. C43H46N2Cl2P2Ru: C, 62.62; H, 5.62; N, 3.40. Found: C, 62.37; H, 5.64; N, 3.15. 31P{XH} NMR (CDC13): 5 56.05 (d, BPN), 31.26 (d, PPh3); 2 J P P = 31.44 Hz. *H NMR (CDC13): 5 6.6-7.8 (25H, m, Ph), 3.64 (3H, s, N(C#3)), 3.1 (3H, s, N(Ci73)), 2.57 (3H, s, N(C#3)), 2.20 (3H, s, N(C#3)), 2.20 ^H^/HQHOC^). 2.7 Syntheses of Ruthenium(m) Aminophosphine Complexes 2.7.1 Trichloro{[o-(A7^V-dimethylamino)phenyl](diphenylphosphine)} (triphenylphosphine)ruthenium(ItT), RuCl3(P-N)(PPh3) (15a)2 A solution of P-N (67.0 mg, 0.22 mmol) in acetone (10 mL) was added to a stirring suspension of RuCl3(PPh3)2(DMA)-(DMA) (200.0 mg, 0.22 mmol) in acetone (10 mL). The homogeneous, orange solution which formed immediately was stirred for 3 h during which time a red solid precipitated. This was collected and washed with acetone (2x5 mL). Yield: 140 mg, 82%. Anal. Calcd. C 3 gH 3 5NCl 3P 2Ru: C, 58.89; H, 4.55; N, 1.81. Found: C, 58.69; H,4.59; N, 1.81. UV-Vis (CH2C12): 336, shoulder, (1760), 398 (1875), 508 (1830). %e = 2.32 x 10"6 cgs, fieff = 2.0 BM. The X-ray structure of 15a was previously determined; the UV-Vis and magnetic data were not obtained in the original reference.2 51 References on page 74 Chapter 2 2.7.2 Trichloro{[o-(7V^V-dimethylamino)phenyl](diphenylphosphine)}(tri-/7-tolylphosphine)ruthenium(IU), RuCb(P-N)(P07-tolyl)3) (15b)2 . The title complex was prepared in the same manner as described for the PPh3 analogue (Section 2.7.2), but using RuCl2(pO>tolyl)3)2(DMA)-(DMA) (220 mg, 0.22 mmol). A bright red solid was isolated. Yield: 150 mg, 84%. Anal. Calcd. C4iH4iNCl3P2Ru: C, 60.26; H,5.06; N, 1.71. Found: C, 60.30; H, 5.11; N, 1.75. UV-Vis (CH2C12): 334, shoulder, (1750), 396 (1840), 504(1800). X g = 2.15 X I O - 6 cgs, p.eff=1.9BM. The UV-Vis and magnetic data were not determined in the original reference.2 2.7.3 Mer-trichloro{bis[o-(/V^V-dimethylamino)phenyl](phenyIphosphine)} ruthenium(lU), Mer-RuCl3(BPN) (16) A solution of BPN (38.0 mg, 0.11 mmol) in CH2C12 (10 mL) was added to a solution of RuCl3(PPh3)2(DMA)-(DMA) (100.0 mg, 0.11 mmol) in CH2C12 (10 mL). The reaction mixture was stirred for 2.5 h during which time an orange solution formed. The volume of CH2C12 was reduced to 3 mL and hexanes (10 mL) was added to precipitate a dark orange solid that was collected and washed with hexanes (2x10 mL). Yield: 55 mg, 90 %. Anal. Calcd. C 2 2H 2 5N 2Cl 3PRu: C, 47.54; H, 4.53; N, 5.04. Found: C, 50.71; H, 4.22; N, 3.47. Satisfactory elemental analysis of 16 could not be obtained even after repeated (3 times) reprecipitations with CEkCyhexanes. %g= 1.23 x 10"6 cgs, 0 ^ = 1.5 BM. Orange, platelet crystals of RuCl3(BPN)-(CDCl3) were obtained by slow evaporation from a CDC13 solution over 2 days in an NMR tube. The ORTEP plot, selected bond lengths and angles of this complex are shown and discussed in Section 3.6, while the full experimental parameters and details are given in Appendix II. 52 References on page 74 Chapter 2 2.1.A Di-u,-chloro-|i-oxo-bis{chloro[o-(Ar^V-dimethylaniino)phenyI] (diphenylphosphine)ruthenium(m)}, (u-0)(n-Cl)2[RuCl(P-N)]2 (17) The title complex was prepared by stirring a suspension of RuCl2(P-N)(PPh3) (200 mg, 0.270 mmol) in acetone (10 mL) under 1 atm of 02. The green precursor dissolved over 1 h to form a dark green solution. The solution was stirred for 16 h during which time a dark green solid precipitated; this was filtered off, washed with hexanes (2x10 mL) and dried in vacuo at 80°C. The green solid was insoluble in acetone, C H C I 3 or and was only slightly soluble in DMSO and CH2C12. Yield: 85 mg, 32%. Anal. Calcd. C4oH4oN2OCl4P2Ru2: C, 49.50; H,4.15; N, 2.89. Found: C, 49.50; H, 4.16; N, 2.75. "P^H} NMR (CsDg): 5 38.74 (d, PA-N), 35.33 (d, PB-N); 4 J P P = 10.44 Hz. *H NMR (CeDe): 6 6.6-8.4 (28H, m, Ph), 3.31 (3H, s, N(CH3)), 2.89 (3H, s, N(CH3)), 2.11 (3H, s, N(CH3)), 2.02 (3H, s, N(CH3)). UV-Vis (DMSO): 348(15300), 652(11200). xg = 0cgs, \ies = 0 BM. Green, platelet crystals of 17 were obtained from the slow evaporation of an acetone solution of RuCl2(P-N)(PPh3) exposed to air over 24 h. The ORTEP plot, selected bond lengths and angles are presented and discussed in Section 3.2.1, while the full experimental parameters and details are given in Appendix III. 2.8 Syntheses of Ruthenium(II) Complexes Containing Coordinated H2S or Thiols: Cw-dichloro{[o-A7^V-dimethylamino)phenyl](diphenylphosphine)}(triaryl phosphine)(ligand)ruthenium(n), C/v-RuX2(P-N)(PRj)(L) The five-coordinate RuCl2(P-N)(PR3) (R = Ph, /7-tolyl) was isolated in low yield (-55 %) because many subsequent precipitations were required to remove PR3 and OPR3 impurities. Unless otherwise specified, RuCl2(P-N)(PR3) was prepared in situ from RuCl2(PR3)3 for the syntheses of six-coordinate complexes of the type RuCl2(P-N)(PR3)(L), where L = a small molecule. The PR3 (2 moles per Ru) produced is simply a spectator in the 53 References on page 74 Chapter 2 reactions. With use of the in situ precursor, high yields of the six-coordinate products were obtained. 2.8.1 Cis-RuCl2(P-N)(PPh3)(SH2)(acetone) (18a) The title complex was prepared using modifications of the method previously reported for synthesis of the non-solvated complex.2'23 A solution of P-N (64 mg, 0.21 mmol) in acetone (3 mL) was added to a suspension of RuCl2(PPh3)3 (200 mg, 0.21 mmol) in acetone (8 mL), and the mixture was stirred at 50°C for 30 min to form the dark green solution of RuCl2(P-N)(PPh3). The reaction flask was placed under reduced pressure and 1 atm of H 2S was introduced. A yellow solution formed immediately, and this was stirred for at least 8 h during which time a yellow precipitate formed. This was filtered off, but no washings were performed as this causes the loss of H2S. The product was dried under vacuum for 1 h at r.t. and subsequent analyses or reactions were carried out immediately. Yield: 140 mg, 80 %. Anal. Calcd. C38H37NCl2SP2Ru-(acetone): C, 59.20; H, 5.21; N, 1.68. Found: C, 58.94; H, 5.32; N, 1.69. 31P{1H} NMR (OAs): 6 51.28 (d, P-N), 44.53 (d, PPh3); 2 J P P = 29.50 Hz. ^ N M R (CsDe): 5 6.4-8.4 (29H, m, Ph), 3.67 (3H, s, N(C#3)), 2.97 (3H, s, N(C#3)), 1.54 (6H, s, acetone), 1.02 (2H, br s, Ru(S#2)). UV-Vis (CH2C12, under 1 atm H2S): 426 (830). IR: V S - H 2476, 2506 (weak), Vco 1707 (acetone, strong). Yellow-brown, prism crystals of 18a were obtained from a saturated acetone solution of the complex left standing for 5 days. The ORTEP plot, selected bond lengths and angles are shown and discussed in Section 4.2.1, while the full experimental parameters and details are given in Appendix IV. 54 References on page 74 Chapter 2 2.8.2 Cis-RuBr2(P-N)(PPh3)(SH2)(acetone) (18b) The title complex was prepared by stirring a solution of RuBr2(P-N)(PPh3) (100 mg, 0.121 mmol) in acetone (3 mL) under 1 atm of H2S. The yellow solution was stirred for 24 h during which time a yellow precipitate formed. The product was obtained by filtration and drying under vacuum for 1 h. Yield: 80 mg, 72 %. Anal. Calcd. C38H37NBr2SP2Ru-(acetone): C, 53.49; H.4.71; N, 1.52. Found: C, 53.28; H, 4.78; N, 1.46. "Pf/H} NMR (CsDe): 8 53.54 (d, P-N), 45.59 (d, PPh3); 2Jpp = 28.41 Hz. lH NMR (CgDg): 8 6.4-8.4 (29H, m, Ph), 3.93 (3H, s, N(C#3)), 2.87 (3H, s, N(C773)), 1.54 (6H, s, acetone), 1.14 (2H. br s, Ru(S#2)). UV-Vis (CH2C12, under 1 atm H2S): 446 (995). IR: v s.H 2506, 2476 (weak), v c o 1707 (acetone, strong). Orange prism crystals of RuBr2(P-N)(PPh3)(SH2)-(C6D6) were obtained from a saturated CeD6 solution of the complex left standing in a sealed NMR tube for 2 days. The ORTEP plot, selected bond lengths and angles are shown and discussed in Section 4.2.2, while the full experimental parameters and details are given in Appendix V. 2.8.3 In situ Preparation of Cis-RuI2(P-N)(PPh3)(SH2) (18c) A dark brown solution formed after the addition of 1 atm H2S to a CDC13 solution of RuI2(P-N)(PPh3). The *H NMR and "Pf/H} NMR spectra were collected within 10 min of adding H2S. n?{lH} NMR (10 min, CDC13): 8 56.0 (d, P-N), 49.5 (d, PPh3); 2 J P P = 25.8 Hz. *H NMR (10 min, CDC13): 8 6.5-8.2 (29H, m, Ph), 4.16 (3H, s, N(C#3)), 2.20 (3H, s, N(Cr73)), 0.95 (Ru(SH2), signal is hidden under free H2S signal). The in situ species decomposes to a paramagnetic, presumably Ru(JJI) species after ~1 h as indicated by noisy NMR spectra containing broad lines. 55 References on page 74 Chapter 2 2.8.4 as-RuQ2(P-N)(P(p-tolyl)3)(SH2)(acetone) (19a) The title complex was prepared in the same manner as described for the PPh3 analogue (Section 2.8.1) but using RuCl2(P(p-tolyl)3)3 (200 mg, 0.18 mmol) and P-N (56.3 mg, 0.18 mmol). Yield: 117mg, 73%. Anal. Calcd. C4iH43NCl2SP2Ru-(acetone): C, 60.48; H, 5.65; N, 1.60. Found: C, 60.23; H, 5.77; N, 1.65. 31P{'H} NMR (CDC13): 8 51.91 (d, P-N), 42.58 (d, PPh3); 2 J P P = 30.41 Hz. *H NMR (CDC13): 8 6.6-8.0 (26H, m, Ph), 3.41 (3H, s, N(C#3)), 3.05 (3H, s, N(C#3)), 2.15 (9H, s, jp-(C6H4)C/f3), 2.04 (6H, s, acetone), 0.95 (2H, br s, Ru(S#2)). UV-Vis (CH2C12): 435 (900). IR: v s.H 2495, 2449 (weak), Vco 1707 (acetone, strong). 2.8.5 Cw-RuBr2(P-N)(P(/?-tolyl)3)(SH2)(acetone) (19b) The title complex was prepared in the same manner as described for the PPh3 analogue (Section 2.8.2) but using Riu3r2(P-N)(P0>tolyl)3 (100 mg, 0.11 mmol). Yield: 86 mg, 78 %. Anal. Calcd. GuH^NBr^Ru-(acetone): C, 54.89; H, 5.13; N, 1.45. Found: C, 55.11; H,5.23; N, 1.49. nV{lH} NMR (CDC13): 8 53.41 (d, P-N), 44.58 (d, PPh3); 2 J P P = 29.20 Hz. >HNMR (CDC13): 8 6.6-8.0 (26H, m, Ph), 3.68 (3H, s, N(C#3)), 2.99 (3H, s, N(C#3)), 2.18 (9H, s, p-(C6lU)CH3), 2.04 (6H, s, acetone), 0.95 (2H, br s, Ru(S#2)). UV-Vis (CH2C12): 452 (935). IR: vs.H2495, 2449 (weak), v c o 1707 (acetone, strong). 2.8.6 In situ Preparation of Ci's-RuI2(P-N)(P0j-tolyl)3)(SH2) (19c) An orange solution formed after adding 1 atm H2S to a CDC13 solution of RuI2(P-N)(P(/7-tolyl)3). Similar to 18c, 19c decomposed after ~1 h. ^Pl'H} NMR (10 min, CDC13): 8 56.2 (d, P-N), 47.5 (d, PPh3); 2 J P P = 25.8 Hz. J H NMR (10 min, CDC13): 8 6.5-56 References on page 74 Chapter 2 8.2 (29H, m, Ph), 4.15 (3H, s, N(C#3)), 2.91 (3H, s, N(C#3)), 5 2.22 (9H, s, p-(C<£U)CHi), 0.90 (Ru(S#2), signal is hidden under free H2S signal). 2.8.7 Cis-RuCl2(P-N)(PPh3)(MeSH)(acetone) (20) Methanethiol was obtained from Aldrich as a liquid and stored at 0°C. A solution of MeSH (0.5 mL, 9.0 mmol) in acetone (2 mL) was cooled to 0°C and purged with N 2 for 1 min. This solution was cannula transferred to a stirring acetone solution (5 mL) containing RuCl2(PPh3)3 (100.0 mg, 0.104 mmol) and P-N (32.0 mg, 0.104 mmol). A homogeneous yellow solution formed immediately and, after being stirred for 16 h, precipitated a yellow solid. The product was filtered off and dried in vacuo (30 min). Yield: 72 mg, 80 %. Anal. Calcd. C39H39NCl2SP2Ru-(acetone): C, 59.64; H, 5.36; N, 1.66. Found: C, 59.46; H, 5.53; N, 1.65. ^Pl/H} NMR (CD2C12): 6 50.37 (d, P-N), 41.33 (d, PPh3); 2 J P P = 30.17 Hz. *H NMR (CD2C12): 8 6.4-7.9 (29H, m, Ph), 3.35 (3H, s, N(C#3)), 3.10 (3H, s, N(C#3)), 2.10 (6H, s, acetone), 0.70 (4H, m, overlap of Ru(S(CH3)#) and Ru(S(C#3)H)). UV-Vis (CH2C12, excess MeSH): 424(835). IR: vs.H2533 (weak), vCo 1707 (acetone, strong). Yellow-brown, prism crystals of 20 were obtained from a saturated acetone solution of the complex left standing for 24 h. The ORTEP plot, selected bond lengths and angles are presented in Section 4.3.1, while the full experimental parameters and details are given in Appendix VI. 2.8.8 as-RuCl2(P-N)(PPh3)(EtSH)(EtSH)(acetone) (21) The title complex was prepared in the same manner as described for 20 (Section 2.8.7) but using excess EtSH (1 mL, 19.2 mmol) at 20°C. The product was a yellow solid. Yield: 65 mg, 78%. Anal. Calcd. C40H4iNCl2SP2Ru-(EtSH)-(acetone): C, 58.62; H, 5.79; N, 1.52. Found: C, 59.08; H, 5.75; N, 1.46.  nV{ lYi} NMR (CD2C12): 8 52.43 (d, P-N), 43.97 (d, 57 References on page 74 Chapter 2 PPhs), 2 J P P = 30.23 Hz. ! H NMR (CD2C12). 5 6.4-8.0 (29H, m, Ph), 3.41 (3H, s, N(C#3)), 3.24 (3H, s, N(C#3)), 2.10 (6H, s, acetone), 2.00 ( I H , m, Ru(S(CHa#bCH3)H)), 0.78 (1H, m, Ru(S(C/^aHbCH3)H)), 0.63 ( I H , ddd, Ru(S(CHaHbCH3)#)), 0.45 (3H, dd, R u ^ C H a H b C / ^ H ) ) , free EtSH signals at 5 2.55 (2H, dq, HSCW2CH3), 1.46 ( I H , t, #SCH2CH3), 1.31 (3H, t, HSCH2C/f3). UV-Vis (CH2C12, excess EtSH). 424(830). IR: VS-H2516 (weak), Vco 1707 (acetone, strong). Yellow, prism crystals of RuCl2(P-N)(PPh3)(EtSH)-1.5(C6D6) were obtained from a saturated CeDe of the complex solution left standing in a sealed NMR tube for 24 h. The ORTEP plot, selected bond lengths and angles are presented in Section 4.3.2, while the full experimental parameters and details are given in Appendix VII. 2.8.9 In situ Preparation of Cis-RuCl2(P-N)(PPh3)(RSH), R = n-Pr, i-Pr, n-Pn, n-Hx, and Bz (Pr = propyl, Pn = pentyl, Hx = hexyl, Bz = benzyl) With use of the RuCl2(PPh3)3 precursor, the title complexes could not be isolated for purposes of elemental analysis because they decompose during the work-up processes due to the loss of RSH; the species are also very 02-sensitive and could only be observed in the 31P{1H} NMR spectra in 02-free conditions with the presence of excess RSH. ! H NMR spectra were not assigned due to the excess RSH. The CDC13 or CeD6 solutions of these species are yellow. 2.8.9.1 Cis-RuCl2(P-N)(PPh3)(/i-PrSH) (22) 31P{1H} NMR (CDC13): 6 51.22 (d, P-N), 42.46 (d, PPh3); 2 J P P - 30.05 Hz. 2.8.9.2 as-RuCl2(P-N)(PPh3)(i-PrSH) (23) 31P{!H} NMR (C6D6): (three sets of doublets, intensities of signals in parenthesis) 8 56.76 (d, P-N), 46.84 (d, PPh3); 2 J P P = 36.54 Hz (strong); 58 References on page 74 Chapter 2 8 49.58 (d, P-N), 41.68 (d, PPh3); 2 J P P = 30.23 Hz (medium); 8 51.31 (d, P-N), 42.74 (d, PPh3); 2 J P P = 29.93 Hz (weak). 2.8.9.3 C7s-RuCl2(P-N)(PPh3)(#i-PnSH) (24) 31P{1H} NMR (C6D6): (two sets of doublets, intensities of signals in parenthesis) 8 51.30 (d, P-N), 42.84 (d, PPh3); 2 J P P = 29.63 Hz (strong); 8 49.57 (d, P-N), 46.35 (d, PPh3); 2 J P P = 36.06 Hz (weak). 2.8.9.4 Cis-RuCl2(P-N)(PPh3)(/i-HxSH) (25) 31P{1H} NMR (CDC13): 8 51.15 (d, P-N), 42.57 (d, PPh3); 2 J P P = 30.23 Hz. 2.8.9.5 Cis-RuCl2(P-N)(PPh3)(BzSH) (26) 31P{1H} NMR (CDC13): 8 50.16 (d, P-N), 42.03 (d, PPh3); 2 J P P = 30.41 Hz. 2.9 In Situ Preparation of Ru(L)X(P-N)(PPh3) (L = SH, OH, H) and Ru(L)2(P-N)(PPh3) (X = CI, Br; L = SH, OH, H) The title species given in this Section were not isolated and were only observed in situ by NMR spectroscopy. The species are 02-sensitive and were prepared in NMR tubes equipped with poly(tetrafluoroethylene) J. Young valves. Discussion concerning their characterization is given in Section 3.3. 2.9.1 Ru(SH)Cl(P-N)(PPh3) (27a) The title species was observed in two different reactions: Reaction 1: To an NMR tube containing RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) and NaSH-xH20 (5 mg), dVacetone (0.75 mL) was vacuum transferred with the aid of liquid N 2 . The resulting orange solution was stored at -78°C (dry ice/acetone), and NMR spectra were 59 References on page 74 Chapter 2 measured at -78°C. "P^H} NMR (d6-acetone): 8 55.26 (d, P-N), 46.33 (d, PPh3); 2 J P P = 30.88 Hz. *H NMR (d6-acetone): 8 6.2-8.1 (29H, m, Ph), 8 3.27 (3H, s, N(Cr73)), 8 3.18 (3H, s, N(C#3)), 8-2.08 (1H, s, Ru-SH). This species was only observed at temperatures below -30°C. Reaction 2: To an NMR tube containing RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) and proton sponge (3 mg, 0.014 mmol), CD2C12 (0.75 mL) was vacuum transferred. The sample was then placed under 1 atm H2S to form an orange solution. Similar to reaction 1 above, 27a is observed at -78°C. ^Pl/H} NMR (CD2C12, -78°C): 8 54.52 (d, P-N), 46.06 (d, PPh3); 2 J P P = 30.96 Hz. 2.9.2 Ru(SH)Br(P-N)(PPh3) (27b) Species 27b was prepared in situ by the procedure described for reaction 1 in Section 2.9.1, but using RuBr2(P-N)(PPh3) (10 mg, 0.012 mmol) as precursor. 31P{XH} NMR (de-acetone, -78°C): 8 56.62 (d, P-N), 46.16 (d, PPh3); 2 J P P = 30.48 Hz. *H NMR (de-acetone, -78°C): 8 6.2-8.1 (29H, m, Ph), 8 3.56 (3H, s, N(C#3)), 8 3.17 (3H, s, N(C^3)), 8-1.63 (1H, s,Ru-S#) 2.9.3 Ru(OH)Cl(P-N)(PPh3) (28a) The species was observed 2 h after dissolving RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) and NaOH (~5 equiv) in d6-acetone and heating the solution at 60°C. The NMR spectra of this orange solution were measured at r.t. 31P{1H} NMR (d6-acetone): 8 64.09 (d, P-N), 50.76 (d, PPh3); 2 J P P = 42.98 Hz. J H NMR (de-acetone): 8 6.6-8.9 (29H, m, Ph), 3.04 (3H, s, N(C#3)), 2.69 (3H, s, N(C#3)). 60 References on page 74 Chapter 2 2.9.4 Ru(OH)Br(P-N)(PPh3) (28b) Species 28b was prepared in the same manner as described for 28a, Section 2.9.3, except using RuBr2(P-N)(PPh3) (10 mg, 0. 12 mmol) as precursor. 31P{1H} NMR (de-acetone): 8 65.95 (d, P-N), 51.23 (d, PPh3); 2 J P P = 41.22 Hz. J H NMR (d6-acetone): 5 6.4-8.2 (29H, m, Ph), 3.22 (3H, s, N(C/f3)), 2.72 (3H, s, N(C#3)). 2.9.5 Ru(H)Cl(P-N)(PPh3) (29)2-21 To a solution of RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) and proton sponge (3 mg, 0.014 mmol) in CD2C12> was added 1 atm H 2 . An yellow-orange solution formed instantaneously. This species is stable at r.t. (20°C). "Pf/H} NMR (CD2C12): 8 82.74 (d, P-N), 67.39 (d, PPh3); 2 J P P = 33.20 Hz. lH NMR (CD2C12): 8 6.5-8.1 (29H, m, Ph), 8 3.49 (3H, s, N(C773)), 8 2.99 (3H, s, N(Cff3)), 8-27.2 (IH, br s, Ku-H). The NMR data correspond to those reported.2'21 2.9.6 Ru(SH)2(P-N)(PPh3) (30) The dithiolate species 30 was formed at r.t. when RuX2(P-N)(PPh3) (X = CI, Br) was reacted with excess NaSHxH20 or H2S in the presence of proton sponge (3 equiv) as described for reactions 1 and 2 of Section 2.9.1, respectively. These yellow-brown solutions were unstable at r.t. and decomposed to dark brown solutions after ~10 min. Species 30 was only observed within 10 min of sample preparation at r.t. 3IP{1H} NMR (de-acetone,): 8 84.06 (d, P-N), 59.53 (d, PPh3); 2 JPP = 33.75 Hz. J H NMR (d6-acetone): 8 6.4-8.1 (29H, m, Ph), 3.20 (6H, s, N(Cr73)2), 8 0.80 (2H, s, Ru-(S#)2). The decomposed species were not identified. 61 References on page 74 Chapter 2 2.9.7 Ru(OH)2(P-N)(PPh3) (31) The dihydroxo species 31 was observed when solutions of RuCl2(P-N)(PPh3) (cf. Section 2.9.3) or RuBr2(P-N)(PPh3) (cf. Section 2.9.4) and NaOH (-5 equiv) were allowed to react for 5 h or more at 60°C. During this time, the solutions changed from orange to orange-brown colour. "Pf^H} NMR (de-acetone): 8 79.11 (d, P-N), 73.44 (d, PPh3); 2 J P P = 67.38 Hz. X H NMR (de-acetone): 8 6.4-8.2 (29H, m, Ph), 2.60 (3H, s, N(C#3)), 2.28 (3H, s, N(C/f3)). 2.9.8 Ru(H)2(P-N)(PPh3) (32) The title species 32 was observed 15 min after reacting RuCl2(P-N)(PPh3) or RuBr2(P-N)(PPh3) with NaH (~5 equiv.) in de-acetone at 60°C. The NMR spectra of this orange solution were measured at r.t. 31P{1H} NMR (de-acetone): 8 61.64 (d, P-N), 50.44 (d, PPh3); 2 J P P = 24.71 Hz. *H NMR (de-acetone): 8 6.5-8.1 (29H, m, Ph), 8 2.51 (6H, s, N(C#3)2), 8 -21.16 (2H, d of d, Ru-(7f)2, 2 J H P = 32.70, 29.10 Hz). 2.10 Syntheses of Ruthenium(II) Complexes Containing Coordinated H20, MeOH, or EtOH 2.10.1 7>a#!S-RuCl2(P-N)(PPh3)(OH2) (33a)2 The title complex was prepared by adding a mixture of H 2 0 (2 mL) and acetone (2 mL) to a stirred solution of RuCl2(PPh3)3 (200 mg, 0.209 mmol) and P-N (64 mg, 0.209 mmol) in acetone (5 mL). The orange-pink solution which formed instantaneously was stirred for 3 h during which time a pink solid precipitated. The product was filtered off, washed with acetone (2x5mL), and dried in vacuo for 24 h. Yield: 115 mg, 73%. Microanalysis indicates the presence of 1 moi acetone solvate. Anal. Calcd. 62 References on page 74 Chapter 2 C38H37NOCl2P2Ru-(acetone): C, 60.37; H, 5.31; N, 1.72. Found: C, 60.37; H, 5.46; N, 1.67. 31P{XH} NMR (CsDg): 8 73.52 (d, P-N), 49.30 (d, PPh3); 2 J P P = 38.00 Hz. *H NMR (CeDg): 8 7.0-8.4 (29H, m, Ph), 3.05 (6H, s, N(C#3)2), 2.15 (2H, br s, Ru-0#2), 155 (6H, s, acetone). UV-Vis (CH2C12, with 0.13 M H 20): 498 (shoulder, 270). IR: V 0 - H 3556, 3295, 1605 (weak), vCo 1707 (acetone, strong). Two different types of crystals of 33a were isolated from evaporation of a saturated CeH6 solution of the complex over 24 h. These crystals differ in appearance as well as having different unit cells. The yellow-brown crystals (33a-1.5C6H6) have primitive triclinic cell dimensions, while the pink needle crystals (33a-2C6H6) have primitive monoclinic cell dimensions. The ORTEP plots, selected bond lengths and angles of 33a-1.5CeH6 are presented in Section 5.3, while the full experimental parameters and details of the two structures are given in Appendix VLTJ. 2.10.2 rra«s-RuCl 2(P-N)(P(p-tolyl) 3)(OH 2) (33b)2 The title complex was prepared in the same manner as described for 33a (Section 2.10.1) but using RuCl2(P(>tolyl)3)3 (200 mg, 0.185 mmol). Yield: 122 mg, 77%. Microanalysis indicates the presence of 1 mol acetone solvate. Anal. Calcd. C4iH43NCl2OP2Ru-(acetone): C, 61.61; H, 5.76; N, 1.63. Found: C, 61.97; H, 5.65; N, 1.77. 31P{!H} NMR (CgDg): 8 63.63 (d, P-N), 45.91 (d, PPh3); 2 J P P = 38.12 Hz. *H NMR (CsDe): 8 6.8-8.2 (26H, m, Ph), 3.10 (6H, s, N(C#3)2), 2.00 (3H, s, ^ - ( C ^ C ^ ) , 2.15 (2H, br s, Ru-0#2), 1.55 (6H, s, acetone). UV-Vis (CH2C12): 496 (shoulder, 280). 2.10.3 Tra«s-RuCJ 2(P-N)(PPh 3)(MeOH) (34) A mixture of MeOH (2 mL) and acetone (1 mL) was purged with Ar and cannula transferred to a stirred solution of RuCl2(PPh3)3 (100 mg, 0.104 mmol) and P-N(32mg, 63 References on page 74 Chapter 2 0.104 mmol) in acetone (5 mL) which had been heated to 50°C. The orange solution which formed instantaneously was stirred at 20°C for 24 h. The volume of the solution was then reduced to ~1 mL and hexanes (10 mL) was added to precipitate a pink solid. This was filtered off and washed with MeOH (2x5 mL). Yield: 45 mg, 56 %. Anal. Calcd. C39H39NOCI2P2RU: C, 60.70; H, 5.09; N, 1.82. Found: C, 61.01; H, 5.12; N, 1.76. 31P{1H> NMR (CD2CI2): 6 77.46 (d, P-N), 47.16 (d, PPh3); 2 J P P = 36.66 Hz. *H NMR (CD2C12): 8 6.9-7.9 (29H, m, Ph), 3.33 (3H, d, Ru(0(C#3)H)), 3.16 (6H, s, N(C#3)2), 133 (IH, q, Ru-(0(CH3)#). 2.10.4 Jrans-RuCl2(P-N)(PPh3)(EtOH) (35) Attempts to prepare 35 following the method described for RuCl2(P-N)(PPh3)(MeOH) (Section 2.10.3) were unsucessfiil. Several different solvent combinations including acetone/hexanes, acetone/Et20 and acetone/EtOH failed to precipitate any solid. In a further attempt to prepare 35, P-N (40.5 mg, 0.133 mmol) in EtOH (2 mL) was added to a brown suspension of RuCl2(PPh3)3 (122.8 mg, 0.128 mmol) in neat EtOH (8 mL). The suspension was stirred for 1 week during which time a pink/orange solution containing a small amount of light brown precipitate formed. This brown solid (~ 20 mg) was collected and washed with EtOH (5 mL), but could not be further characterized as it was found to be insoluble in common solvents (acetone, CDC13, C6D6, CD2CI2). Also, the EtOH was removed under vacuum from the combined pink filtrates collected earlier and hexanes (10 mL) was added to the oily residue. The solvent was once again removed and EtOH (2 mL) was added to dissolve the residue. This solution was then stirred for 15 min when a pink precipitate formed. Hexanes (10 mL) was added to precipitate more solid, which was collected by filtration and washed with hexanes (5 mL). Yield: 33 mg, 33 %. Anal. Calcd. 64 References on page 74 Chapter 2 3lT>fW QoH^NOCy^Ru: C, 61.15; H, 5.26; N, 1.78. Found: C, 62.22; H, 5.06; N, 1.89. 31P{lH} NMR (CD2C12): 5 79.79 (d, P-N), 46.90 (d, PPh3); 2 J P P = 36.24 Hz. *H NMR (CD2C12): 8 6.9-7.9 (29H, m, Ph), 3.61 (2H, dofq, Ru(0(C#2CH3)H)), 3.18 (6H, s, N(C#3)2), 1.40 (1H, t, Ru(0(CH2CH3)/7)), 1.16 (3H, t, Ru(0(CH2C#3)H)). 2.11 Syntheses of Ruthenium(II) Complexes with Other Coordinated Gases 2.11.1 Cis-RuCl2(P-N)(PPh3)(r|2-H2) (36)2'21 The five-coordinate complex, RuCl2(P-N)(PPh3) (6a), was prepared in situ by stirring a solution of RuCl2(PPh3)3 (85.1 mg, 0.09 mmol) and P-N (29.2 mg, 0.09 mmol) in acetone (10 mL) at 50°C for 30 min. H 2 gas was then passed through the solution for 2 h during which time the dark green colour changed to orange. The mixture was stirred for another 48 h when a pale yellow precipitate formed. This was quickly collected and stored under Ar. This yellow solid was susceptible to loss of H 2 with re-formation of the green RuCl2(P-N)(PPh3). Yield: 35 mg, 52 %. Anal. Calcd. C 3 gH 3 7NCl 2P 2Ru: C, 61.54; H, 5.03; N, 1.89. Found: C, 61.47; H, 4.89; N, 1.75. ^Pl/H} NMR (CgLY): 8 49.30 (d, P-N), 45.49 (d, PPh3); 2 J P P = 26.83 Hz. *H NMR (CgDe): 8 6.4-8.4 (29H, m, Ph), 3.68 (3H, s, N(CrY3)), 3.17 (3H, s, N(C#3)), -10.90 (2H, br s, Ru(r|2-#2)). Yellow, block crystals of 36 were obtained from a saturated acetone solution of the complex left standing for 2 days. The ORTEP plot, selected bond lengths and angles are presented in Section 6.1, while the full experimental parameters and details are given in Appendix IX. 65 References on page 74 Chapter 2 2.11.2 Reactions with NH 3 2.11.2.1 Reaction of RuCl2(P-N)(PPh3) with NH 3 2.11.2.1.1 Isolation of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) To a solution of RuCl2(P-N)(PPh3) (50 mg, 0.068 mmol) in 5 mL CeHsA atm of NH 3 was introduced, and the dark green solution was stirred for 1 h. Hexanes (5 mL) was added to precipitate a blue-green solid. Yield: 35 mg, 68 %. Anal. Calcd. C38H4iN3Cl2P2Ru: C, 58.99; H, 5.34; N, 5.43. Found: C, 59.14; H, 5.40; N, 5.21. Due to the loss of NH 3 when this solid was dissolved in solution (CDC13) (see Section 6.2), three products were observed in the NMR spectra. [37a, [RuCl(P-N)(PPh3)(NH3)2-Cl], 31P{XH} NMR: 8 57.20 (d, P-N), 53.24 (d, PPh3); 2 J P P = 32.05 Hz. *H NMR: 8 6.2-8.2 (m, Ph), 3.19 (3H, s, N(C#3)), 3.00 (3H, s, N(C#3)), 3.72 (3H, s, Ru-N/f3), 1.70 (3H, s, Ru-Nif3). 38a, /raws-RuCl2(P-N)(PPh3)(NH3), NMR spectra are identical to those recorded in Section 2.11.2.1.2. 39a, cw-RuCl2(P-N)(PPh3)(NH3), 31P{1H} NMR: 8 59.27 (d, P-N), 51.45 (d, PPh3); 2 J P P = 32.29 Hz. *H NMR: 8 6.2-8.2 (m, Ph), 3.61 (3H, s, N(C#3)), 2.94 (3H, s, N(Cr73)), 0.39 (3H, s, Ru-N#3)]. Of note, the integrations of the phenyl protons in the *H NMR spectrum were not assigned because of overlapping signals of 37a, 38a and 39a in this region. Conductivity in acetone under 1 atm NH 3: A M = ~ 0. 2.11.2.1.2 Synthesis of *ra/is-RuCl2(P-N)(PPh3)(NH3) (38a) from a solid state reaction Solid RuCl2(P-N)(PPh3) (20 mg, 0.027 mmol)) was stirred under 1 atm of NH 3 for 3 h. The colour of the starting material changed from green to beige-brown. Yield: 20 mg, 100%. Anal. Calcd. C 3 gH 3 8N 2Cl 2P 2Ru: C, 60.32; H, 5.06; N, 3.70. Found: C, 60.26; H, 5.23; N, 3.71. "Pf/H} NMR (CDC13): 8 53.86 (d, P-N), 50.79 (d, PPh3); 2 J P P = 36.48 Hz. *H NMR (CDC13): 8 6.2-8.2 (m, Ph), 2.72 (6H, s, N(C#3)2), 1.64 (3H, s, Ru-N#3). 66 References on page 74 Chapter 2 2.11.2.1.3 In situ reaction in the presence of excess NH 3 To a solution of RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) dissolved in 0.7 mL CDC13 in a NMR tube was added 1 atm NH 3 when a dark green solution formed. NMR analyses indicate the presence of one product, ^uCl(P-N)(TJPh3)(NH3)2"-Cl]; see NMR data in Section 2.11.2.1.1 for 37a. 2.11.2.2 Reaction of RuBr2(P-N)(PPh3) with NH 3 Reactions analogous to those for RuCl2(P-N)(PPh3) (Section 2.11.2.1) were performed on RuBr2(P-N)(PPh3). 2.11.2.2.1 NMR data for [RuBr(P-N)(PPh3)(NH3)2 -Br] (37b) and cw-RuBr2(P-N)(PPh3)(NH3) (39b) All samples were prepared in CDC13: [RuBr(P-N)(PPh3)(NH3)2-Br] (37b), ^Pf/H} NMR: 8 57.40 (d, P-N), 56.08 (d, PPh3); 2 J P P = 31.81 Hz. *H NMR: 8 6.2-8.2 (m, Ph), 3.34 (3H, s, N(C#3)), 2.78 (3H, s, N(C#3)), 3.64 (3H, s, Ru-N#3), 1.75 (3H, s, Ru-N#3). Cw-RuBr2(P-N)(PPh3)(NH3) (39b), ^Pl/H} NMR: 8 62.86 (d, P-N), 51.85 (d, PPh3); 2 J P P = 31.75 Hz. *H NMR: 8 6.2-8.2 (m, Ph), 3.97 (3H, s, N(C#3)), 2.74 (3H, s, N(C^3)), 0.48 (3H, s, Ru-N^3). 2.11.2.2.2 Synthesis of frans-RuBr2(P-N)(PPh3)(NH3) (38b) The title complex was synthesized with a 100 % yield in a solid state reaction similar to that described for 38a (Section 2.11.2.1.2). Anal. Calcd. C 3 gH 3 gN 2Br 2P 2Ru: C, 53.98; H, 4.53; N, 3.31. Found: C, 53.61; H, 4.46; N, 3.05. NMR (CDC13): 8 55.25 (d, P-N), 50.65 (d, PPh3); 2 J P P = 36.66 Hz. ! H NMR (CDC13): 8 6.2-8.2 (m, Ph), 3.01 (6H, s, N(C#3)2), 1.58 (3H, s, Ru-N#3). 67 References on page 74 Chapter 2 2.11.2.3 In situ preparation of [Ru(P-N)(PPh3)(NH3)3"Cl][PF6] (40a) The title species was observed in situ when [RuCl(P-N)(PPh3)(NH3)2-"Cl] and 1 equiv of NH4PF6 were stirred under 1 atm of NH 3 in d6-acetone. 31P{1H} NMR (d6-acetone): 8 54.94 (d, P-N), 51.47 (d, PPh3); 2 J P P = 32.05 Hz. X H NMR (d6-acetone): 8 6.2-8.2 (29H, m, Ph), 3.18 (3H, s, N(C#3)), 3.13 (3H, s, N(Cr73)), 3.05 (3H, s, Ru-N#3), 1.06 (3H, s, Ru-N/Y3). Removal of excess NH 3 resulted in formation of species 41 (Section 2.11.2.5). Conductivity of 40a after removal of NH4CI in acetone under 1 atm NH 3: AM =139 ohm"1 cm2 mol'1. 2.11.2.4 In situ preparation of [Ru(P-N)(PPh3)(NH3)3] [PF6]2 (40b) The title species was prepared in situ by dissolving RuCl2(P-N)(PPh3) (10 mg, 0.014 mmol) and 2 equiv NH4PF6 (2.2 mg, 0.014 mmol) in de-acetone (~ 1 mL) in the presence of 1 atm NH 3 when the original solution changed from green to yellow. The reaction was allowed to proceed at r.t. for 16 h. The NH4CI was removed by filtration through Celite and the filtrate was subjected to NMR. 31P{JH} NMR (d6-acetone): 8 55.26 (d, P-N), 51.67 (d, PPh3); 2 J P P = 32.05 Hz. lH NMR (d6-acetone): 8 6.2-8.2 (29H, m, Ph),3.21 (3H, s, N(C#3)), 3.14 (3H, s, N(C#3)), 3.08 (3H, s, Ru-N#3), 1.10 (3H, s, Ru-N/73). Conductivity of 40b after removal of NH4CI in acetone under 1 atm NH 3 : A M = 288 ohm"1 cm2 mol"1. 2.11.2.5 [RuCl(P-N)(PPh3)(NH3)2][PF6](41) To a solution of [RuCl(P-N)(PPh3)(NH3)2-Cl] (100 mg, 0.0013 mmol) in acetone (10 mL), a solution of NH4PF6 (22 mg, 0.0014 mmol) in acetone (5 mL) was added, and the pale yellow-green solution was stirred under 1 atm NH 3 for 16 h. A dark yellow solution with a suspension of NH4CI was formed. This mixture was filtered through Celite to remove the 68 References on page 74 Chapter 2 insoluble salts. The dark yellow-brown residue which remained after removal of solvent from the filtrate was redissolved in 3 mL CH2CI2. Addition of E t 2 0 (10 mL) resulted in the formation of a yellow solid, which was collected and washed with E t 2 0 (2x5 mL). Yield: 45 mg, 39 %. Anal. Calcd. CsgH^NjClFgPsRu: C, 51.68; H, 4.68; N, 4.76. Found: C, 53.68; H, 6.41; N, 6.68. Several repeated preparations of 41 failed to give satisfactory elemental analysis data. "P^H} NMR (dg-acetone): 5 58.87 (d, P-N), 51.70 (d, PPh3); 2 JPP = 31.40 Hz! ! H NMR (d6-acetone): 6 6.2-8.2 (29H, m, Ph), 3.53 (3H, s, N(C#3)), 3.02 (3H, s, N(C#3)), 2.65 (3H, s, Ru-N#3), 0.53 (3H, s, Ru-N#3). Conductivity in acetone (with or without the presence of excess NH3): A M = 146 ohm'1 cm2 moi"1. 2.11.2.6 [RuCl(P-N)(PPh3)(NH3)][PF6] (42) The title complex is a dark green solid and can be prepared by removal of NH 3 by drying a sample of rRuCl(P-N)(PPh3)(NH3)2]PF6 (41) (10 mg) in vacuo at 80°C. The complex is 02-sensitive and decomposes in air to a brown solid. Yield: 10 mg, 100 %. Anal. Calcd. C3gH38N2ClF6P3Ru: C, 52.69; H, 4.42; N, 3.23. The inability to obtain pure 41 also led to unsatifactory analysis for 42. Found: C, 53.84; H, 4.92; N, 3.10. "pf^H} NMR (de-acetone): 8 48.64 (d, P-N), 47.85 (d, PPh3); 2 J P P = 36 Hz (broad doublets). J H NMR signals were not assigned due to many overlapping peaks in the spectrum (8 6.0-8.5 (m, Ph), 0.5-3.5 (brm)). 2.11.3 Cis-RuCl2(P-N)(PPh3)(ri1-N2) (43) The title complex was prepared in situ by the "condensation" of ~6 atm N 2 into an NMR tube (equipped with a poly(tetrafluoroethylene) valve) containing a solution of RuCl2(P-N)(PPh3) (10 mg) in CD2C12 (0.7 mL). ("Condensation" refers to the vacuum 69 References on page 74 Chapter 2 transfer of 1 atm N 2 in a 18 mL vessel into a 3 mL NMR tube.) The solution was slowly warmed to r.t. when a colour change from dark green to light green-yellow was apparent. The 31P{*H} NMR spectrum indicate 100% formation of the N 2 adduct. ^P^H} NMR (CD2C12): 8 47.54 (d, P-N), 37.90 (d, PPh3); 2 J P P = 27.02 Hz. J H NMR (CD2C12): 8 6.6-7.9 (29H, m, Ph), 3.63 (3H, s, N(C#3)), 3.04 (3H, s, N(C#3)). The NMR data correspond with those previously reported, where a V N 2 value of 2161 cm"1 was measured.21 2.11.4 Cis-RuCl2(P-N)(PPh3)(N20) (44) The N 20 adduct was prepared in situ using the same method as for the N 2 complex described in Section 2.11.3 but using ~6 atm N 20. When the sample was warmed to r.t., a light green solution formed, but the 31P{1H} NMR spectrum was very noisy with broad peaks at 8 79.93 and 8 47.16. When this sample was cooled to -88°C, three species were observed: the starting five-coordinate complex 6a (18 %); the N 2 adduct 43 (8 %); and the assumed N 20 adduct 43 (74 %). 31P{XH} NMR (-88°C, CD2C12) for 44: 8 49.52 (d, P-N), 40.06 (d, PPh3); 2 J P P = 27.93 Hz. J H NMR (-88°C, CD2C12): 8 6.4-8.1 (m, Ph), 3.60 (3H, s, N(C#3)), 2.85 (3H, s, N(C#3)). 2.12 Synthesis and Reactions of Ruthenium(II) Carbene Complexes The following carbene complexes were prepared employing the method described by Bianchini and co-workers for the corresponding RuCl2(PNP)(PPh3) (PNP = CH3CH2CH2N(CH2CH2PPh2)2) derivatives.24 70 References on page 74 Chapter 2 2.12.1 C«-RuCl 2(P-N)(PPh 3)(=C=CHPh) (45) A solution of PhOCH (0.60 mL, 5.46 mmol) in CH2C12 (3 mL) was added to a solution of RuCl2(P-N)(PPh3) (385.0 mg, 0.52 mmol) in CH2C12 (20 mL). The dark yellow solution which formed was then refluxed at 40°C for 2 h. The solution was cooled to r.t. and stirred for another 16 h at ambient conditions when a dark red solution formed. The volume of the solvent was reduced to 5 mL and hexanes (20 mL) was added to precipitate a dark orange solid that was collected and washed with hexanes (4x5 mL). Yield: 380 mg, 86 %. Anal. Calcd. C46H4iNCl2P2Ru: C, 65.64; H, 4.91; N, 1.66. Found: C, 65.45; H, 4.92; N, 1.55. 31P{lH} NMR (CDC13): 8 37.85 (d, P-N), 36.40 (d, PPh3); 2 J P P = 26.50 Hz. *H NMR (CDC13): 8 6.2-8.2 (34H, m, Ph), 3.60 (3H, s, N(C/f3)), 3.11 (3H, s, N(C/f3)), 2.43 (IH, d of d, CCHPh). Red-orange crystals of 45 grew over 2 days by slow evaporation of CDC13 from an NMR tube sample of the complex. The ORTEP plot, selected bond lengths and angles are shown in Section 6.4.1, while the full experimental parameters and details are given in Appendix X. 2.12.2 Cis-RuCl2(P-N)(P(p-tolyl)3)(=C=CHPh) (46) Complex 46 was prepared in the same manner as described for the PPh3 analogue (Section 2.12.1) but using RuCl2(P-N)(P(p-tolyl)3) (390 mg, 0.50 mmol). The product was a dark orange solid. Yield: 350 mg, 80 %. Anal. Calcd. GjgHnNCy^Ru: C, 66.59; H, 5.36; N, 1.58. Found. C, 66.43; H, 5.29; N, 1.55. n?{lH) NMR (CDC13): 8 35.86 (d, P-N), 32.96 (d, PPh3); 2 JPP = 26.62 Hz. *HNMR (CDC13): 8 6.2-7.8 (31H, m, Ph), 3.54 (3H, s, N(C#3)), 3.08 (3H, s, N(CH3)), 2.40 (1H, d of d, CC#Ph), 2.16 (9H, s,p-(C£U)CH3). 71 References on page 74 Chapter 2 2.12.3 Cis-RuCl2(P-N)(PPh3)(=C=CHPhCH3) (47) The title complex was prepared in the same manner as described for 45 (Section 2.12.1) but using five equiv of 4-ethynyltoluene. The product is a dark yellow solid. Yield: 270 mg. 61 %. Anal. Calcd. C47H44NCI2P2RU: C, 65.89; H, 5.18; N, 1.63. Found: C, 65.75; FL5.02; N, 1.52. "Pf/H} NMR (CDCI3): 5 38.33 (d, P-N), 36.72 (d, PPh3); 2 JPP = 26.10 Hz. X H NMR (CDC13): 8 6.1-8.1 (33H, m, Ph), 3.59 (3H, s, N(C#3)), 3.08 (3H, s, N(C#3)), 2.43 (1H, dd, CC#PhCH3), 2.16 (3H, s, CCHPhC#3). 2.12.4 as-RuCl2(P-N)(PPh3)(SCHCH2Ph) (48) Complex 48 was prepared by bubbling H2S through a solution of RuCl2(P-N)(PPh3)(=C=CHPh) (45) (100 mg, 0.12 mmol) in CD2C12 (15 mL) under reflux (45°C) for 5 h, when the original orange solution became brown. The solution was then concentrated to ~5 mL and hexanes (15 mL) was added to precipitate a brown solid (65 mg) which was collected and washed with hexanes (2x10 mL). Analytically pure 48 could not be isolated even after several reprecipitations from CH2Cl2/hexanes. NMR analysis, however, indicate that 48 is the major species in the brown solid. ^Pl'H} NMR (CDC13): 8 59.61 (d, P-N), 42.36 (d, PPh3); 2 J P P = 28.22 Hz. *H NMR (CDC13): 8 6.1-8.7 (29H, m, Ph), 3.04 (3H, s, N(CrY3)), 2.52 (3H, s, N(Cff3)), 3.18 (1H, t, S=C#, 3 J H H = 15 Hz), 1.30 (2H, d, CH2, 3 J H H = 1 5 H Z ) . 2.12.5 Reaction of Cis-RuCl2(P-N)(PPh3)(=C=CHPh) (45) with H 20 To a solution of 45 (100 mg, 0.12 mmol) in CH2C12 (15 mL), H 2 0 (1 mL) was added. This mixture was refluxed for 5 h during which time the original orange solution became brown. Hexanes (20 mL) was added to precipitate a brown solid which is composed of a 72 References on page 74 Chapter 2 mixture of 49 and RuCl2(P-N)(PPh3)(CO) (50) as indicated by 31P{JH} NMR data. The two species 49 and 50 were not separated for purposes of microanalysis. 31P{1H} NMR (CDC13): for 49, 5 44.57 (br, P-N), 38.28 (br, PPh3); for 50, 8 50.55 (br, P-N), 18.74 (br, PPh3). The 31P{XH} NMR data for 50 agree with those previously reported.2 lH NMR spectra were not assigned because of overlapping signals due to both species (8 6.0-8.5 (m, Ph), 1.2-3.5 (m)). IR: vco 2046 (49), 1990 (50). 49 is thought to be RuCl(P-N)(PPh3)(CH2Ph)(CO) (see Section 6.4.2). 73 References on page 74 Chapter 2 2.13 References 1. Perrin, D. D.; Armarego, W. L. F.; Perrin, D. R. Purification of Laboratory Chemicals; 2nd ed.; Pergamon: Oxford, 1980. 2. Mudalige, D. C. Ph.D. Thesis, The University of British Columbia, 1994. 3. Alder, R. W.; Bowman, P. S.; Steele, W. R. S.; Winterman, D. R. J. Chem. Soc, Chem. Commun. 1968, 723. 4. Dixon, K. R. InMultinuclear NMR; Mason, J., Ed.; Plenum: New York, 1987; Chapter 13. 5. MacFarlane, K. W. Ph.D. Thesis, The University of British Columbia, 1995. 6. (a) Selwood, P. W. Magnetochemistry; 2nd ed.; Interscience Publishers, Inc.: New York, 1956, p. 78. (b) Figgis, B. N.; Lewis, J. InModern Coordination Chemistry; Lewis, J.; Wilkins, R. G. Eds.; Interscience Publishers, Inc.: London, 1960, p. 402. (c) Carlin, R. L. Magnetochemistry; Springer-Verlag: New York, 1986, p. 3. 7. Fritz, H. P.; Gordan, I. R; Schwarzhans, K. E.; Venanzi, L. M. J. Chem. Soc. 1965, 5210. 8. Gilman, H.; Banner, I. J. Am. Chem. Soc. 1940, 62, 344. 9. Rauchfuss, T. B.; Patino, F. T.; Roundhill, D. M. Inorg. Chem. 1975,14, 652. 10. Cairns, S. M.; McEwen, W. E. Heteroatom Chem. 1990,1, 9. 11. Meessen, P. H.; Rettig, S. J.; James, B. R. Unpublished data. 12. Payne, N. C ; Stephan, D. W. Inorg. Chem. 1982, 21, 182. 13. Pine, S. H ; Sanchez, B. L. J. Org. Chem. 1971, 36, 829. 14. (a) Horner, L.; Simons, G. Phosphorus and Sulfur 1983, 75, 165. (b) Dekker, G. P. C. M.; Buijs, A ; Elsevier, C. J.; Vrieze, K.; van Leeuwen, P. W. N. M.; Smeets, W. J. J.; Spek, A. L.; Wang, Y. F.; Stam, C. H. Organometallics 1992, 11, 1937. 74 Chapter 2 15. Hayashi, T.; Konishi, M.; Fukushima, M.; Kanehira, K.; Hioki, T.; Kumada, M. J. Org. Chem. 1983, 48, 2195. 16. Bowman, R. E.; Stroud, H. H. J. Chem. Soc. 1950, 1342. 17. Hallman, P. S.; Stephenson, T. A.; Wilkinson, G. Inorg. Syn. 1970,12, 237. 18. Armit, P. W.; Sime, W. J.; Stephenson, T. A ; Scott. L. J. Organomet. Chem. 1978, 161, 391. 19. (a) Evans, I.P.; Spencer, A ; Wilkinson, G. J. Chem. Soc, Dalton Trans. 1973, 204. (b) Mercer, A.; Trotter, J. J. Chem. Soc, Dalton Trans. 1975, 2480. 20. (a) Stephenson, T. A.; Wilkinson, G. J. Inorg. Nucl. Chem. 1966, 28, 945. (b) Dekleva, T. W.; Thorburn, I. S.; James, B. R. Inorg. Chim. Acta 1985,100, 49. (c) Fogg, D. E. Ph.D. Thesis, The University of British Columbia, 1994. 21. Mudalige, D. C ; Rettig, S. J.; James, B. R.; Cullen, W. R. J. Chem. Soc, Chem. Commun. 1993, 830. 22. Shen, J.-Y.; Slugovc, C ; Wiede, P.; Mereiter, K.; Schmid, R.; Kirchner, K. Inorg. Chim. Acta 1998, 268, 69. 23. Mudalige, D. C ; Ma, E. S.; Rettig, S. J.; James, B. R.; Cullen, W. R. Inorg. Chem. 1997, 36, 5426. 24. Bianchini, C ; Innocenti, P.; Peruzzini, M.; Romerosa, A.; Zanobini, F. Organometallics 1996,15, 272. 75 Chapter 3 Synthesis and Reactivity of Ruthenium Aminophosphine Precursors 3.1 Introduction Ruthenium(II) aminophosphine (PN) complexes of the type RuCl2(PN)(PR3) (R = Ph, p-tolyl) have been prepared in this laboratory by phosphine exchange reactions of PN ligands with the well known precursor complexes RuCl 2(PR3)3 1' 3 A similar route involving phosphine exchange has been successful for the synthesis of Ru(II) tertiary (PR'3), ditertiaryphosphine (P-P) and 2-pyridylmono- or diphosphine (Ppy) complexes of the types RuCl2(PR'3)3,4 RuCl2(P-P)(PPh3),5'6 and RuCl2(Ppy)(PPh3),7 respectively. Synthetic methods via other precursors such as RuCl2(DMSO)4,6'8 [RuCl2(benzene)]29 and [RuCl2(COD)]n,10 that are useful in the preparation of Ru(P-P) complexes, give complex mixtures of products when PN ligands are used.2 In this chapter, both successful and attempted syntheses of Ru(II) complexes containing PN ligands are described. The reactivities of these complexes are also briefly discussed. 3.2 Preparation of RuCl2(P-N)(PR3) (R = Ph (6a), R= /Molyl (7a)) PR3 N M e 2 P ^ \ , - - P R 3 1 PPh2 , - m CI Ril-—CI + fi^V^ Cl—Rii'—CI R 3 P ^ [^J - 2 P R 3 RsP^ P-N Figure 3.1 The preparation of RuCl2(P-N)(PR3) (R = Ph (6a), R = p-tolyl (7a)). The title complexes were prepared by the exchange reaction of two monodentate phosphine ligands in RuCl2(PR3)3 with one equivalent of the P-N ligand as indicated by 76 References on page 107 Chapter 3 Figure 3.1.2'3 Only one P-N ligand is coordinated to the Ru centre regardless of the amounts of P-N added. The reactions of RuCl2(PR3)3 and P-N in CH2C12, C 6 H6 or acetone produce deep green solutions containing RuCl2(P-N)(PR3), and the liberated PR3 species are identified by 31P{1H) NMR spectroscopy (5 -3.98 for PPh3 and 5 -4.5 for P0?-tolyl)3 in CDC13). To obtain products with high purity, as many as four repeated recrystallized steps using CH2Cl2/hexanes were required. The yields of the dark green solids 6a and 7a were consequently low (55 %). Of note, however, use of the aquo complexes fra/w-RuCl2(P-N)(PR3)(OH2) (R = Ph (33a), /?-tolyl (33b)) provided indirect routes to RuCl2(P-N)(PR3) of high purities and yields. Detailed discussion on the properties of 33a and 33b is presented in Chapter 5. The aquo complexes are readily obtained by reactions of RuCl2(PR3)3 with P-N in solvent mixtures of H20/acetone (1:5 volume) with 73 to 85% yields. Heating 33a and 33b in the solid state in vacuo at 80°C leads to complete conversion to 6a and 7a, respectively. X-ray quality crystals of 7a were obtained by Mudalige, previously of this laboratory.2'3 The structure (Figure 3.2) reveals a distorted square pyramidal geometry with the Ru atom 0.42 A above the plane defined by Cl(l), Cl(2), N(l), P(2). The Cl-atoms are trans to one another, the PPh3 ligand is trans to the N arm of the P-N ligand, and the P-atom of the P-N ligand resides at the apical position. This structure is analogous to those of RuCl2(isoPFA)(PPh3) (isoPFA = l-[a,a-dimethylethyl]-2-(diisopropylphosphino)ferrocene),1 RuCl2(PPh3)3,n RuBr2(PPh3)312 and RuCl2(dppb)(PPh3) (dppb = Ph2P(CH2)4PPh2).12 However, in contrast to these other structures, the vacant site trans to the apical P atom in 7a is not occupied by an ortho H-atom of the PPh3 ligand, and this property may contribute significantly to the highly reactive nature of 7a (and presumably 6a); 6a and 7a have similar 77 References on page 107 Chapter 3 characteristics and reactivities (as described in succeeding chapters), and thus 6a is presumed to have the same structure as that of 7a. C 5 C 4 C 2 7 Figure 3.2 The ORTEP plot of RuCl 2(P-N)(P(p-tolyl)3) (7a).2'3 Thermal ellipsoids for atoms shown are drawn at 33 % probabilty. 78 References on page 107 Chapter 3 NMR spectroscopic analyses show that, in solution, 6a and 7a remain monomeric with no phosphine dissociation. For the analogous RuCi2(PR 3) 3 systems (R = Ph and /7-tolyl)13 and RuCl2(P-P)(PR3) (P-P = dppp, dppb, dppn, binap, chiraphos, and bdpp),5'6,1214 the dinuclear complexes (|j.-Cl)2[RuCl(PR3)2j2 and (n-G)2[RuCl(P-P)2]2 are formed, respectively. The "Pf/H} NMR spectra (in CeDe) of 6a [8 83.69 (d, P-N), 5 48.87 (d, PPh3), 2 J P P = 36.54 Hz] and 7a [5 81.46 (d, P-N), 5 47.64 (d, P(/?-tolyl)3), 2 J P P = 37.15 Hz] depict characteristic AX spin pattern resonances. The coupling constants are consistent with cis P-atom coupling.615 In the *H NMR spectra, the equivalent NMe groups of 6a and 7a are indicated by singlets at 6 3.07 and 3.13, respectively. 3.2.1 Decomposition of RuCl2(P-N)(PPh3) (6a) to (u-0)(u-Cl)2[RuCl(P-N)]2 (17) When CH2CI2 or C<5H6 solutions of 6a and 7a are exposed to air, a colour change from green to dark green-blue rapidly occurs. Addition of hexanes led to precipitation of dark green solids that were only sparingly soluble in the common organic solvents (CHC13, CH2CI2, C6H6, MeOH, acetone and DMSO). Dark green crystals of X-ray quality were obtained when a concentrated acetone solution of 6a was slowly evaporated in air. The ORTEP plot for these crystals is shown in Figure 3.3 and reveals the Ru dinuclear complex (|i-0)(|i-Cl)2[RuCl(P-N)]2 (17). Selected bond lengths and angles of 17 are given in Tables 3.1 and 3.2, respectively. Each Ru centre is coordinated in a pseudo-octahedral fashion to one P-N ligand, one terminal CI ligand, two bridging CI ligands and one bridging O ligand. 79 References on page 107 Chapter 3 Figure 3.3 The ORTEP plot of (^-0)(u-Cl)2[RuCl(P-N)]2 (17). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix III. 80 References on page 107 Chapter 3 Table 3.1 Selected bond lengths (A) for (u.-0)(u-Cl)2[RuCl(P-N)]2 (17) with estimated standard deviations in parentheses.3 Bond Length (A) Bond Length (A) Ru(l)-Cl(l) 2.570(2) Ru(2)-Cl(l) 2.3921(15) Ru(l)-Cl(2) 2.396(2) Ru(2)-Cl(2) 2.604(2) Ru(l)-Cl(3) 2.411(2) Ru(2)-Cl(4) 2.390(2) Ru(l)-P(l) 2.224(2) Ru(2)-P(2) 2.230(2) Ru(l)-0(1) 1.921(4) Ru(2)-0(1) 1.926(4) Ru(l)-N(l) 2.193(5) Ru(2)-N(2) 2.187(5) Ru(l)-Ru(2) 2.9173(7) x s i—e. 1 . — gj — "Some of the bond lengths listed here and elsewhere in the thesis are given to the 4 decimal place as provided by the crystallographers; whether such accuracy is justified is open to discussion. Table 3.2 Selected bond angles (°) for (|a-0)(u-Cl)2[RuCl(P-N)]2 (17) with estimated standard deviations in parentheses. Bonds Angle (°) Bonds Angle (°) Bonds Angle (°) Ru(l)-0(1)-Ru(2) 98.6(2) Cl(2)-Ru(l)-N(l) 178.03(15) Cl(l)-Ru(2)-N(2) 177.18(14) Ru(l)-Cl(l)-Ru(2) 71.92(4) Cl(3)-Ru(l)-P(l) 93.74(6) Cl(2)-Ru(2)-Cl(4) 92.68(6) Ru(l)-Cl(2)-Ru(2) 71.25(5) Cl(3)-Ru(l)-0(1) 170.54(12) Cl(2)-Ru(2)-P(2) 177.50(6) Cl(l)-Ru(l)-Cl(2) 85.62(6) Cl(3)-Ru(l)-N(l) 88.20(14) Cl(2)-Ru(l)-0(1) 78.86(12) Cl(l)-Ru(l)-Cl(3) 92.44(5) P(l)-Ru(l)-0(1) 95.46(11) Cl(2)-Ru(2)-N(2) 93.34(14) Cl(l)-Ru(l)-P(l) 173.00(6) P(l)-Ru(l)-N(l) 84.48(14) Cl(4)-Ru(2)-P(2) 88.80(6) Cl(l)-Ru(l)-0(1) 78.51(11) 0(1)-Ru(l)-N(l) 94.9(2) Cl(4)-Ru(2)-0(1) 171.33(12) Cl(l)-Ru(l)-N(l) 92.43(14) Cl(l)-Ru(2)-Cl(2) 84.94(5) Cl(4)-Ru(2)-N(2) 87.99(14) Cl(2)-Ru(l)-Cl(3) 92.11(6) Cl(l)-Ru(2)-Cl(4) 94.31(6) P(2)-Ru(2)-0(1) 99.72(12) Cl(2)-Ru(l)-P(l) 97.44(6) Cl(l)-Ru(2)-P(2) 96.96(6) P(2)-Ru(2)-N(2) 84.70(14) Cl(2)-Ru(l)-0(1) 84.54(13) Cl(l)-Ru(2)-0(1) 83.11(11) 0(1)-Ru(2)-N(2) 94.4(2) 81 References on page 107 Chapter 3 The Ru-Ru distance of 2.9173 A is within the range (2.632 - 3.034 A) generally found for a Ru-Ru single bond,1"'16 and this leads to an electron count of 18 at each formally Ru(III) atom. The presence of a Ru-Ru bond also results in reduced Ru(l)-0-Ru(2) (98.6°), Ru(l)-Cl(l)-Ru(2) (71.92°) and Ru(l)-Cl(2)-Ru(2) (71.25°) bond angles. Complexes containing longer Ru-Ru bond distances are known to have enlarged angles between the metal atoms and the bridging ligands. For example, the Ru-Ru distance of 3.266 A in [{(l-MeIm)3Ru}2(|a-0)(|a-02CMe)2][C104]2 (l-Melm = 1-methylimidazole) is accompanied by the relatively large Ru-O-Ru angle of 122.3°.,7d The Ru(l)-0 and Ru(2)-0 bond distances of 1.921 and 1.926 A, respectively, are somewhat longer than those of other reported Ru(III) [i-0 species (1.801 - 1.891 A) 1 7 but are significantly shorter than those of Ru(IH) u-OH (2.093 A) 1 8 or Ru(UI) u-OH2 (2.02 A for rRu2(ii-OH2)2(^ -S04)2py4][02CCH3]2)19 complexes. While the O-atom is centred equally between the Ru atoms, the bridging Cl-atoms are subjected to the trans influence of the P-atom of the P -N ligand. The Ru(l)-Cl(l) (2.570 A) and Ru(2)-Cl(2) (2.604 A) distances are significantly longer than those of the Ru(l)-Cl(2) (2.396 A) and Ru(2)-Cl(l) (2.392 A) bonds because the former bonds are trans to P(l) and P(2), respectively. This phenomenon is also observed in Ru(JJ)-Ru(n) dimers such as [(dppb)ClRu(u-D20)(u-Ci)2 RuCl(dppb)].16 Here, the Ru-Cltenniiui bond distances (trans to 0(1)) of 2.411 (Ru-Cl(3)) and 2.390 A (Ru-Cl(4)) are comparable to those of the monomelic Ru(III) complex RuCl3(P-N)(PPh3) (15a) (2.3338 - 2.4005 A).2 The Ru-P (2.224 and 2.230 A) and Ru-N (2.193 and 2.187 A) distances in 17, however, are significantly shorter than the corresponding ones in 15a (2.3606 and 2.338 A, respectively), and this is presumably due to the reduced steric effects in 17 as a result of the absence of PPh3 ligands. Comparison 82 References on page 107 Chapter 3 of the augmented bite angles (P-Ru-N) of 17 (84.48 and 84.70°) with that of 15a (79.25°) reinforces this suggestion. The two Ru(UI) d 5, one unpaired electron centres in 17 consitute a diamagnetic system as evidenced by a magnetic susceptibility measurement (%e = 0). The electron-spin coupling may result from the Ru-Ru interaction but partial antiferromagnetism (superexchange mechanism) through the bridging oxo ligand (Figure 3.4) cannot not be ruled out . n b , 2 ° Net antiferromagnetic coupling Orbitals are drawn for a linear Ru-O-Ru bond. The 3 1P{ 1H} and lH NMR spectra of 17 show weak signals compared to those of related Ru(II) complexes. The 3 1P{1H} NMR spectrum shows two doublets (8 38.74 and 35.33,4JPP = 10.44 Hz, in CiAs) and indicates coupling of the P-atoms of the two P-N ligands through four bonds. The X H N M R spectrum (CeDe) reveals four inequivalent NMe groups with singlets at 8 3.31, 2.89, 2.11 and 2.02. Of note, the above NMR data were previously assigned to a speculative [i-Oi complex.2 The UV-Vis spectrum of 17 in DMSO (3.91 x 10"5 M) is shown in Figure 3.5. Strong ligand to metal charge-transfer bands are found at Xi = 348 nm (si = 15300 M 1 cm"1) and X2 = 652 nm (62 = 11200 M 1 cm"1), the positions and magnitudes of the e values of X\ and X2 being 83 References on page 107 Chapter 3 comparable to those of complexes containing bis(p.-carboxylato or p.-phosphato)(u.-oxo) diruthenium moieties.171"0'20 In particular, the low energy band at 652 nm is responsible for the intense blue-green colour of 17. [Although 17 is less soluble in CH2CI2 than in DMSO, the UV-Vis spectrum in CH2C12 showed identical absorbances (ki and X2) as in DMSO.] 1.40 T 1 0.00 1 1 1 1 1 1 1— 200 300 400 500 600 700 800 Wavelength (nm) Figure 3.5 UV-Vis spectrum of (u-0)(p.-Ci)2[RuCl(P-N)]2 (17) (3.91 x 10"5 M) in DMSO at 25°C. The source of the oxo ligand is 02. The possibility of H 2 0 as the origin seems less likely as 17 is formed from the reaction of 6a with 0 2 in a strictly H20-free environment. Furthermore, 17 is not formed in the absence of 02. In an in situ reaction between 6a and 0 2 in CeDe at r.t., 17 and 0=PPh3 were observed by "P^H} NMR spectroscopy. In fact, 6a catalytically converts any excess PPh3 added to 0=PPh3 before any 17 is observed (Figure 84 References on page 107 Chapter 3 3.6). A plausible intermediate is an 0 2 adduct formed prior to oxidation of PPh3 to 0=PPh3. However, the possibility of the oxidation occuring via H2O2 generated within a catalytic Ru(n)/Ru(IV) system requiring trace protons cannot be ruled out; a Pt(0)/Pt(II) catalyzed 02-oxidation of PPh3 via such a mechanism is well substantiated.21 Q 2 + 2PPb3 2 0=PPh3 2 CI PbjP Ru" . N - C I C l ^ l R u ^ ^ ^ R u 1 — CI 6 a 17 Figure 3.6 The catalytic oxidation of PPh3 to 0=PPh3 by 6a in the presence of 0 2. 3.3 Metathesis Reactions It is desirable to prepare bromo and iodo analogues of RuCl2(P-N)(PPh3) in order to study and compare their reactivities. A logical entry into the preparation of these analogues would be the use of the precursor complexes RuBr2(PPh3)3 and Rul2(PPh3)3. Unfortunately, the bromo and iodo precusor complexes could not be obtained in pure form. Two common synthetic routes to RuBr2(PPh3)3 have been utilized:12bl4a-22 RuCl 3 xH 2 0 + xsLiBr + 6 P P h 3 M ^ » RuBrjCPPh^ RuBr 3 xH20 + 6 P P h 3 M ^ » RuBr2(PPh3)3 However, pure product could only be obtained occasionally. For the former reaction, a mixture of the chloro and bromo complexes is often isolated while, for the latter, RuBr 3-xH20 85 References on page 107 Chapter 3 is not a good starting material as it has limited solubility in MeOH. In this thesis work, similar difficulties were encountered when RuBr2(PPh3)3 and RuJ.2(PPh3)3 were prepared using the above methods. Thus, alternatives route to RuBr2(P-N)(PPh3) (6b) and RuI2(P-N)(PPh3) (6c) were required. 3.3.1 Synthesis and Characterization of RuBr2(P-N)(PR3) (6b) and RuI2(P-N)(PR3) (6c) NaX + 2PPh3 x s N a X 2NaCl / \ / RuC^CPPh^ + P - N *^ » RuCl2(P-N)(PPb3) — S » RuX 2(P-N)(PPh3) Hcctouc pectoris 1 6a X = Br , I 6bX = Br 6cX = I Figure 3.7 Synthesis of RuBr2(P-N)(PPh3) (6b) and RuI2(P-N)(PPh3) (6c). Analytically pure 6b and 6c were obtained from the metathesis reactions of RuCl2(P-N)(PPh3) (6a) with NaX (X = Br, I) as shown in Figure 3.7. For good yields, 6a is formed in situ by reaction of 1 with P-N. Addition of NaX is accompanied by precipitation of NaCl; acetone was used because it readily dissolves Nal, while NaBr and NaCl are slightly soluble and insoluble, respectively. Complete precipitation of NaCl drives the reactions to completion, and microanalysis and NMR spectroscopy confirm the absence of 6a. In the solid state, 6b is dark green while 6c is dark red. 31P{1H} NMR spectra (CeD6) illustrating the P A and P x chemical shifts for 6a, 6b and 6c are shown in Figure 3.8. The P A and Px resonances shift downfield with X = CI -> Br -> I. In the *H NMR spectra (CeDe), singlets due to NMe 2 are located at 8 3.07, 3.17 and 3.33 for 6a, 6b and 6c, respectively. The similarities between 8 6 References on page 107 Chapter 3 the NMR spectra suggest strongly that 6b and 6c have the same structure as 6a, square pyramidal about the Ru centre with the halide atoms mutually trans. 8 82.05 ,..N X — ? R i i - X 8 48.89 (a) X = C1 PP 2 J P  = 36.86 Hz 8 84.59 5 49.76 (b) X = Br 2JPP = 36.45 Hz 8 88.46 8 53.95 (c) X = I 2 J P P = 34.83 Hz 90 80 70 60 50 4 0 ppm Figure 3.8 31P{ *H} NMR spectra (81.0 MHz, C 6 D 6 , 20°C) for (a) RuCl2(P-N)(PPh3) (6a), (b) RuBr2(P-N)(PPh3) (6b), and (c) RuI2(P-N)(PPh3) (6c). 87 References on page 107 Chapter 3 Both 6b and 6c are more stable in the solid state than the chloro analogue 6a in that they do not react with the H 2 0 in air. The formation and characterization of /raws-RuCl2(P-N)(PPh3)(OH2) (33a), is described in Chapter 5. In solution, 6b adds H 2 0 (observed in situ by31?!1!!} NMR spectroscopy) in the same way as 6a, and more generally behaves like 6a; in particular the reaction with H2S and the syntheses and X-ray crystal structures of cw-RuX2(P-N)(PPh3)(SH2) (X = CI (18a), Br (18b)) are described in Chapter 4 (Sections 4.2.1 and 4.2.2). In solution, 6c is relatively less stable than 6a and 6b. For example, c/j-RuI2(P-N)(PPh3)(SH2) (18c) is initially formed when H2S is added to a CDC13 solution of 6c; however, the initially dark yellow solution decomposes to a dark brown solution containing unidentifiable species. The formation and decomposition of 18c were monitored by 31P{1H} NMR spectroscopy (Section 4.2.3). 3.3.2 In situ Formation of Ru(OH)X(P-N)(PPh3) (X = CI (28a), Br (28b)) and Ru(OH)2(P-N)(PPh3) (31) Monomelic late transition metal hydroxo complexes are thought to be intermediates in catalytic processes such as Wacker oxidations and the hydration of olefins to alcohols.23 Such complexes, however, are unstable and generally difficult to isolate, presumably due to weak metal-oxygen bonds resulting from a mismatch of hard ligands and soft metal centres.24 The most common method for their preparation is via metathesis reactions. For example, Wilkinson and co-workers have prepared RuCl(OH)(PPh3)2(H20)2 by reaction of RuCl2(PPh3)3 with NaOH or KOH in THF, acetone or f-butanol in the presence of H 2 0. 2 5 In this thesis work, this method was employed in the synthesis of Ru hydroxo complexes. A bright orange solution is formed when excess NaOH is added to an de-acetone solution of 6a. 31P{1H} NMR spectroscopic analysis of this reaction in situ after 2 h reveals 88 References on page 107 Chapter 3 the presence of three products, 28a (major species), 31 (minor product) and 33a (aquo complex) (Figure 3.9(a)). The presence of 33a is presumably due to the reaction of 6a with H 20 from the hygroscopic NaOH. The AX P-spin coupling is retained in 28a and 31 as indicated by two sets of doublets at 5 64.09 (PA) and 50.76 (Px) with 2 J P P = 42.98 Hz and 8 79.11 (PA) and 73.44 (Px) with 2 J P P = 67.38 Hz, respectively, and there is no dissociation of either PPh3 or P-N. After ~ 5 h, the concentration of 31 has increased while that of 28a has diminished, and the conversion of 28a to 31 is complete after ~ 20 h (Figure 3.9(b)). The species 28a and 31 are tentatively identified (see below) as the stepwise substitution products Ru(OH)Cl(P-N)(PPh3) and Ru(OH)2(P-N)(PPh3), respectively (Figure 3.10). Inequivalent NMe singlets for 28a (8 3.04, 2.69) and 31 (8 2.60, 2.28) are also assigned in their *H NMR 31 (b) 20 h 31 33a (a)2h 3 1 3 1 28a 28a 33a i i i I i i i i I i i i 1 i 1 1 I ' | i i ' i | i i i i | i i i i | i i i i | i i i i | i i i i | i i i i | i i i i | i i i i | i i i i 100 90 80 70 p p m 60 50 40 30 Figure 3.9 31P{JH} NMR spectra (121.4 MHz) for the in situ reaction of RuCl2(P-N)(PPh3) (6a) with NaOH in d6-acetone after (a) 2 h and (b) 20 h at 25°C. 89 References on page 107 Chapter 3 spectra. The resonance of a coordinated OH, however, has not been located, although in genera], Ru(U)-OH chemical shifts are found between 8-7.0 and 0.0.25 2 7 In the present system, complicated ! H NMR spectra are obtained because of the presence of H 2 0 and insoluble NaOH. Repeated attempts to isolated these hydroxo complexes were unsuccessful as, during work-up procedures, decomposition occurred giving dark green solutions containing uncharacterizable species. The exact structure of 31 is uncertain from the presently available data; however, the presence of two inequivalent NMe resonances in the *H NMR spectrum suggests, an 'unsymmetrical' five-coordinate complex. In the above reactions H 20 probably play the role of solubilizing the NaOH. Upon addition of - 10 % H 20, the rates at which 28a and 31 are formed increased significantly; in fact, 31 is now completely formed after 5 h. *H NMR spectra show no evidence for the coordination of H 2 0 to either hydroxo species. Figure 3.10 The substitution of CI" ligands by OH" ligands. Verification for the stepwise displacement of CI" ligands by OH" was made by study of the analogous reaction of RuBr2(P-N)(PPh3) (6b) with NaOH. The "Pf/H} and *H NMR spectra for the above reaction indicate initial formation of Ru(OH)Br(P-N)(PPh3) (28b) after ~ 2 h, with complete conversion to 31 after 20 h. The n?{lH} and *H NMR data for 28a, 28b and 31 are shown in Tables 3.3 and 3.4, respectively. Because of the difference in the halide ligands, NMR signals of 28b are shifted slightly downfield from those of 28a and this 6a 28a 31 90 References on page 107 Chapter 3 trend parallels that observed for 6a and 6b. The fact that both reactions involving 6a and 6b with NaOH give identical species after 20 h demonstrates that the coordination sphere of 31 does not contain halide ligands. In situ reactions of 31 with H2S and H 2 were performed, but the resulting species could not be characterized. Addition of H2S (1 atm) to a solution of 31 in the presence of excess NaOH resulted in a dark brown solution, that gave no 31P{1H} NMR signals; this suggests that paramagnetic Ru species are formed. Similar results were observed for the reaction of 31 with H 2 . Table 3.3 31P{*H} NMR data for the in situ reactions of RuX2(P-N)(PPh3) (X = CI, Br) with NaOH in d6-acetone. Reaction Product 8 PA 8Px 2JPP (Hz) RuCl2(P-N)(PPh3) (6a) + NaOH, after 2 h Ru(OH)Cl(P-N)(PPh3) (28a) 64.09 50.76 42.98 RuBr2(P-N)(PPh3) (6b) + NaOH, after 2 h Ru(OH)Br(P-N)(PPh3) (28b) 65.95 51.23 41.22 6a or 6b + NaOH, after 20 h Ru(OH)2(P-N)(PPh3) (31) 79.11 73.44 67.38 Table 3.4 *H NMR data for the in situ reactions of RuX2(P-N)(PPh3) (X = CI, Br) with NaOH in d6-acetone. Reaction Product 5 NMe RuCl2(P-N)(PPh3) (6a) + NaOH, after 2 h Ru(OH)Cl(P-N)(PPh3) (28a) 3.04, 2.69 RuBr2(P-N)(PPh3) (6b) + NaOH, after 2 h Ru(OH)Br(P-N)(PPh3) (28b) 3.22, 2.72 6a or 6b + NaOH, after 20 h Ru(OH)2(P-N)(PPh3) (31) 2.60, 2.28 3.3.3 In Situ Reactions of 6a or 6b with NaSHxH.O The reactions of 6a or 6b with NaSH-xH20 parallel those with NaOH. The species, Ru(SH)Cl(P-N)(PPh3) (27a) or Ru(SH)Br(P-N)(PPh3) (27b), are initially formed when excess 91 References on page 107 Chapter 3 NaSH-xH20 is added to 6a or 6b in d6-acetone at -78°C. At r.t., both reactions give Ru(SH)2(P-N)(PPh3) 30 which, unlike dihydroxo complex 31, is thermally unstable and decomposes within 10 min of its initial formation. NMR evidence for the formations of 27a, 27b, and 30 will be presented in Section 4.7. 3.3.4 In Situ Formation of Ru(H)2(P-N)(PPh3) (32) The metathesis reaction of 6a with NaH in situ gave exclusively Ru(H)2(P-N)(PPh3) (32) as suggested by 31P{1H} and *H NMR data. Heating a suspension of 6a and NaH in d6-acetone at 50°C leads to the formation of a bright orange solution. The reaction is complete after ~ 15 min, and a single product 32 is observed in the 31P{1H} NMR spectrum. Doublets are found at 8 61.64 (PA) and 50.44 (Px) (2Jpp = 24.71 Hz) and indicate that P-N and PPh3 remain coordinated to the Ru centre. The above chemical shifts differ from those of Ru(H)Cl(P-N)(PPh3) (29) which are found at 8 82.74 and 67.39 ( 2JP P = 33.20 Hz).2 The monohydrido species 29 is prepared from the reaction of 6a with PS (proton sponge) under 1 atm H 2 . The *H NMR spectrum of 32 at 25°C shows a singlet at 8 2.51 due to the NMe 2 resonance, and a doublet of doublets at 8-21.16 (Figure 3.11) due to the dihydride is observed. The 2 J H P coupling constants of 29.10 and 32.70 Hz suggest that the two hydride ligands are equivalent and are coupled to P A and Px, although specific assignments of the coupling constants are not obvious. In comparison, the hydride chemical shift of 29 is observed as a broad signal at 8 -27.6 at 25°C, while at -80°C, this is resolved into a pseudo-triplet ( 2JHP = 28 Hz).2 , 3 Typical c/'s-hydride-phosphine coupling constants in Ru(U) complexes range from 24 to 30 Hz.2 5'2 8 The proposed structure for 32 is square pyramidal containing mutually trans H-ligands (Figure 3.11). 92 References on page 107 Chapter 3 .N H — R i l - H Ph3Pr 32 ^ ^ ^ ^ ^ 1 [ 11111111111111111111 111111111111111111 11 11111111111111111111 1111111111111111111111 ~" ' - 20 .8 - 2 1 . 0 - 2 1 . 2 - 2 1 . 4 - 2 1 . 6 -20 .4 - 2 0 . 6 -21 .8 PPM - 2 2 . 0 Figure 3.11 High field *H NMR spectrum (300 MHz) for the in situ reaction of 6a with NaH in de-acetone at 25°C. Proposed structure of the product 32 is shown in the inset. As with the reactions of 6a with NaOH and NaSH, it is reasonable to assume that the mono-hydride species 29 is an intermediate in the formation of 32. However, attempts to observe 29 were unsuccessful as 32 is formed immediately upon addition of NaH to 6a. Of interest, when the relatively less reactive CaH2 was used, 29 was observed to form slowly (over 2 weeks), and indeed no 32 was detected. 3.4 Synthesis of RuCl2(BPN)(PR3) (R = Ph (13),/Molyl (14)) BPN contains one more dimethylamine group than P-N and is a potential tridentate ligand. Platelet crystals of BPN were obtained from saturated EtOH solutions of the compound. As expected, the ORTEP diagram (Figure 3.12) reveals trigonal pyramidal geometry about the P-atom. The average P-C bond length (1.84 A) of BPN is comparable to that of PPh3 (1.83 A), while the bond angles for C(l)-P(l)-C(7) (103.5°), C(7)-P(l)-C(13) 93 References on page 107 Chapter 3 (101.9°) and C(l)-P(l)-C(13) (97.9°) are slightly deviant from the average C-P-C bond angle of 103° of PPh3, the difference being presumably because of the repulsion of the NMe 2 groups.29 The dihedral angles for the P(l)-C(l)-C(2)-N(l) and P(l)-C(7)-C(8)-N(2) planes are -1.2(7) and 3.7(8)°, respectively, indicating that the two amine groups and the lone electron pair of the P-atom point essentially in the same direction. Figure 3.12 The ORTEP plot of BPN. Thermal ellipsoids for non-hydrogen atoms are drawn at 33 %. Full experimental parameters and details are given in Appendix I. 94 References on page 107 Chapter 3 When BPN is reacted with RuCl2(PPh3)3 or RuCl2(P(/?-tolyl)3)3 i n CH2C12, dark orange solids can be isolated from the reaction mixtures. Microanalysis and NMR spectroscopic measurements are consistent with the formulations RuCl2(BPN)(PPh3) (13) and RuCl2(BPN)(P(/?-tolyl)3) (14). The ^P^H} NMR resonances are given in Table 3.5, and the 2 JPP coupling constants are consistent with the presence of cis P-atoms.6'15 Two possible structures for six-coordinate 13 or 14 are shown in Figure 3.13. The presence of four inequivalent NMe groups observed in the *H NMR spectra (Table 3.6) strongly indicates an unsymmetrical structure such as Figure 3.13(a) for 13 and 14. The possibility of ci-R3P: Ru Me Me -Me ^Me Me2N-R3P: CI (a) CI Ru NMe 2 CI (b) R = Ph,/>-toM Figure 3.13 Possible structures of RuCl2(BPN)(PR3). Table 3.5 31P{lK) NMR spectroscopic data for RuCl2(BPN)(PR3) in CDC13. 8 PA 6Px 2 J P P ( H Z ) R = Ph(13) 56.00 33.67 32.05 R = p-tolyl(14) 56.05 31.26 31.44 Table 3.6 J H NMR chemical shifts for RuCl2(BPN)(PR3) in CDC13; assignments of the phenyl region have been omitted. 8 NMe 5p-(C6tU)CH3 R = Ph (13) R = p-tolyl(14) 3.63 3.15 2.60 2.20 3.64 3.10 2.57 2.20 2.20 95 References on page 107 Chapter 3 five-coordinate species (with a dangling -NMe.) cannot be ruled out entirely, but the complexes are unreactive in d6-acetone solution when subjected to 1 atm of H 2 , CO, H 2 0 or H2S at r. t, implying six-coordinate geometry. Decomposition to paramagnetic species and phosphine oxides was observed when 13 and 14 were exposed to air for 2 days. 3.5 Synthesis of Mer-RuCl3(BPN) (16) Reaction of BPN with RuCl3(PPh3)2(DMA)-(DMA) in CH2C12 gave species 16, and platelet crystals containing one CHC13 per molecule of complex were obtained from saturated CHC13 solutions of the complex. The ORTEP plot is shown in Figure 3.14, with selected bond lengths and angles given in Tables 3.7 and 3.8, respectively. A pseudo octahedral geometry around the Ru centre with mer Cl-atoms is evident, analogous to that seen in the previously crystallographically characterized RuCl3(P-N)(PPh3) (15a) and RuCl3(AMPHOS)(PPh3) complexes.2 Two Cl-atoms are weakly hydrogen-bonded (Cl(2)-H(26) 2.65 A and Cl(3)-H(26) 2.86 A) to the H-atom of the solvated CHC13 molecule and, as a result, the Ru-Cl(2) (2.359(2) A) and Ru-Cl(3) (2.482(2) A) bonds are elongated relative to Ru-Cl(l) (2.316(2) A). The further lengthening of the Ru-Cl(3) bond results from the strong trans influence of the P-atom of the BPN ligand. The Ru(l)-P(l) (2.199(2) A), Ru(l)-N(l) (2.207(5) A) and Ru(l)-N(2) (2.209(5) A) bond lengths are considerably shorter than the Ru-P (average 2.37 A) and Ru-N (average 2.35 A) bonds in 15a and RuCl3(AMPHOS)(PPh3) probably because BPN is bonded rigidly in a meridional geometry. Furthermore, the N(l)-Ru-N(2) angle is only 160.0(2)° because of this strain. 96 References on page 107 Chapter 3 Figure 3.14 The ORTEP plot of/wer-RuCl3(BPN)-CHCl3 (16). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix II. 97 References on page 107 Chapter 3 Table 3.7 Selected bond lengths (A) for /weA*-RuCl3(BPN) (16) with estimated standard deviation in parentheses. Bond Length (A) Bond Length (A) Ru(l)-Cl(l) 2.316(2) Ru(l)-P(l) 2.199(2) Ru(l)-Cl(2) 2.359(2) Ru(l)-N(l) 2.207(5) Ru(l)-Cl(3) 2.482(2) Ru(l)-N(2) 2.209(5) Cl(2)-H(26) 2.65 Cl(3)-H(26) 2.86 Table 3.8 Selected bond angles (°) for /we/--RuCl3(BPN) (16) with estimated standard deviation in parentheses. Bonds Angles (°) Bond Angles (°) Cl(l)-Ru(l)-Cl(2) 177.65(6) Cl(2)-Ru(l)-N(2) 83.0(1) Cl(l)-Ru(l)-Cl(3) 87.81(7) Cl(3)-Ru(l)-P(l) 179.88(6) Cl(2)-Ru(l)-Cl(3) 90.03(6) Cl(3)-Ru(l)-N(l) 95.2(2) Cl(l)-Ru(l)-P(l) 92.12(6) Cl(3)-Ru(l)-N(2) 98.4(1) Cl(l)-Ru(l)-N(l) 98.6(1) P(l)-Ru(l)-N(l) 84.7(1) Cl(l)-Ru(l)-N(2) 96.5(1) P(l)-Ru(l)-N(2) 81.7(1) Cl(2)-Ru(l)-P(l) 90.05(5) N(l)-Ru(l)-N(2) 160.0(2) Cl(2)-Ru(l)-N(l) 82.5(1) The u,eff value of 1.5 BM is comparable with the spin only value of 1.73 BM for a low spin, Ru(III) d5 structure. 98 References on page 107 Chapter 3 3.6 The Reactions of TPN with Ru(II) and ( I I I ) Figure 3.15 ORTEP plot of TPN, whose structure was determined by other members of this group.30 Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability. TPN contains three dimethylamine groups and can potentially function as a tetradentate ligand. Similar to the structure of BPN (Figure 3.12), that of TPN (Figure 3.15) shows that the P-atom and the amine groups point in the same direction as indicated by the small dihedral angles of -2.4(2), -10.9(2) and 4.4(2)° for the P(l)-C(l)-C(2)-N(l), P(l)-C(9)-C(10)-N(2) and P(l)-C(17)-C(18)-N(3) planes, respectively. When TPN was added to solutions of RuCl2(PPh3)3 or RuCl3(PPh3)2(pMA)-(D]vIA), no reactions were observed. This was surprising because TPN does coordinate to Pt(JJ) and Pd(U) forming 99 References on page 107 Chapter 3 four-coordinate, square planar complexes.31 Presumably, the coordination of TPN to form six-coordinate Ru(U) species is disfavoured due to mutual replusion of the sterically demanding PPh3 and TPN ligands. 3.7 Characterization and Reactivity of RuCl2(PAN)(PR3) (R = Ph (9),/»-tolyl2 (10)) Dark green solids, isolated from the reactions of RuCl2(PPh3)3 or RuCl2(P(p-tolyl)3)3 with the bulky and rigid PAN ligand (Sections 2.6.8 and 2.6.9), analyze for the species 9 and 10. These complexes are assumed to have square pyramidal geometries based on their NMR data which are comparable to those of 6a and 7a, the P-N analogues (Section 3.2). The "Pf/H} NMR spectra of 9 (5 97.10 and 41.39, 2 J P P = 32.05 Hz in CDC13) and 10 (8 97.71 and 39.57, 2 J P P = 33.39 Hz in C 6D 6) consist of AX cis P-spin coupling patterns, while the *H NMR spectra show inequivalent NMe groups with singlets at 8 3.68 and 2.96 for 9 and 8 3.50 and 2.90 for 10. The NMR data do not distinguish between trans- or cis-Cl-atoms (Figure 3.16), but the former would require the presence of a rigid Ru(PAN) chelate ring. (a) (b) R = Ph, ^ -tolyl Figure 3.16 Possible structures for RuCl2(PAN)(PR3). 100 References on page 107 Chapter 3 Mudalige found that 10 did not react with small molecules such as H 2 , H2S, S0 2 or CH3OH under conditions identical to those used for the reactions with RuCl2(P-N)(PR3).2 In this present thesis work, reactions of 9 and 10 with H 2 or H2S were re-investigated but, even with the H 2 and H2S pressures increased from 1 to 3 atm and the mixtures heated to 80°C in C6H6, no reactions were observed. The inability of RuCl2(PAN)(PR3) to coordinate to small molecules is attributed to the steric bulk of the PAN ligand hindering access to the Ru centre. 3.8 Attempted Synthesis and Reactivity of RuCl2(AMPHOS)(PPh3) (11) The isolation of analytically pure 11 using the preparative method for RuCl2(P-N)(PR3) and RuCl2(PAN)(PR3) was not successful. Although >99 % product formation is observed by NMR when RuCl2(PPh3)3 and AMPHOS is reacted in situ in CeDe, mixtures containing 11, RuCl2(PPh3)3, OPPh3 and PPh3 are often isolated (Section 2.6.10). Mudalige also found such difficulties but was able to synthesis 11 employing the indirect method shown in Figure 3.17.2 RuCl3(AMPHOS)(PPh3), initially prepared from the reaction of RuCl3(PPh3)2(DMA)-(DMA) with AMPHOS, is reduced to "Ru(H)Cl(AMPHOS)(PPh3)" by H 2 in the presence of 3 equiv. of PS. Chloride abstraction from CHCI3 by the hydrido complex resulted in the production of 11. However, complications also arise because of the extreme 02-sensitivity of "Ru(H)Cl(AMPHOS)(PPh3)" and contamination by phosphine oxides. As a result, when this procedure was followed, 11 was isolated in low yield and was not pure. The structure of 11 is presumed to be square pyramidal with trans Cl-atoms as in the P-N analogue. The ^P^H} NMR chemicals shifts of 11 appear at 5 84.56 and 40.32 ( 2JP P = 37.03 Hz), while the diastereotopic NMe2 groups in AMPHOS result in the observation of two singlets at 8 2.86 and 2.33 in the *H NMR spectrum. 101 References on page 107 Chapter 3 RjuCl3(PPh3)2(DMA) (DMA) ( R ) - A M P H O S ^ N M e 2 CI—Ru^—CI CHCL Ph CH2C12 11 CI Ph ci -Cl PS (3 equiv.) 1 atmH2 C 6 H 6 'Ru(H)Cl(AMPH0S)(PPh3)' Figure 3.17 Synthesis of RuCl2(AMPHOS)(PPh3) (11). *The actual structure of Ru(H)Cl(AMPHOS)(PPh3) is in question as the dimeric formulation (H-Cl)2[Ru(H)(AMPHOS)(PPh3)]2 has also been proposed.2 The reaction of H 2 (1 atm) with an impure sample of 11 (~ 20 mg) was carried out at r. t. in C7H-8 (~ 1 mL), when red-brown crystals were isolated from the mixture after 24 h. The 31P{1H} NMR spectrum of these crystals in C 7 D 8 at 20°C shows two broad resonances at 8 71.4 and 46.4, identical to those of the previously known [(T>Ph3)2(Ti2-H2)Ru(|i-H)(^-Cl)2Ru(H)(PPh3)2].la-13c-32 A broad *H resonance at 8 -12.9 is due to unresolved signals from the u-H, r| 2-H 2 and the terminal H. The formation of the dimer is presumably due to the presence of PPh3, while AMPHOS is thought to act as a base and form AMPHOSHC1 (Figure 3.18). o d d u latmH 2 Ph^p,,,^cL ^ P P h 3 2RuCl2(AMPHOS)(PPh3) + 2PPh3 . 2 A M m o s m » H Figure 3.18 Synthesis of [(PPh3)2(ri2-H2)Ru(n-H)(^-Cl)2Ru(H)(PPh3)2]. 102 References on page 107 Chapter 3 For preparations of RuCl2(P-N)(PR3)(L) (L = small molecule, see Sections 2.8, 2.10 and 2.11) generally, L is added to a solution of RuCl2(P-N)(PR3) which is initially formed in situ from the reaction of RuCl2(PR3)3 with P-N. It was thought that RuCl2(AMPHOS)(PPh3)(L) might also be synthesized without the isolation of 11. Thus, to a solution of 11, formed in situ from RuCl2(PPh3)3 (0.02 mmol) and AMPHOS (0.02 mmol) in CDC13 (~ 1 mL) in a NMR tube, was added 1 atm H 2 ; a dark brown solution formed immediately and dark purple crystals precipitated overnight. The 31P{1H} (5 59.2, br) and *H NMR spectra (5 -17.5, q, 2JHP = 26 Hz) of these crystals in CDC13 show that the compound is Ru(H)Cl(PPh3)3.28 The observations clearly indicate that coordination of the amine group of AMPHOS to Ru(II) is disfavoured, AMPHOS preferentially reacting with H 2 in the presence of RuCl2(PPh3)3 to form AMPHOSHC1 (Figure 3.19). The inability to isolate pure 11 precluded studies of its reactivity with small molecules. RuCl2(PPh3)3 + AMPHOS »• RuCl2(AMPHOS)(PPh3) + 2PPh 3 1 atmH2 - AMPHOS.HC1 CI Figure 3.19 Synthesis of Ru(H)Cl(PPh3)3 using AMPHOS as the base. 103 References on page 107 Chapter 3 3.9 Attempted Preparations of RuCI2(ALAPHOS)2 (12) When one or two equiv of ALAPHOS was added to a solution of c«-RuCl2(DMSO)4 or RuCl2(PPh3)3 in CH2CI2, a bright pink solid was isolated after precipitation with hexanes (Section 2.6.11). The 31P{1H} NMR spectrum of this product indicated the presence of several species with the major one characterized by a 31P{1H} resonance at 8 55.60 (s) and tentatively identified as 12. The structure (Figure 3.20) is thought to be analogous to that of RuCl2[K2(P,AO-PM>CH2CH2NMe2]2, which has been crystallographically characterized and gives a singlet at 8 56.5 in the 31P{1H} NMR spectrum;33 furthermore, this complex is also pink and was isolated from the reaction of c/s-RuCl2(DMSO)4 or RuCl2(PPh3)3 with 2 equiv of Ph 2PCH 2CH 2NMe 2. 3 3 3 4 The *H NMR spectrum of the pink solid containing 12 and other contaminants is complicated because of overlapping resonances of coordinated chiral ALAPHOS, and ] H assignments were not made. Because 12 could not be obtained pure, further experiments to probe its reactivity were not carried out. "P-, ci H Mi P \ — „ _ \ . RVL p N / \ / \ T J r l y Mf&N PPlB , M«N PPh2 N (S)-ALAPHOS CI Figure 3.20 Structure of RuCl2(ALAPHOS)2 (12) (proposed) and RuCl2[K2(P,7V)-Ph2PCH2CH2NMe2]2. 3.10 MisceUaneous: Reactivity of Jrans-RuCl2(PO)2 (5) with H 2S Complex 5 was prepared by the reaction of RuCl2(PPh3)3 with 1 or 2 equiv of PO (o-diphenylphosphineanisole) in acetone (Section 2.5).35 The 31P{1H} NMR spectrum of 5 in CDC13 consists of a singlet at 8 64.20 due to equivalent P-atoms, and the J H NMR spectrum 104 References on page 107 Chapter 3 shows a singlet at 8 4.57 due to equivalent OMe groups. When 1 atm H2S was added to a CDCI3 solution of 5, no reaction was observed even after 2 weeks at 60°C. However, when excess PPh3 was present, 5 reacted slowly with H2S at 60 to 100°C, and the "Pl/H} NMR spectrum of the in situ product mixture showed new resonances corresponding to two products, I and n. AX P-spin patterns were observed: for I, 8 57.38, 45.34 (d, 2JPP = 33.81 Hz), and for IL 8 67.94, 56.79 (d, 2 J P P = 76.60 Hz). In the *H NMR spectrum, new signals at 8 4.69 (s, 3H, OMe) and 8 1.13 (br, 2H, SH2) were seen. Unfortunately, the above reaction did not go to completion (^Pl/H} NMR data suggest -10% conversion), and species I and II could not be isolated. The tentative structures for I and II are shown in Figure 3.21. Figure 3.21 Possible reactions of RuCl2(PO)2 (5) with H2S. 3.11 Summary The very reactive RuCl2(P-N)(PR3) (R = Ph (6a), /?-tolyl (7a)) complexes have been prepared and characterized. The coordination of H2S, H 20, H 2 , N 2 , N 2 0 and other small molecules to 6a and 7a will be discussed in Chapters 4, 5 and 6. In solution, these complexes are 02-sensitive and decompose to give the Ru(III) diamagnetic dinuclear (H-0)(|i-Cl)2[RuCl(P-N)]2 (17). The metathesis reactions of 6a with NaX (X = Br, I, OH, SH 105 References on page 107 Chapter 3 and H) result in the formation (isolated or observed in situ) of RuX2(P-N)(PPh3) species. Other Ru(II) aminophosphine complexes, such as RuCl2(BPN)(PR3) and RuCl2(PAN)(PR3), have also been isolated but they are unreactive toward the small molecules. The ability of aminophosphine ligands to coordinate to Ru(II) is dependent upon their steric bulk and electronic nature. For instance, the sterically hindered TPN does not react with RuCl2(PPh3)3, while the reaction of the basic AMPHOS ligand with H 2 and RuCl2(PPh3)3 results in the formation of Ru(H)Cl(PPh3)3 and AMPHOSHC1. 106 References on page 107 Chapter 3 3.12 References 1. (a) Hampton, C. R. S. M.; Ph.D. Thesis, The University of British Columbia, 1989. (b) Hampton, C. R. S. M.; Butler, I. R; Cullen, W. R; James, B. R; Charland, J.-P.; Simpson, J. Inorg. Chem. 1992, 31, 5509. 2. Mudalige, D. C. Ph.D. Thesis, The University of British Columbia, 1994. 3. Mudalige, D. C ; Rettig, S. J.; James, B. R; Cullen, W. R. J. Chem. Soc, Chem. Commun. 1993, 830. 4. Armit, P. W.; Boyd, A. S. F.; Stephenson, T. A. J. Chem. Soc, Dalton Trans. 1975, 1663. 5. Jung, C. W.; Garrou, P. E.; Hoffman, P. R; Caulton, K. G. Inorg. Chem. 1984, 23, 726. 6. (a) Joshi, A. M. Ph.D. Thesis, The University of British Columbia, 1990. (b) Joshi, A. M.; Thorburn, I. S.; Rettig, S. J.; James, B. R. Inorg. Chim. Acta 1992, 198-200, 283. 7. Jones, N. D.; MacFarlane, K. S.; Schutte, R. P.; Smith, M. B.; Rettig, S. J.; James, B. R. Inorg. Chem. 1999, 38, 3956. 8. (a) Evans, I. P.; Spencer, A.; Wilkinson, G. J. Chem. Soc, Dalton Trans. 1973, 204. (b) Carmichael, D.; Floch, P. L.; Ricard, L.; Mathey, F. Inorg. Chim. Acta 1992,198, 437. 9. (a) Mashima, K.; Kusano, K.; Ohta, T.; Noyori, R.; Takaya, H. J. Chem. Soc, Chem. Commun. 1989, 1208. (b) Bennett, M. A.; Ennett, J. P. Inorg. Chim. Acta 1992,198, 583. (c) Fogg, D. E.; James, B. R; J. Organomet. Chem., 1993, 462, C21. 10. (a) Bennett, M. A.; Wilkinson, G. Chem. Ind. (London) 1959, 1516. (b) Ohta, T.; Noyori, R; Takaya, H. Inorg. Chem. 1988, 27, 566. (c) Kawano, H.; Ikariya, T.; Ishi, Y.; Saburi, M.; Yoshikawa, S.; Uchida, Y.; Kumobayashi, H. J. Chem. Soc, Perkin Trans. 1 1989, 1571. 11. LaPlaca, S. J.; Ibers, J. A. Inorg. Chem. 1965, 4, 778. 107 Chapter 3 12. (a) MacFarlane, K. S. Ph.D. Thesis, The University of British Columbia, 1995. (b) MacFarlane, K. S.; Joshi, A. M.; Rettig, S. J.; James, B. R. Inorg. Chem. 1996, 35, 7304. 13. (a) James, B. R.; Thompson, L. K.; Wang, D. K. W. Inorg. Chim. Acta 1978, 29, 1231. (b) Jardine, F. H. Prog. Inorg. Chem. 1984, 31, 265. (c) Dekleva, T. W.; Thorbum, I. S.; James, B. R. Inorg. Chim. Acta 1985,100, 49. 14. (a) Bressan, M.; Rigo, P. Inorg. Chem. 1975,14, 2286. (b) James, B. R.; Wang, D. K. W. Inorg. Chim. Acta 1976,19, L17. (c) Wang, D. K. W. Ph.D. Thesis, The University of British Columbia, 1978. (d) Thorburn, I. S. Ph.D. Thesis, The University of British Columbia, 1985. (e) James, B. R.; Pacheco, A.; Rettig, S. J.; Thorburn, I. S.; Ball, R. G.; Ibers, J. A. Moi. Catal. 1987, 41, 147. 15. (a) Pregosin, P. S.; Kunz, R. W. NMR: Basic Princ. Prog. 1979,16, 28. (b) Krassowski, D. W.; Nelson, J. H.; Brower, K. R.; Hauenstein, D.; Jacobson, R. A. Inorg. Chem. 1988, 27, 4294. 16. MacFarlane, K. S.; Thorburn, I. S.; Cyr, P. W.; Chau, D. E. K.-Y.; Rettig, S. J.; James, B. R. Inorg. Chim. Acta 1998, 270, 130. 17. (a) Smith, P. M.; Fealey, T.; Earley, J. E.; Silverton, J. V. Inorg. Chem. 1971,10, 1943. (b) Llobet, A.; Curry, M. E.; Evans, H. T.; Meyer, T. J. Inorg. Chem. 1988, 28, 3131. (c) Saski, Y.; Suzuki, M.; Nagasawa, A.; Tokiwa, A.; Ebihara, M.; Yamaguchi, T.; Kabuto, C ; Ochi, T.; Ito, T. Inorg. Chem. 1991, 30, 4903. (d) Sudha, C ; Mandal, S. K.; Chakravarty, A. R. Inorg. Chem. 1993, 32, 3801. 18. Orpen, A. G ; Brammer, L.; Allen, F. H.; Kennard, O.; Watson, D. G.; Raylor, R. J. Chem. Soc, Dalton Trans. 1989, SI. 19. Zhilyaev, A. N.; Kuz'menko, I. V.; Fomina, T. A.; Katser, S. B.; Baranovskii, I. B. Russ. J. Inorg. Chem. (Engl. Transl), 1993, 38, 847. 20. Weaver, T. R.; Meyer, T. J.; Adeyemi, S. A ; Brown, G. M.; Eckberg, R. P.; Hatfield, W. E.; Johnson, E. C ; Murray, R. W.; Untereker, D. Am. Chem. Soc. 1975, 97, 3039. 21. Sen, A.; Halpern, J. J. Am. Chem. Soc 1977, 99, 8337. 22. Dekleva, T. W. Ph.D. Thesis, The University of British Columbia, 1983. 108 Chapter 3 23. Bryndza, H. E.; Tarn, W. Chem. Rev. 1988, 88, 1163, and references therein. 24. (a) Pearson, R. G. J. Am. Chem. Soc. 1963, 85, 3533. (b) Pearson, R. G. J. Chem. Educ. 1968, 45, 643. (c) Pearson, R. G. Inorg. Chem. 1988, 27, 734. 25. Chaudret, B. N.; Cole-Hamilton, D. J.; Nohr, R. S.; Wilkinson, G. J. Chem. Soc, Dalton Trans. 1977, 1546. 26. Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tarn, W.; Bercaw, J. E. J. Am. Chem. Soc 1987,109, 1444. 27. Kaplan, A. W.; Bergman, R. G. Organometallics 1998, 17, 5072. 28. Hallman, P. S.; McGarvey, B. R; Wilkinson, G. J. Chem. Soc (A) 1968, 3143. 29. (a) Daly, J. J. J. Chem. Soc. 1964, 3799. (b) Dunne, B. J.; Orpen, A. G. Acta Cryst. C 1991, 47, 345. 30. Meessen, P. H.; Rettig, S. J.; James, B. R. unpublished data. 31. Fritz, H. P.; Gordan, I. R; Schwarzhans, K. E.; Venanzi, L. M. J. Chem. Soc 1965, 5210. 32. (a) Hampton, C ; Dekleva, T. W.; James, B. R; Cullen, W. R. Inorg. Chim. Acta 1988, 145, 165. (b) MacFarlane, K. S.; Joshi, A. M.; Rettig, S. J.; James, B. R. J. Chem. Soc, Chem. Commun. 1997, 1363. 33. Guo, Z.; Habtemariam, A.; Sadler, P. J ; James, B. R. Inorg. Chim. Acta 1998, 273, 1. 34. Shen, J.-Y.; Slugovc, C ; Wiede, P.; Mereiter, K.; Schmid, R; Kirchner, K. Inorg. Chim. Acta 1998, 268, 69. 35. Rauchfuss, T. B.; Patino, F. T.; Roundhill, D. M. Inorg. Chem. 1975,14, 652. 109 Chapter 4 Transition Metal H2S and Thiol Complexes: Synthesis and Characterization of as-RuX2(P-N)(PR3)(L); L = H2S, Thiols 4.1 Introduction A recent review on the coordination chemistry and catalytic conversions of H2S indicates that such chemistry has received little attention in the literature.1 The synthesis and isolation of H2S and thiol transition metal complexes are rare because they are often unstable even in an 02-free atmosphere and at low temperatures.2 The instability of these complexes is often due to the acidic nature of H2S and thiols; upon coordination, the acidic protons are often lost and metal thiolate or sulfide-bridged complexes are formed (see Chapter 1). In this Chapter, a brief summary of the H2S and thiol metal complexes synthesized or observed prior to this work is described; and then the preparation and characterization of czs-RuX2(P-N)(PPh3)(L) (X = Br, CI; L = H2S, MeSH, EtSH) are discussed. 4.1.1 Transition Metal H 2S Complexes The first reported crystal structure of a transition metal H2S complex is that of [Ru(SH2)(PPh3)('S4')]-THF ('S4'2" = l,2-bis[(2-mercaptophenyl)thio]ethane(2-)), obtained by Sellmann and co-workers.3 This complex was isolated by the reaction of polymeric [Ru(PPh3)('S4')]x with liquid H2S at -70°C (Figure 4.1(a)). Careful recrystallization from THF/pentane gave yellow crystals that were stable at 25°C under 02-free conditions but slowly lost H2S when stored in vacuo. In the unit cell, enantiomeric units of 110 References on page 169 Chapter 4 [Ru(SH2)(PPh3)CS4')] are associated via two S-H-S bridges and are bound to THF molecules via S-H—O bridges (see Figure 4.1(b)). The coordinated H2S ligand is stabilized by strong hydrogen bonds with H—S and H—O distances of 2.58 and 2.16 A, respectively. The two S-H bond lengths are 1.19 and 1.21 A, shorter than those of gaseous H2S, 1.33 A.4 The V S H - S is found at 2290 cm"1 and the vSH..o at 2410 cm"1. A broad X H NMR signal at 8 1.96 is attributed to the H2S ligand. Without solvated THF, this complex is highly labile even under an H2S atmosphere. In the presence of 0 2, both complexes (solvent-free or solvated THF) are oxidized to the bridged disulfide complex [(u-S2){Ru(PPh3)'S4'}2] (Figure 4.1(c)). (a) IRutPPhO'SV] + H2S "/^ > [PutfSHJCPPbays^  (b) (C) ip^ SHzXPPhaySV] [(^ -SzXRuCPPhO'SVh] Figure 4.1 The (a) preparation, (b) structure and (c) oxidation of [Ru(SH2)(PPh3)(' S4')]. The unstable salts, [Ru(NH3)5(SH2)][BF4]2 and fraw5-[Ru(NH3)4(SH2)(isn)][BF4]2 (isn = isonicotinamide), reported by Kuehn and Taube, were prepared by the displacement of H 2 0 or S042" ligands by H2S in [Ru(NH3)5(OH2)][BF4]2 and /raw5-[Ru(NH3)4(S04)(isn)]Cl, 111 References on page 169 Chapter 4 respectively.2 Characterization included microanalysis, UV-Vis spectra and tentative assignment of a VSH band at 2547 cm"1 from the Raman spectrum of [Ru(NH3)s(SH2)][BF4]2. Even in the absence of 0 2 and H 20, [Ru(NH3)5(SH2)][BF4]2 decomposes to the Ru(III)-SH complex, [Ru(NH3)5(SH)][BF4]2 and H 2 , the H 2 being detected by low resolution mass spectrometry. rraw5-[Ru(NH3)4(SH2)(isn)][BF4]2 appeared to be indefinitely stable when stored in vacuo, and this was attributed to Ru(NH3)4(isn)2+ being less susceptible to oxidation thanRu(NH3)52+. The Pt(0) species [Pt(PPh3)2(SH2)] was detected by Ugo et al.5 A broad *H NMR signal at 8 1.9 indicated the coordinated H2S ligand, but this species is unstable and quickly formed [Pt(PPh3)2(SH)(H)] via oxidative addition (Figure 4.2). The Pt(H) product was evidenced by *H NMR peaks at 8 -1.4 (Pt-Stf) and -9.2 (Pt-//). H . S H PKPPh^ + H2S • | • HS, i ^, . .PPh 3 Ph 3 P^ P t ^PPh 3 Ph 3 P^ Figure 4.2 Formation of [Pt(PPh3)2(SH2)]. The formation of W(CO)5(SH2) can be achieved by the following methods: the photolysis of hexacarbonyltungsten(O) in the presence of H 2S, 6 displacement of THF with H 2S from W(CO)5(THF),6 or hydrolysis of W(CO)5(S(EMe3)2) (E = Si, Sn)7 (Figure 4.3). Complex formation was detected by mass spectrometry (detection of the molecular ion [W(CO)5(SH2)]+); IR data (vSH at 2560 cm"1); and a *H NMR singlet at 8 0.60 due to the H 2S ligand. The stability of this complex was attributed to the inert carbonyl fragment W(CO)5. 112 References on page 169 Chapter 4 At 90°C under N 2 , or at 20°C under vacuum, the green crystals of W(CO)5(SH2) underwent decomposition. W(CO) 6 H 2S,hu -CO W(CO) 5(THF) -THF H2S „ -Q(EMe3)2 W(CO) 5 S(EMe 3 ) 2 E = Si,Sn Figure 4.3 Formation of W(CO)5(SH2). The displacement of H 2 0 by H2S in c/s-[Mn(CO)4(T?Ph3XOH2)]rBF4] is thought to result in the formation of c/5-[Mn(CO)4(PPh3)(SH2)][BF4] (Figure 4.4(a)).8 A very weak v S H band is located at 2535 cm"1 and a lH NMR multiplet is observed at 5 -0.40 due to coordinated H2S. Exposure of this complex to air or moisture resulted in the reformation of cw-[Mn(CO)4(PPh3)(OH2)][BF4]. Previously, a similar manganese carbonyl complex, [Mn(CO)2(r|5-C5H5)(SH2)], had been reported but was unstable and poorly characterized.9 Other reports of metal carbonyl H2S complexes include [Re(CO)5(SH2)][BF4]10 (Figure 4.4(b)) and [M(CO)3(ri5-C5H5)(SH2)]X (M= Mo, X = BF 4; M = W, X = AsF6) (Figure 4.4(c))11. The complexes are unstable at ambient conditions and their formations were supported only by IR V S H bands at 2510, 2590 and 2548 cm'1, respectively. 113 References on page 169 Chapter 4 (a) |M<CO)4(PPl^XOH2)]PF4] + H 2 S >• [Mn(CO)4(PPb3)(SH2)][BF4] ~H20 (b) [Re(CO)5FBF3] + H 2 S [ R e C C O M S H ^ p ^ ] (c) M(CO)3(TI5-C5H5)X + H 2 S *• [M(CO)3(TI5-C5H5)(SH2)PC M = M o , X = BF 4; M=W,X=AsF 6 Figure 4.4 Formation of metal carbonyl H2S salts. The proposed unstable white product from the solid state reaction of [Ir(H)2(Me2CO)2(PPh3)2][BF4] with H2S was claimed to be [Ir(H)2(H2S)2(PPh3)2][BF4],12 although no evidence of H2S coordination was presented. Amarasekera and Rauchfuss observed formation of [CpRu(PPh3)2(SH2)][OTfJ upon protonation of CpRu(PPh3)2(SH) with HOTf, or treatment of CpRu(PPh3)2OTf with H 2S. 1 3 The *H NMR signal of coordinated H2S appeared at 5 3 . 5 8 (t) (3JHP = 7 . 2 Hz), but isolation of this complex was not possible because of reversion to CpRu(PPh3)2OTf. A similar complex [(ThiCp)Ru(PPh3)2(SH2)][OTf] was observed as the intermediate formed during the protonation of (ThiCp)Ru(PPh3)2(SH) with HOTf en route to [(ThiCp)Ru(PPh3)2][OTf]; conversion of the SH to H2S provided a liable coordination site for weak ligands such as thiophenes (Figure 4 . 5 ) . 1 3 Figure 4.5 Formation of [(ThiCp)Ru(PPh3)2][OTfJ. 1 1 4 References on page 169 Chapter 4 4.1.2 Transition Metal Thiol Complexes Although thiol ligands contain one less acidic proton than H2S, thiol complexes are also rare, and only a few have been well characterized either spectroscopically or crystallographically. In the same report describing formation of [CpRu(PPh3)2(SH2)][OTfJ and [(ThiCp)Ru(PPh3)2(SH2)][OTfJ, the crystal structure of [CpRu(PPh3)2(HSPrn)][BF4] was determined.13 The crystals were unintentionally obtained from the reaction of CpRu(PPh3)2Cl, thiophene and AgBF4 (Figure 4.6(a)); the HSPr" ligand is undoubtedly an impurity in the thiophene solution. The Ru-S and S-H bond distances are 2.377 and 1.25 A, respectively. Other thiol complexes of this type were also prepared directly from the reactions of thiols with CpRu(PPh3)2OTf4 or the alkylation of CpRu(PPh3)2SH.13 For example, [CpRu(PPh3)2(CH3SH)][OTfJ was prepared by treatment of CpRu(PPh3)2SH with CH 3OTf (Figure 4.6(b));13 in the lH NMR spectrum, the SH proton appears as a multiplet at 8 4.22, and the C773 protons as a doublet at 8 2.23. Draganjac and co-workers have also shown that similar thiol complexes, [CpRu(PPh3)2(RSH)][BF4] (R = benzyl and phenethyl), can be obtained by the reaction of CpRu(PPh3)2Cl and AgBF4 with the appropriate mercaptan (Figure 4.6(c)).15 For [CpRu(PPh3)2(C6H5CH2SH)][BF4] and [CpRu(PPh3)2(C6H5CH2CH2SH)][BF4], the thiol ligands are detected by IR (vSH = 2525 and 2515 cm"1, respectively) and J H NMR spectroscopy (triplet at 8 4.17 and quintet at 8 3.99 due the SH groups, respectively). Furthermore, the crystal structure of the phenethyl complex was solved and the thiol hydrogen was located with the Ru-S and S-H bond distances being 2.36(2) and 1.18 A, respectively. The electron rich CpRu moiety could also stabilize sterically bulky thiols as shown by the formation of [CpRu(PPh3)(ButNC)(ButSH)][PF6] (IR: v S H = 115 References on page 169 Chapter 4 2544 cm-1; *H NMR: SH doublet at 5 3.03) and [CpRu(dppm)(ButSH)][PF6] ( !H NMR: SH triplet at 8 2.74).16 These complexes were obtained from the reaction of CpRu(PPh3)(ButNC)Cl or CpRu(dppm)Cl with Bu'SH and NH4PF6 (Figure 4.6(d)). The crystal structure of [CpRu(dppm)(ButSH)][PF6] was obtained and the Ru-S and S-H bond lengths were determined to be 2.371(2) and 1.349(77) A, respectively. Although no spectroscopic or crystallographic evidence was provided, the air-sensitive species [CpRu{PPh2(OMe)}2(Bu,SH)][PF6]17 and [CpM(P(OMe)3)2(PhSH)][PF6] (M = Ru, Fe)18 were reported by Treichel et al. (Figure 4.6(f)). Oxidation in air resulted in the formation of the paramagnetic Ru(HI)-thiolate complexes, [CpRu{PPh2(OMe)}2(SBut)][PF6] and [CpM(P(OMe)3)2(SPh)][PF6]. It was also found that [CpRu(P(OMe)3)2(PhSH)][PF6] could be easily deprotonated by LDA to form CpRu(P(OMe)3)2(SPh). a) CpRu(PPh3)2Cl + AgBF4 + HSPr" a W i > [CpRu(PPh3)2(HSPrn)]BF4 b) CpRu(PPh3)2SH + CH3OTf afea2 „ [CpRu(PPh3)2(CH3SH)]OTf c) CpRu(PPh3)2Cl + AgBF4 + RSH o*a, > [CpRu(PPh3)2(RSH)]BF4 R=benzyl, phenethyl d) CpRu(PPh3)(ButNC)Cl + NH4PF6 + Bu'SH MeOH ^ [CpRu(PPh3)(ButNC)(ButSH)]]PF e) CpRu(dppm)Cl + NH4PF6 + Bu'SH MeOH ^ [CpRu(dppm)(ButSH)]]PF6 (e) CpM(P(OMe)3)2Cl + XPF 6 + PhSH Meo H ^ [CpM(P(OMe)3)2(PhSH)]]PF6 X=NH(,M=Ru; X=Ag,M=Fe Figure 4.6 Preparation of thiol complexes containing the electron rich CpM (M = Ru, Fe) moieties. 116 References on page 169 Chapter 4 More recently, Tocher's group has reported the formation of [Ru(ri3:r|3-CioHi6)Cl2(HSR)] (R = Me, Et, Pr\ Bu1, Ph) from the reaction of the Ru(IV) chloro-bridged dimer [{Ru(r]3:ri3-CioHi6)Cl(p.-Cl)}2 with thiols (Figure 4.7).19 Supporting evidence for the coordination of thiols was given by IR and *H NMR data. The VSH bands for the above complexes were found at 2424, 2423, 2471, 2458 and 2460 cm"1, respectively. Sharp *H NMR SH resonances (5 3.46 (t), R = Et; 5 3.51 (q), R = Me) were interpreted as resulting from strong intramolecular hydrogen-bonding of the thiol hydrogen to the chlorine, while broad SH resonances (5 3.48, R = Pr"; 6 3.29, R = Bu'; 5 5.56, R = HSPh) indicated that these thiol complexes are in dynamic equilibrium with the starting material. Figure 4.7 Formation of [Ru(ri3:ri3-CioHi6)Cl2(HSR)]. Darensbourg et al. have reported a series of Cr(0) thiol complexes containing carbonyl ligands, Cr(CO)4(RSH)L (L = CO, PEt3; R = Bu1, Et, Pr\ Ph), which were prepared by the reaction of Cr(CO)5(THF) with RSH or the protonation of Cr(CO)4(RS)L" with HBF 4 . 2 0 These species were characterized by *H NMR SH resonances at 8 ~ 1.0. The crystal structure of C^CO^u'SH) revealed Cr-S and S-H bond lengths of 2.439(2) and 1.2(1) A, respectively. Treatment of TiCL» with cyclohexane- or cyclopentanethiol afforded the moisture-sensitive, yellow solids, [TiCU(RSH)2].21 In addition to sharp IR VSH bands found at + RSH 117 References on page 169 Chapter 4 ~ 2500 cm-1, the crystal structure of [TiCLtCCeHuSH ]^ was determined, but the thiol H-atoms were not located. The X-ray crystal structure of FeTPPCCeHsXCeHsSH) (TPP = tetraphenylporphyrin), was determined by Collman et al.22 This complex was used as a dynamic model to study substrate binding in the catalytic cycle of P450 enzymes. Electronic structures based on single-crystal ESR measurements were obtained at low temperatures (77-173 K) for the above complex and the similar ferric complexes: Fe(NH2TPP)(SPh)(HSPh), FeTPP(S-/w-tolyl)(HS-w-tolyl), FeTPP(SCH2C6H5)(HSCH2C6H5) and FeTPP(S(CH2)2CH(CH3)2)(HS(CH2)2CH(CH3)2).23 Both types of structural determination, however, were unsuccessful in locating the thiol H-atoms. The thiol group can also coordinate to metal centres as part of a bidentate ligand as shown by the structure of [IrH(SCH2CH2PPh2)(HSCH2CH2PPh2)(CO)]Cl, formed by the reaction of /raw5-Ir(PPh3)2(CO)Cl with excess HSCH2CH2PPh2 (Figure 4.8)24. X-ray structural determination showed an S-H bond distance of 1.354(10) A. Stabilization of the S-H group was attributed to the chelating mixed P-S ligand. H Ph2 OC.,, .iPPbj PhjPCHjCHjSH OC I ,.<'F-| Ph^CHzCHzSH PlbP^ NC1 ^ Ph,P^YNS^ ^ CI Figure 4.8 Preparation of [IrH(SCH2CH2PPh2)(HSCH2CH2PPh2)(CO)]Cl. Morris and co-workers have prepared a series of metal-thiol complexes obtained by the protonation of metal-thiolate complexes with HBF4. The reaction of MH(CO)(N-S)(PPh3)2 (M = Ru, Os; N-S = pyridine-2-thiolate, quinoline-8-thiolate) with H PPh, OC,.. I „ , P > 2 PPh2P^ | ^S- 1 CI 118 References on page 169 Chapter 4 excess HBF 4 at 193 K gave [MH(CO)(N-SH)(PPh3)2][BF4] (Figure 4.9),25 the intermediate [M(r|2-H2)(CO)(N-S)(PPh3)2][BF4] being observed by NMR spectroscopy at 213 K en route to the formation of the thiol species. Both species, however, decompose at temperatures above 273 K. NMR spectroscopy located the protons of the coordinated thiol groups as doublet of doublets (coupling to two inequivalent P atoms) at 5 ~ 4.7. Similarly, reactions of /ra/?5-M(H)(SPh)(dppe)2 (M = Ru, Os; dppe = l,2-bis(diphenylphoshino)ethane) with HBF 4 resulted in /ra«5-[M(H)(HSPh)(dppe)2][BF4].26 Only the more stable Os complex was characterized by X H NMR where a broad resonance at 5 4.4 was assigned to the coordinated thiol. PPhg PPh, H B F / 193 K M = Ru ,Os iO -PPho O C | * . N T T ' " M d 1 H P P h 3 PPI13 PPha H Figure 4.9 In situ formation of rMH(CO)(N-SH)(PPh3)2][BF4]. 4.2 Synthesis and Characterization of Qs-RuX2(P-N)(PPh3)(SH2), X = CI, Br, I When acetone or CD2C12 solutions of RuX2(P-N)(PPh3) are stirred under 1 atm of H2S, the complexes c/5-RuX2(P-N)(PPh3)(SH2) are rapidly formed. These complexes are dark yellow, diamagnetic, stable at ambient conditions, and decompose only slowly due to the loss of H2S. The cw-RuX2(P-N)(PPh3)(SH2) species with X = CI and Br were characterized by X-ray crystallography. 119 References on page 169 Chapter 4 4.2.1 aj-RuCl2(P-N)(PPh3)(SH2) (18a) The prismatic crystals of cw-RuCl2(P-N)(PPh3)(SH2) (18a) containing one acetone molecule per molecule of complex formed from a concentrated acetone solution containing RuCl2(P-N)(PPh3) (6a) under 1 atm H2S. The X-ray crystal structure of 18a (Figure 4.10) was determined and was found to be isostructural with that of cw-RuCl2(P-N)(P(p-tolyl)3)(SH2) (19a), previously determined in this laboratory.271*28 However, contrary to the case with 19a, where only one H-atom of the H2S was located, both H-atoms bonded to the S-atom were isotropically refined for 18a. Figure 4.10 reveals a pseudo-octahedral geometry around the Ru with c/s-chloro ligands and the H2S trans to one chlorine. Selected bond lengths and angles for 18a and 19a are shown in Tables 4.1 and 4.2, respectively. The chelate bite angle P(l)-Ru(l)-N(l) in 18a is 83.09(5)°, slightly larger than 81.81(8) and 81.3(3)° of the RuCl2(P-N)(P(p-tolyl)3) precursor 7a and 19a, respectively. For 18a, the average trans-bond angle at Ru is ~ 172°; with the exception of 103.11(2)° for P(l)-Ru(l)-P(2) which can be attributed to the repulsion of the phenyl groups on the P-atoms, the cw-bond angles are approximately 89°. No significant differences were observed for the bond lengths around the Ru between 18a and 19a. The Ru-S bond distances, 2.3503(3) and 2.330(4) A, are comparable to that of 2.399(5) A in Sellmann's complex, [Ru(SH2)(PPh3)('S4')],3 but are significantly shorter than those of terminal Ru-SH complexes (2.46 A).29'30 However, in contrast to [Ru(SH2)(PPh3)('S4')] where the H-S-H angle is 77° due to hydrogen bridges (see Figure 4.1), the 101.7(17)° angle is much larger in 18a; the H-S-H bond angle is 92.2° for gaseous H 2S 3 1. While the two S-H bond 120 References on page 169 Chapter 4 Figure 4.10 The ORTEP plot of czs-RuCl2(P-N)(PPh3)(SH2) (18a). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix IV. 121 References on page 169 Chapter 4 Table 4.1 Selected bond lengths (A) for c/5-RuCl2(P-N)(PPh3)(SH2) (18a) and cw-RuCl2(TJ-N)(P(p-tolyl)3)(SH2) (19a) with estimated standard deviations in parentheses. Bond Length (A) 18a 19a Bond Length (A) 18a 19a Ru(l)-S(l) 2.3503(3) 2.330(4) Ru(l)-P(l) 2.2712(6) 2.256(4) Ru(l)-P(2) 2.3110(7) 2.304(3) Ru(l)-N(l) 2.338(2) 2.37(10) Ru(l)-Cl(l) 2.4238(6) 2.429(3) Ru(l)-Cl(2) 2.4721(5) 2.469(4) S(l)-H(l) 1.20(3) 1.25 S(l)-H(2) 1.30(3) N/A Table 4.2 Selected bond angles (°) for c/s-RuCl2(P-N)(PPh3)(SH2) (18a) and c/5-RuCl2(P-N)(P(p-tolyl)3)(SH2) (19a) with estimated standard deviations in parentheses. Bond Angles (°) Bond Angles (°) 18a 19a 18a 19a H(l)-S(l)-H(2) 101.7(17) N/A S(l)-Ru(l)-P(l) 90.54(2) 93.8(1) Ru(l)-S(l)-H(l) 110.7(12) 124.2 S(l)-Ru(l)-P(2) 93.76(2) 92.7(1) Ru(l)-S(l)-H(2) 103.3(11) N/A S(l)-Ru(l)-N(l) 89.18(5) 89.8(2) Cl(l)-Ru(l)-S(l) 175.18(2) 174.6(1) Cl(2)-Ru(l)-P(l) 168.03(2) 170.0(1) Cl(2)-Ru(l)-S(l) 82.63(2) 83.1(1) Cl(2)-Ru(l)-P(2) 87.21(2) 88.0(1) Cl(l)-Ru(l)-P(l) 91.95(2) 88.0(1) Cl(2)-Ru(l)-N(l) 86.97(4) 89.1(3) Cl(l)-Ru(l)-P(2) 89.70(2) 91.9(1) P(l)-Ru(l)-P(2) 103.11(2) 101.7(1) Cl(l)-Ru(l)-N(l) 87.03(5) 85.4(2) P(l)-Ru(l)-N(l) 83.09(5) 81.3(3) Cl(l)-Ru(l)-Cl(2) 94.19(2) 94.3(1) P(2)-Ru(l)-N(l) 173.09(5) 175.9(3) 122 References on page 169 Chapter 4 lengths are nearly identical (1.19 and 1.21 A) in Sellmann's complex, they are slightly different in 18a with lengths of 1.20(3) and 1.30(3) A. Upon coordination of the H2S to Ru, the S-H bonds are shortened with respect to those of gaseous H2S, 1.33 A4'31. The S(l)-H(l) bond length compares with 1.25 A of 19a, while the longer S(l)-H(2) bond distance of 1.30 A is attributed to intramolecular hydrogen-bonding between H(2) and Cl(2); the H—Cl distance is 2.69(3) A, which is less than the van der Waals distance of 3.00 A.32 The non-linear S-H—CI angle of 100(1)° indicates that this interaction is quite weak as maximum orbital overlap is not attained. As a result of hydrogen-bonding, the Cl(2)-Ru-S and Ru-S-H(2) planes differ by only 20.85°, while H(l) is positioned at 60° under the C1(1)-C1(2)-S-P(1) plane. There are no apparent interactions between the coordinated H2S and acetone solvate. Both H-atoms of the coordinated H2S point toward the planes of phenyl groups of PPh3 and P-N. Osakada et al. suggested that SH/TC interactions (2.69 A and 2.63 A) exist between bridging mercapto groups and the planes of phenyl groups in the dinuclear complex (PhMe2P)3Ru(|a-SH)3Ru(SH)(PMe2Ph)2 (Figure 4.11).29 In 18a, the closest phenyl/SH distances are H(l)-C(9) and H(2)-C(21) with values of 2.80 and 2.97 A, respectively. These are slightly less than the sum of 2.99 A for the van der Waals radii of the two atoms. Therefore, weak SH/TC interactions may play a role in stabilizing the H2S in 18a. Figure 4.11 Bond distances between H-atom and nearest C-atom of phenyl ring to indicate SH/TC interactions in (PhMe2P)3Ru(u-SH)3Ru(SH)(PMe2Ph)2. 123 References on page 169 Chapter 4 The 31P{!H} NMR spectrum of 18a in CD2C12 and under 1 atm H 2S gave an AX pattern at 8 49.81 and 43.30 ( 2JP P = 28.78 Hz) characteristic of cis-? atoms (Figure 4.12(a)).27 In the *H NMR spectrum, the Ru-SH2 resonances gave a broad peak at 8 1.03 in C 6 D 6 (Figure 4.13) but this must be obscured by the free H2S peak in CD2C12 (Figure 4.14(a)). The signals due to the two -N(C773) groups are seen at 8 3.40 and 3.13, characteristic of the symmetry imposed by the cz's-Cl atoms. These observations are very similar to those previously found by Mudalige et al.27 A variable temperature NMR study of 18a was carried out in CD2C12. Figure 4.12 shows the Px signal is shifted downfield slightly, while the PA peak is shifted upfield more significantly as the temperature is decreased from 20 to -90°C. The changes in chemical shifts are perhaps due to the diminishing rates of Ru-SH2 bond rotation or sulfur ligand inversion at low temperatures. 124 References on page 169 Chapter 4 Figure 4.12 31P{ 1H} NMR spectra (202.47 MHz) of c7s-RuCl2(P-N)(PPh3)(SH2) (18a) in CD2C12 at various temperatures. Sample is under 1 atm of H2S. 125 References on page 169 Chapter 4 acetone NMe2 of 6a Figure 4.13 lH NMR spectra (121.4 MHz) of cw-RuCl2(P-N)(PPh3)(SH2)-(acetone) (18a) in CeDe. Note: 18a is in equilibrium with RuCl2(P-N)(PPh3) (6a) (8 3.07, NMe2) and free H2S (5 0.35). At -50°C, the ! H NMR spectrum (Figure 4.14(b)) is the most informative, giving well resolved peaks; these became broader as the temperature approaches the freezing point of CD2C12 (-95°C). At -50°C, the signals due to the two -N(CH3) groups become closer together (6 3.22 and 3.19) than at 20°C. The Ru-SH2 resonances, originally hidden under the free H2S signal at 20°C, are now resolved into a doublet of doublets at 6 1.49 (HB) and a doublet at 6 0.30 (HA). The doublets show that H A and H B are mutually coupled (2JHH = 12.3 Hz), while H B must be coupled to a P-atom while H A is not (3JHP = 3.50 Hz). The ^{^P} NMR spectrum (Figure 4.15) was also measured at -50°C, and the H B multiplet was reduced to a doublet while the H A resonance remains unchanged. From these data, it was not apparent whether H B was coupled to P A or Px. 'HI31?} GARP (Globally optimized Alternating-phase Rectangular Pulses)33 NMR experiments were performed to observe 126 References on page 169 Chapter 4 N NMe2 / i a —R i i ' ^ s . . . H A p h 3 p Y a1 Free H2S Ru-S#2 (a) 20°C Figure 4.14 VT *H NMR spectra (500 MHz) of c7s-RuCl2(P-N)(PPh3XSH2) (18a) in CD2C12 (under 1 atm H2S) for the region 5 0.0 to 5 4.0. Note: the NMe 2 peak of RuCl2(P-N)(PPh3) (5 3.19 in CD2C12) is no longer seen due to the presence of excess H2S. 127 References on page 169 Chapter 4 effects on the HB signal. With the first scanning radiofrequency set at 500.1386730 MHz to observe the *H region, the second irradiating frequency is centred either on the resonance of P A at 202.4685838 MHz, 8 47.0, or P B at 202.4677665 MHz, 5 43.0. The decoupler power was then varied by changing the attenuation (dB). With the decoupler set at 8 47.0, the H B resonance became more decoupled to P A as the decoupler power was increased (Figure 4.16). The above experiment was repeated with the decoupler transmitter centred at 202.4677665 MHz. However, variation of the attenuation power at this frequency had no effect on HB . Evidently, H B is coupled to PA (a) ^ N M R H n H A (b) ^{"P} NMR 1.4 1.2 - > — i — 1.0 0.8 0.6 0.40 ppm Figure 4.15 *H and ^{"P} NMR spectra (500 MHz) of cz5-RuCl2(P-N)(PPh3)(SH2) (18a) in CD2C12 (under 1 atm H2S) at -50°C for the region 8 0.2 to 1.6. 128 References on page 169 Chapter 4 i — • — 1 — 1 — • — i — 1 — 1 — • — 1 — i 1 1 1 1 i 1 1 r ~ 1.55 1.50 1.45 1.40 ppm Figure 4.16 *H NMR (500 MHz) signal at 8 1.49 for c/5-RuCl2(P-N)(PPh3)(SH2) (18a) with decoupler transmitter centred at 202.4685838 MHz with increasing 3 1P decoupler power (decreasing dB). Spectra recorded at -50°C and in CD2C12. At -50°C, the exchange of the two diastereotopic hydrogens of the coordinated H2S diminishes (Figure 4.14(b)) and the structure of 18a in solution presumably approaches the 129 References on page 169 Chapter 4 solid state structure. With reference to the crystal structure of 18a (Figure 4.10 and Table 4.1), HB is assigned to the H(2) proton that is hydrogen-bonded to Cl(2), as this would result in a higher chemical shift due to the deshielding effect of the electron-withdrawing group. The magnitude of the 3JHP coupling constant (3.50 Hz) at 5 1.49 is consistent with those observed for Ru(SH)(SR)(CO)2(PPh3)2 (6.8 Hz, R =H; 7.1Hz, R=p-tolyl; 7.3 Hz, R = CeHs)34'35 and [CpRu(PPh3)2(SH2)][OTfJ (7.2 Hz).13 Two logical questions to ask at this point are (1) why is H B coupled to P A and not Px, and (2) why is H A coupled to neither? Coupling between atoms on vicinal atoms depends primarily on the overlap of the orbitals within the bonding framework, and therefore the dihedral angle o) between the planes. In the present case, these are the P-Ru-S and Ru-S-H planes. In organic molecules, the vicinal coupling of protons ( 3 J , H-C-C-H) is described by the Karplus relationship,36 and this correlation may be extended to systems containing P-C-C-H, P-O-C-H, P-N-C-H, and P-S-C-H31 The Karplus curves for the H-C-C-H, P-C-C-H, and P-O-C-H systems are Figure 4.17 The vicinal Karplus correlation. Relationship between dihedral angle (())) and 3 J . 130 References on page 169 Chapter 4 plotted in Figure 4.17. Coupling is at a maximum when <}> is 180° when the hydrogens are antiperiplanar and orbitals are overlapping most efficiently; there is no coupling when <|> is 90°. The magnitude of 3 J is dependent on the types of atoms connected to the three bonds. For 18a, the dihedral angles for P-Ru-S-H can be visualized by an end-on view of the Ru-S bond shown in Figure 4.18. The absolute dihedral angles for non-coupling P and H atoms are 60.79°, 42.40° and 65.84°. These correspond to P(l)-H(l), P(2)-H(l) and P(2)-H(2) interactions where the orbital overlaps are negligible. For the P(l)-H(2) coupling pair, the dihedral angle is at 169.03° where coupling is observed (3JHP = 3.5 Hz). Such a P(l)-Ru-S-H(2) arrangement is likely the result of interactions of H(2) with Cl(2) and a phenyl group of PPI13. P(l)-Ru-S-H(l) 60.79 P(l)-Ru-S-H(2) 169.03 P(2)-Ru-S-H(l) -42.40 P(2)-Ru-S-H(2) 65.84 Figure 4.18 End-on schematic view of the solid state structure of 18a, with dihedral angles (°) corresponding to P-Ru-S and Ru-S-H planes. 4.2.2 Cis-RuBr2(P-N)(PPh3)(SH2) (18b) Orange prismatic crystals of cw-RiiBr2(P-N)(PPh3)(SH2)-(C6H6) (18b) were isolated from a saturated benzene solution of RuBr2(P-N)(PPh3) (6b) under 1 atm of H2S. The X-ray crystal structure is shown in Figure 4.19, with selected bond lengths and angles given in Tables 4.3 and 4.4, respectively. Similar to 18a, a pseudo octahedral geometry around the Ru centre is observed for 18b. The two S-H bond lengths (1.25(7)) A and 1.34(6) A) in 18b are 131 References on page 169 Chapter 4 inequivalent. However, contrary to 18a where the longer S-H(2) distance (1.30 A vs. 1.20 A for S-H(l)) is attributed to H(2)—Cl(2) bonding, the H—Br bonding is observed between Br(l) and H(l), which is bonded to S with a shorter distance of 1.25 A. The H—Br distance of 2.85(6) A and the S(l)-H(l)-Br(l) angle of 94(3)° suggest weak hydrogen-bonding. The above data suggest that hydrogen-bonding has a negligible effect on the S-H bond lengths. The H-atoms of the coordinated H2S are situated under the Br(l)-Br(2)-P(l)-S plane and are positioned close to the planes of phenyl groups. The larger Br groups force the hydrogens close enough to the phenyl groups for possible SH/71 interactions to occur. The distances of 2.52 A and 2.59 A found for H(l)-C(20) (phenyl from P-N) and H(2)-C(28) (phenyl from PPh3), respectively, are considerably shorter than corresponding ones in 18a. Such phenyl group (from thiophene rings) and mercapto proton interactions are important because they have been implicated in hydrodesulfurization mechanisms.38 The "P^H} NMR spectrum of 18b recorded in CD2C12 under 1 atm of H 2S is very similar to that of 18a, an AX pattern with P A at 8 53.41 and P B at 8 44.36 ( 2JP P = 29.20 Hz). In the ! H NMR spectrum, the NMe2 resonances are located at 8 3.70 and 5 3.02 while the Ru-SH2 protons resonate at 8 1.03 and are no longer obscured by the free H2S signal. When the sample was cooled to -50°C, signals due to H(2) and H(l) (the H-atom bonded to Br(l)) were resolved into a doublet at 8 0.48 and a doublet of doublets at 8 1.23, respectively, with 2 J H H and 3Jm> coupling constants of 12.2 and 4.3 Hz. When the 3 1P decoupler was turned on, the signal at 5 1.23 became a doublet. Therefore, H(l), bonded to the S-atom at a distance of 1.25 A, is coupled to P(l) of the P-N ligand, as discussed for 18a. The absolute dihedral angle between P(l)-Ru-S and Ru-S-H(l) planes is 144.02° (see Figure 4.20). 132 References on page 169 Chapter 4 C(27) Figure 4.19 The ORTEP plot of c/5-RuBr2(P-N)(PPh3)(SH2) (18b). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix V. 133 References on page 169 Chapter 4 Table 4.3 Selected bond lengths (A) for czs-RuBr2(P-N)(PPh3)(SH2) (18b) with estimated standard deviations in parentheses. Bond Length (A) Bond Length (A) Ru(l)-S(l) 2.3330(10) Ru(l)-Br(l) 2.6343(5) Ru(l)-P(l) 2.2617(10) Ru(l)-Br(2) 2.5540(4) Ru(l)-P(2) 2.3011(11) S(l)-H(l) 1.25(7) Ru(l)-N(l) 2.372(3) S(l)-H(2) 1.34(6) Table 4.4 Selected bond angles (°) for czs-RuBr2(P-N)(PPh3)(SH2) (18b) with estimated standard deviations in parentheses. Bond Angles (°) Bond Angles (°) H(l)-S(l)-H(2) 98.0(39) S(l)-Ru(l)-P(l) 93.87(4) Ru(l)-S(l)-H(l) 100.9(26) S(l)-Ru(l)-P(2) 93.48(4) Ru(l)-S(l)-H(2) 115.2(22) S(l)-Ru(l)-N(l) 89.43(9) Br(l)-Ru(l)-S(l) 79.77(3) Br(2)-Ru(l)-P(l) 91.57(3) Br(2)-Ru(l)-S(l) 172.31(3) Br(2)-Ru(l)-P(2) 90.94(3) Br(l)-Ru(l)-P(l) 169.09(3) Br(2)-Ru(l)-N(l) 86.01(8) Br(l)-Ru(l)-P(2) 89.54(3) P(l)-Ru(l)-P(2) 99.76(4) Br(l)-Ru(l)-N(l) 89.55(8) P(l)-Ru(l)-N(l) 81.47(8) Br(l)-Ru(l)-Br(2) 94.00(2) P(2)-Ru(l)-N(l) 176.75(9) 134 References on page 169 Chapter 4 Br(l) P(l)-Ru-S-H(l) -144.02 P(l)-Ru-S-H(2) -39.68 P(2)-Ru-S-H(l) -43.97 P(2)-Ru-S-H(2) 60.36 Figure 4.20 End-on schematic view of the solid state structure of 18b, with dihedral angles corresponding to P-Ru-S and Ru-S-H planes. 4.2.3 In situ Preparation of G's-RuI2(P-N)(PPh3)(SH2) (18c) and Cw-RuI2(P-N)(P(p-tolyl)3)(SH2) (19c) The above title complexes could not be isolated as they are less stable than the CI" and Br" analogues. However, formation of the H2S adducts is observed by NMR spectroscopy when RuI2(P-N)(PPh3) (6c) or RuI2(P-N)(P(p-tolyl)3) (7c) in CDC13 are exposed to 1 atm H2S. In the 31P{JH} NMR spectra, the AX signals for 18c and 19c appear at 8 56.0, 49.5 ( 2JP P = 25.8 Hz) and 8 56.2, 47.5 ( 2JP P = 25.8 Hz), respectively. The *H NMR spectra show inequivalent NMe resonances (8 4.16, 2.20 for 18c; 8 4.15, 2.91 for 19c) and broad Ru(SH2) resonances (8 0.95 for 18c; 8 0.90 for 19c). The dark yellow solutions of 18c and 19c decompose to unidentifiable brown species within 1 h of sample preparation, even in the absence of air. The instability of the iodo complexes indicates that the larger size of the iodine does not create an optimal cavity size in the five-coordinate complex with respect to H 2S coordination. Whether the iodo systems are photosensitive remains to be explored; iodo Pd(dpm) systems are known to be photosensitive.39 135 References on page 169 Chapter 4 4.3 The Synthesis and Characterization of Ci's-RuCl2(P-N)(PPh3)(RSH) Species (R = alkyl) 4.3.1 Cis-RuCl2(P-N)(PPh3)(MeSH) (20) Yellow-brown, prismatic crystals of c/'5-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) were isolated from a saturated acetone solution containing RuCl2(P-N)(PPh3) (6a) and excess MeSH. In the solid state, 20 is stable in air at r.t. for ~ 24 h after which time it slowly decomposes to an uncharacterizable brown solid with the loss of MeSH (as evidenced by NMR spectra of solutions of the brown solid, as well as the smell of MeSH). The X-ray structure is shown in Figure 4.21, with selected bond lengths and angles given in Tables 4.5 and 4.6, respectively. The overall geometry, and bond lengths and angles of 20 are similar to those of c/'5-RuCl2(P-N)(PPh3)(SH2) (18a). A search of the Cambridge Structural Database indicates that 20 is the first structure of a coordinated MeSH complex. Furthermore, the bond length of 1.03(4) A is the shortest S-H distance yet reported for a thiol complex. There is no hydrogen bonding between the H-atom of the coordinated thiol and a Cl-atom. Both the Me and H groups of the coordinated thiol are situated below the C1(1)-C1(2)-P(1)-S plane. The thiol H-atom points towards the planes of phenyls bonded to P(l) and P(2); the H—C(15) and H—C(22) distances of 2.84 and 2.49 A indicate SH/TI (phenyl rings) interactions. 136 References on page 169 Chapter 4 C(33) C(21) Figure 4.21 The ORTEP plot of cz5-RuCl2(P-N)(PPh3)(MeSH) (20). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix VI. 137 References on page 169 Chapter 4 Table 4.5 Selected bond lengths (A) for cz5-RuCl2(P-N)(PPh3)(MeSH) (20) with estimated standard deviations in parentheses. Bond Length (A) Bond Length (A) Ru(l)-S(l) 2.3403(7) Ru(l)-Cl(l) 2.4241(7) Ru(l)-P(l) 2.2803(7) Ru(l)-Cl(2) 2.4472(7) Ru(l)-P(2) 2.3100(7) S(l)-H(l) 1.03(4) Ru(l)-N(l) 2.335(2) S(l)-C(39) 1.805(3) Table 4.6 Selected bond angles (°) for c7s-RuCl2(P-N)(PPh3)(MeSH) (20) with estimated standard deviations in parentheses. Bond Angles (°) Bond Angles (°) H(l)-S(l)-C(39) 100.1(18) S(l)-Ru(l)-P(l) 86.17(3) Ru(l)-S(l)-H(l) 101.5(21) S(l)-Ru(l)-P(2) 94.83(3) Ru(l)-S(l)-C(39) 116.49(11) S(l)-Ru(l)-N(l) 87.09(6) Cl(l)-Ru(l)-S(l) 176.61(3) Cl(2)-Ru(l)-P(l) 169.27(3) Cl(2)-Ru(l)-S(l) 90.07(3) Cl(2)-Ru(l)-P(2) 86.67(3) Cl(l)-Ru(l)-P(l) 92.50(3) Cl(2)-Ru(l)-N(l) 86.51(6) Cl(l)-Ru(l)-P(2) 88.51(3) P(l)-Ru(l)-P(2) 103.65(3) Cl(l)-Ru(l)-N(l) 89.66(6) P(l)-Ru(l)-N(l) 83.26(6) Cl(l)-Ru(l)-Cl(2) 90.69(3) P(2)-Ru(l)-N(l) 172.92(6) The ^Pl/H} NMR spectrum of 20 in CD2C12 shows an AX pattern with P A and P x signals at 6 49.77 and 5 41.22 ( 2JP P = 30.17 Hz), respectively. The *H NMR spectrum at 20°C (Figure 4.22(a)), showing two inequivalent NMe groups at 6 3.42 and 5 3.17, is 138 References on page 169 Chapter 4 consistent with the cis orientation of the Cl-atoms. The resonances due to the SMe and SH groups overlap giving a multiplet at 8 0.77, but at -50°C (Figure 4.22(b)) these signals resolve into a doublet for SMe at 8 0.65 (2JHH = 6.97 Hz) and a broad multiplet for SH at 8 0.60. The 'H{31P} NMR spectrum at -50°C is unchanged, and coupling of the thiol hydrogen to a P-atom is not evident; the Karplus correlation, for the dihedral angle of 73.89° between the P(l)-Ru-S and Ru-S-H planes, predicts only a small coupling constant between P(l) and H. NMe I | ' M | I M I | I I I I | I I I I | I I I I | I I I I | I I I I | | I I I | I I I I | I I 3.4 3.0 2.6 2.2 1.8 1.4 1.0 ppm Figure 4.22 *H NMR spectra of c/'s-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) in CD 2C1 2 (a) 20 °C and (b) -50°C. Note: 20 is in equilibrium with RuCl 2(P-N)(PPh 3) (6a) (8 3.08 (d, 20°C), NMe 2) and free MeSH (*8 1.95 (d), C# 3SH; 8 1.33 (q), CHsSfl); • = 8 2.04 ((C# 3) 2CO). 139 References on page 169 Chapter 4 4.3.2 Cis-RuCl2(P-N)(PPh3)(EtSH) (21) From a saturated C 6D 6 solution of RuCl2(P-N)(PPh3) (6a) in excess EtSH, yellow prismatic crystals of cw-RuCl2(P-N)(PPh3)(EtSH)-1.5(C6D6) (21) were collected. The X-ray structure of the EtSH complex is shown in Figure 4.23 with selected bond lengths and angles listed in Tables 4.7 and 4.8, respectively. The S -H bond distance is 1.27(2) A, intermediate between the values of 1.25 A and 1.33 A obtained for the analogous H 2 S complex 18a. No S-H—CI interactions were detected for 21. One of the hydrogen atoms, H(2), bonded to C(l), the a-carbon of the ethylthiol moiety, is hydrogen-bonded to Cl(2) with a distance of 2.90 A and angle of 97.4°. The Et and H groups of the coordinated thiol are situated below the C1(1)-C1(2)-P(1)-S plane with the H-atom pointing toward a phenyl group. SH/7t interaction distances of 2.30 A and 2.83 A were found for H(l)—C(24) (a phenyl group belonging to P(l)) and H(l)—C(l 1) (a phenyl group belonging to P(2)), respectively. The 3 1 P { 1 H } NMR spectrum of 21 in CD2C12 indicates the presence of the c/s-dichloro isomer and approximately 10 % of the five-coordinate precursor 6a. The P A and Px doublets of 21 appear at 8 52.43 and 8 43.97 (2JP P = 30.23 Hz), respectively, and are consistent with the data obtained from the previous in situ work by Mudalige.27b However, contrary to this earlier work, no trans isomer was detected. The species previously assigned as the trans isomer may be due to the use of impure EtSH. The * H NMR spectrum of 21 (Figure 4.24) reveals that the H b and H e methylene protons are inequivalent as indicated by multiplets at 8 2.00 and 5 0.88, respectively. The S-atom becomes chiral when coordinated to the Ru centre; the H b and H e protons are diastereotopic and therefore anisochronous.40 140 References on page 169 Chapter 4 Figure 4.23 The ORTEP plot of czs-RuCl2(P-N)(PPh3)(EtSH) (21). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix VII. 141 References on page 169 Chapter 4 Table 4.7 Selected bond lengths (A) for ezs-RuCl2(P-N)(PPh3)(EtSH) (21) with estimated standard deviations in parentheses. Bond Length (A) Bond Length (A) Ru(l)-S(l) 2.3391(6) Ru(l)-Cl(l) 2.4204(6) Ru(l)-P(l) 2.2753(5) Ru(l)-Cl(2) 2.4674(5) Ru(l)-P(2) 2.3100(6) S(l)-H(l) 1.27(2) Ru(l)-N(l) 2.362(2) S(l)-C(l) 1.825(2) C(l)-C(2) 1.502(4) Table 4.8 Selected bond angles (°) for c/5-RuCl2(P-N)(PPh3)(EtSH) (21) with estimated standard deviations in parentheses. Bond Angles (°) Bond Angles (°) H(l)-S(l)-C(l) 96.0(9) S(l)-Ru(l)-P(l) 87.37(2) Ru(l)-S(l)-H(l) 104.1(9) S(l)-Ru(l)-P(2) 97.16(2) Ru(l)-S(l)-C(l) 115.84(9) S(l)-Ru(l)-N(l) 85.33(5) Cl(l)-Ru(l)-S(l) 174.63(2) Cl(2)-Ru(l)-P(l) 167.88(2) Cl(2)-Ru(l)-S(l) 87.15(2) Cl(2)-Ru(l)-P(2) 91.78(2) Cl(l)-Ru(l)-P(l) 96.25(2) Cl(2)-Ru(l)-N(l) 86.18(4) Cl(l)-Ru(l)-P(2) 86.17(2) P(l)-Ru(l)-P(2) 99.63(2) Cl(l)-Ru(l)-N(l) 91.19(5) P(l)-Ru(l)-N(l) 82.61(4) Cl(l)-Ru(l)-Cl(2) 88.54(2) P(2)-Ru(l)-N(l) 176.71(5) S(l)-C(l)-C(2) 109.4(2) The coupling constants of the protons of the coordinated EtSH group were obtained from the *H NMR spectrum of 21 (Figure 4.24) with the help of simulated spectrum (Figure 142 References on page 169 Chapter 4 4.25(a)). The C(Hd )3 methyl protons at 8 0.46 are coupled to Hb and He ( 3 J H B H D = 3 J H C H D = 7.36 Hz) while the Hb and He methylene protons at 8 2.00 and 8 0.88, respectively, are coupled to each other, to the thiol H a proton, and to H j . The downfield shift of Hb is a result of hydrogen-bonding to a Cl-atom. The coupling constants are: 3 J H B H E = 13.74 Hz, 3 J H A = 10.74 Hz,. 3 J H A = 5.83, 3 J H B H D = ' J H ^ = 7.36 Hz, which were also obtained from the doublet of doublet of doublets assigned to Ha. Further confirmation of i 1 1 1 • i • 1 1 1 1 1 • • • i • • • • i ' • • • i • 1 1 1 1 1 1 1 • i • • • 1 1 1 1 1 1 1 • • • ' i 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ' i • 1 1 1 1 • ' 1 1 1 • 1 1 • 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 ppm Figure 4.24 JH NMR spectrum (500 MHz) of 21 in CD2C12 at 20°C. Note: 21 is in equilibrium with x6a (8 3.09, NMe2) and free *EtSH ((8 2.55 (dq), CH3C#2SH; 8 1.46 (t), CH3CH2S#; 8 1.31 (t), C#3CH2SH); • = 8 2.1 (C#3)2CO. these correlations was performed by a 2D COSY JH NMR experiment. The further splitting of the H , doublet of doublets at 8 0.65 into doublet of doublet of doublets is due to coupling of H a to a P-atom. As the structure of 21 is similar to that of 18a, the H 2S analogue, H . is assumed to be coupled to PA with a small coupling constant 3JB^A = 1.92 Hz due to the small dihedral angle of 69.81° between the P(l)-Ru-S and Ru-S-H(l) planes. When a XH{ 3 1 P}NMR spectrum was measured (Figure 4.26(b)), H a is partially decoupled to P A . 143 References on page 169 Chapter 4 Ha, ( d d * = 7.36 Hz Hb, (m): 2 J H B H C = 13.74 Hz 3 J H b H a = 10.74 Hz ^ = 7 . 3 6 Hz (a) // (b) // 2.00 Ho, (m): J H c H b = 13.74 Hz H , , (ddd): 3 J H a H b = 10.74 Hz 3T 5.83 Hz ^ = 5 . 8 3 Hz ^ = 7.36 Hz J J H a P A = 1.92 Hz 0.90 0.80 0.70 0.60 0.50 ppm Figure 4.25 *H NMR spectra of 21 (500 MHz, CD2C12). Spectra only show resonances due to the protons of coordinated EtSH: (a) simulated spectrum; (b) expanded regions from actual spectrum, Figure 4.24. 144 References on page 169 Chapter 4 , 1 , , , , 1 , , 1 . 1 . 1 . . 1 . i i i 1 ' ' ' r-0.68 0.66 0.64 0.62 0.60 ppm Figure 4.26 ! H NMR resonance of Ru-S-FL. in cw-RuCl2(P-N)(PPh3)(EtSH) (21): (a) J H NMR spectrum; (b) 'H^PJNMR spectrum (500 MHz, 20°C, CD2C12). 4.3.3 In situ Preparation of Cis-RuCl2(P-N)(PPh3)(RSH) Species, R = n-Pr, i-Pr, n-Pn, n-Hx, Bz To expand the series of coordinated thiol complexes, longer alkyl chain thiols were reacted with RuCl2(P-N)(PPh3) (6a). Addition of excess RSH (R = w-Pr, i-Pr, w-Pn, w-Hx, Bz) to a solution of 6a in CDC13 or CeD6 yielded yellow solutions. Attempts to isolate products were unsucessful because of the facile loss of RSH, but the 31P{1H} NMR spectra of the in situ reactions indicate the formation of the thiol adducts, cw-RuCl2(P-N)(PPh3)(RSH) (22 - 26). The *H NMR spectra were uninformative because product peaks were obscured by those of added excess thiol required for product formation. The 31P{1H} NMR chemical shifts of RuCl2(P-N)(PPh3)(RSH) depend very little on the nature of the thiol as shown in Table 4.9. 145 References on page 169 Chapter 4 Table 4.9 31P{XH> NMR chemical shifts (121.4 MHz) for czs-RuCl2(P-N)(PPh3)(RSH),in the presence of added RSH (except for data labeled unknown) at 20°C. RSH 5 P A (P-N) 8 P B (PPh3) 2 JPP(HZ) Solvent H2S,(18a) 51.28 44.53 29.50 C 6 D 6 MeSH, (20) 51.49 45.58 29.63 C 6 D 6 EtSH, (21) 51.17 42.75 29.50 C 6 D 6 w-PrSH, (22) 51.22 42.46 30.05 CDC13 z-PrSH, (23) 49.58 41.68 30.23 C 6 D 6 unknown A (trans isomer ?) 56.76 46.84 36.54 C 6 D 6 unknown B (impurity ?) 51.31 42.74 29.93 C 6 D 6 H-PnSH, (24) 51.30 42.84 29.63 C 6 D 6 unknown C (trans isomer ?) 49.57 46.35 36.06 CeDe n-HxSH, (25) 51.15 42.57 30.23 CDC13 BzSH, (26) 50.16 42.03 30.41 CDC13 With the exception of z-PrSH and zz-PnSH, all reactions of RuCl2(P-N)(PPh3) (6a) with RSH gave single products of the type cw-RuCl2(P-N)(PPh3)(RSH). The 31P{1H} assignments were based by comparison with those for the characterized H2S, MeSH and EtSH complexes. Figure 4.27 shows the 31P{1H} NMR spectra for reactions of 6a with z'-PrSH and w-PnSH. Unknown A and C are probably the zra«s-RuCl2(P-N)(PPh3)(RSH) isomers because of the similarity of the larger coupling constants 2JpP (-36 Hz) to those of other trans complexes such as *rc*ra-RuCl2(P-N)(PPh3)(L) (L = H 20, MeOH and EtOH); see also Sections 5.3 and 5.6.27b Unknown B perhaps results from impurities in the z'-PrSH used. 146 References on page 169 Chapter 4 A A i 24 24 | — i — i — i — i — | — i — i — i — i — | — r — l — I — I — | — i — I — i — i — | — i — i — i — i — | — i — i — i — i — | 60 55 50 45 40 35 ppm Figure 4.27 3*P {1H} NMR (300 MHz) spectra of in situ reactions of 6a with (a) z'-PrSH and(b) w-PnSH in CeDg at 20°C. Clearly, the steric bulk of RSH plays an important role in the coordination of thiols to 6a, as the cw-RuCl2(P-N)(PPh3)(RSH) complexes are not isolable as the R group becomes more bulky. No reactions were observed when excess PhSH or thiophene were added to 6a in CDCI3. The reaction solutions remained green and the 31P{1H} NMR spectra showed only the presence of 6a. 147 References on page 169 Chapter 4 4.4 Comparison of Coordinated S-H Vibrational Frequencies for 18a, 18b, 19a, 20 and 21 The vibration modes for a triatomic molecule are shown in Figure 4.28. In the IR spectrum of gaseous H2S, absorptions at 2629, 2615 and 1180 cm"1 were assigned as the U i o 2 ^ 3 stretching bending stretching symmetric antisymmetric Figure 4.28 The vibrational modes for H2S (or any bent triatomic molecules). V3, vi and v 2 bands, respectively.41 The infrared spectra of 18a, 18b, 19a, 20 and 21 were obtained from solid KBr pellets of each sample. The VS-H frequencies of each complex and those of the gaseous H2S or thiol are listed in Table 4.10. Upon coordination of H2S, vi and V3 can still be observed while v 2 is obscured by other bands of the spectrum. For gaseous MeSH and EtSH, only one stretching band (vi) is observed for each at 2580 and 2573 cm"1, respectively.31 In all cases but one (including literature data from Sections 4.1.1 and 4.1.2), coordination to transition metals results in lower wavenumbers that are consistently in the range of 2423 to 2590 cm"1 for H2S and thiol complexes; the exception is in the much lower frequencies of 2290 and 2410 cm'1 reported for [Ru(SH2)(PPh3)'S4'] which were attributed to hydrogen-bonding to O-and S-atoms (Section 4.1.1).3 148 References on page 169 Chapter 4 Table 4.10 VS-H (cm'1) frequencies (vi and v 3 bands) for H2S and Thiols, in the free gaseous state and upon coordination to Ru cw-RuX2(P-N)(PR3)(L) VS-H of Gaseous L (cm"1) VS-H of Coordinated Complex (cm"1) R = Ph,X = C L L = H2S (18a) R = Ph,X = Br,L = H2S (18b) R = /7-tolyl, X = CI, L = H2S (19a) R= Ph, X = CI, L = MeSH (20) R = Ph, X = CI, L = EtSH (21) 2615 (vi), 2629 (v3) 2615 (vi), 2629 (v3) 2615 (vi), 2629 (v3) 2580 2573 2506 (vi), 2476 (v3) 2506 (vi), 2476 (v3) 2495 (vi), 2449 (v3) 2533 2516 The substitution of CI by Br (18a —» 18b) does not affect V i and v3, but substitution of Ph by p-Xo\y\ (18a -» 19a) results in significantly lower V SH stretching frequencies, possibly because of increased SH/TC interactions between H 2S protons and the ring system of the p-io\y\ group. Unfortunately, a direct comparison between structures of 18a and 19a can not be made because only one H-atom of the coordinated H 2S was located in 19a. 4.5 The UV-Vis Spectra of RuX2(PN)(PR3) (X = halogen; PN = P-N, PAN or AMPHOS; R = Ph or p-to\y\) and Cis-RuX2(P-N)(PPh3)(L) (L = H 2S, MeSH or EtSH) Species UV-Vis spectroscopy is a good tool to observe the occurrence of a reaction in this type of chemistry. The five-coordinate, square pyramidal complexes, RuX2(PN)(PR3), studied in this work have characteristic X\ (450 to 460 nm) and X2 (622 to 780 nm) bands (Table 4.11). Upon coordination of L to RuCl2(P-N)(PPh3), Xi shifts to a shorter wavelength and X2 is no longer observed in the 300 to 820 nm region. 149 References on page 169 Chapter 4 Table 4.11 Xi and X2 UV-Vis bands for RuX2(PN)(PPh3)(L) in CH2C12 RuX2(PN)(PR3)(L) (nm) E l ( M 1 cm-1) x2 (nm) e2 ( M 1 cm"1) X = CLPN = P-N, R = Ph, L = vacant (6a) 454 1100 678 480 X = Br, PN = P-N, R = Ph, L = vacant (6b) 472 1170 706 615 x = I,PN = P-N, R = Ph, L = vacant (6c) 510 900 774 510 x = C1,PN = P-N, R = p-tolyl, L = vacant (7a) 452 1155 672 555 x = Br, PN = P-N, R = p-tolyl, L = vacant (7b) 474 1150 700 560 x = I,PN = P-N, R = p-tolyl, L = vacant (7c) 512 780 780 435 x = C1,PN = PAN, R = Ph, L = vacant (9) 450 1210 622 490 x = C1,PN = PAN, R = p-tolyl, L = vacant (10) 450 1280 622 520 X = CI, PN (prepared in = AMPHOS, R = Ph, L = vacant, (12) situ) 460 1050 636 570 X = CLPN = P-N, R = Ph, L = H 2S a (18a) 426 830 - -X = Br, PN = P-N, R = Ph, L = H 2S a (18b) 446 995 - -x = CLPN = P-N, R = /?-tolyl, L = H 2S a (19a) 435 900 - -X = Br, PN = P-N, R = p-tolyl, L = H 2S a (19b) 452 935 - -x = CI, PN = P-N, R = Ph, L = MeSH8 (20) 424 835 - -x = C1,PN = P-N, R = Ph, L = EtSHa (21) 424 830 - -"Measured in the presence of excess sulfur ligand. Figure 4.29 shows the absorption spectra before and after the addition of H2S to RuCl2(P-N)(PPh3) (6a). The band originally at Xi = 454 nm (e = 1100 M 1 cm"1) shifts to 426 nm (e = 830 M 1 cm"1) while the absorption at X2 = 678 nm (s = 480 M 1 cm'1) is no longer observed. Although low spin d6 Ru(JJ) is a good n donor, the electronic bands observed for all the complexes are mostly likely due to halogen to metal charge transfer 150 References on page 169 Chapter 4 transitions, as the energies decrease in the sequence CI > Br >I (Table 4.11), in parallel with the ionization energies of the halide ions. Upon coordination of the sulfur ligands, the A.2 band may have shifted to lower energy transitions. 3.0 6a 18a 4 5 4 1 1 1 1 1 426 nm 6a 678 nm 580 630 W avelength (nm) Figure 4.29 UV-Vis spectra for RuCl2(P-N)(PPh3) (6a) and cz5-RuCl2(P-N)(PPh3)(SH2) (18a) in CH2C12 at 20°C. The formation of cz\s-RuCl2(P-N)(PPh3)(SH2) (18a) and its distinctive UV-Vis spectrum were thought to provide an opportunity to study the kinetics and provide information on the binding of H2S. However, formation of 18a proved to be too fast for study by UV-Vis spectroscopy because of the 'immediate' completion of the reaction upon the addition of 1 atm H2S to RuCl2(P-N)(PPh3) (6a). Repeated attempts to slow the reaction sufficiently at lower temperatures down to -10°C were also unsuccessful for monitoring the rate of formation of 18a. Stopped-flow experiments were also performed by injections of separate, more dilute solutions of H 2S and 6a into the spectrophotometer. However, even with rigorous exclusion of air, the samples tended to decompose and reproducible data could 151 References on page 169 Chapter 4 not be obtained; furthermore, these experiments were not pursued because of the offensive odour and therefore non-containability of the toxic H2S. 4.6 Solution Thermodynamics for Reversible Formation of H2S and Thiol complexes The affinities of RuX2(P-N)(PR3) for L = H2S, MeSH and EtSH can be compared by determining the equilibrium constant, K, for the following equilibrium equation: K ^ RuCl2(P-N)(PPh3) + L c/5-RuCl2(P-N)(PPh3)(L) Equilibrium concentrations were obtained from *H NMR integrations of each species, the samples being prepared by dissolving c/'s-RuCl2(P-N)(PPh3)(L) in C 6 D 6 or C7D8 and under 1 atm Ar. K values were determined at various temperatures (within the range 10 - 70°C) and AH° AS° the corresponding Van't Hoff plots (Van't Hon equation: InK = - +——) are given in RT R Figure 4.30. As an example of the determination of K, Figure 4.31 illustrates the ! H NMR spectra showing the region of interest for the c/5-RuCl2(P-N)(PPh3)(SH2) (18a) system at 20, 36 and 50°C. As the temperature is raised, the integrations of the signal due to 6a (6 3.07, NMe2) and free H2S (8 0.30) increase while those of 18a (8 3.67, 2.97, NMe2; 8 1.02, Ru-SH2) decrease; that is, formation of 18a is exothermic. The equilibrium expression for the [18a] formation of 18a is: K = T i r _ r T T . Because [Ru]toui is known (= [18a] + [6a]), and [6aJ[H2S]s x _ [18a]_ —a / _ 3— _ —e_ / 2— _ J^a] _ ( P — 6 ^ e c a i c u i a t e ( j [6a] (p-a) /6 (p-a) /6 [mS], © / 2 xy(l + x) K = — can be determined (a, P, e and co are integrated peak areas of the resonances [Ru]total shown in Figure 4.31). Of note, [6a] = |Ti2S]rac0ordinated = [H2S]S + [H2S]hs (s refers to H2S dissolved in solution, while hs refers to H2S in head space of the NMR tube), although 152 References on page 169 Chapter 4 Figure 4.30 Van't Hoff plots for the K equilibria (see p. 42) for (a) 18a, (b) 18b, (c) 19a, (d) 20 and (e) 21 in C 6D 6 . Bars indicate estimated error based on repeated experiments. Data for each complex were collected from a minimum of three experiments with the average values plotted. 153 References on page 169 Chapter 4 6a (a) 20°C (b) 36°C (c) 50°C i i i i I i i i i l i i i i I i i i i l i i i i I i i i i I i i i i I i i i i I i i i i I i i i i I 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -0.5 Figure 4.31 *H NMR spectra in the region 8 -0.5 to 4.5 (300 MHz, C 6D 6) for the equilibrium between 18a, 6a and H2S at (a) 20°C, (b) 36°C and (c) 50°C. 154 References on page 169 Chapter 4 this relationship is not needed for calculation of the K values. Some raw data for the equilibrium calculations involving 18a, 18b, 19a, 20 and 21 are given in Appendix XI. Table 4.12 gives AH°, AS° and AG° data for the formation of 18a, 18b, 19a, 20, and 21. Ignoring the effects of the trans to cis halide rearrangement on the thermodynamics, the negative AS° values are consistent with binding of a small molecule to a metal site, while the low value exothermicities imply relatively weak Ru-S bond energies. At 25°C, the relatively large magnitude of K = 296 M 1 (AG0 = -14 kJ/mol) indicate 20 is most thermodynamically favoured. In solution, the tendency for MeSH to dissociate is relatively weak, and this fact is confirmed by qualitative, visual observations and by UV-Vis spectroscopy: when 20 was dissolved in solution, the solution remained yellow, characteristic of cz's-RuCl2(P-N)(PPh3)(L), while when 18a, 18b, 19a or 21 was dissolved, the solution become green, characteristic of the five-coordinate RuX2(P-N)(PPh3). Table 4.12 Thermodynamic parameters for the formation of c/5-RuX2(P-N)(PR3)(L) in CeD6. Errors for K were estimated from repeated experiments; and errors for AH° and AS° were estimated from maximum and minimum slopes and intercepts of Van't Hoff plots, respectively. RuX2(P-N)(PR3)(L) K(25°C) M 1 AG 0 (25°C)a kJ/mol AH°b kJ/mol AS o C J/mol K R = Ph,X = Cl ,L = H2S (18a) 153 ± 5 -12.5 + 0.1 -46 + 4 -112 + 14 R = Ph,X = Br,L = H2S (18b) 51+4 -9.7 + 0.2 -33 ± 4 -77 + 13 R = ^ -tolyl, X = CI, L = H2S (19a) 120 + 15 -11.9 + 0.3 -54 ± 9 -140 + 35 R= Ph, X = CI, L = MeSH (20) 296 ± 20 -14.1+0.2 -28 ± 3 -48 ± 10 R = Ph,X = Cl ,L = EtSH (21) 154 ± 8 -12.5+0.1 -22 ± 4 -32 ± 14 aAG° values are calculated from the equation AG° = -RTln(K). bAH° and CAS° values are obtained from the slopes and intercepts of the Van't Hoff plots shown in Figure 4.30, respectively. 155 References on page 169 Chapter 4 The choice to use CeD6 rather than chlorinated solvents such as CD2CI2 or CDCI3 was governed by the fact that samples in CeD6 gave better resolution and better separated peaks in the lH NMR spectra for integration purposes at 0°C or higher. Furthermore, the reproducibility of K values in the chlorinated solvents is poor. 4.7 The Ru-S Bond Strengths in the Solid State: DSC Experiments Differential scanning calorimetry (DSC) measures the difference in temperature between a sample and an inert reference material as a function of temperature.42 Quantitative enthalpy changes may be obtained from a DSC cell if the sample and reference temperatures are maintained at the same temperature during heating and extra heat input into the sample (if endothermic) or to the reference (if exothermic) is measured. When solid samples of 18a, 20 or 21 (which exists as acetone solvated species, Section 2.8) are heated in the DSC chamber under N 2 , the enthalpy change (AH°) for the loss of H2S, MeSH or EtSH (ignoring loss of the acetone) is measured, respectively. The DSC curves for the thermal reactions are shown in Figure 4.32. The Ru-S bond strengths in 18a (85 ± 2 kJ/mol) and 20 (94 ± 2 kJ/mol) are comparable, while the bond is weakest in 21 (64 + 3 kJ/mol), possibly due to the increased size of the EtSH ligand. Of note, the formation of 21 from the five-coordinate precursor in solution also reveals the smallest exothermicity; however, the solid state reactions are thought to be of a somewhat different nature. The loss of H2S or thiols can also be visually observed when solid samples of 18a, 20 or 21 are placed under vacuum and heated at 50°C for 2 h. During this time, the originally yellow solids become green materials which are air-sensitive and instantaneously decompose to uncharacterizable black powders once exposed to O2. When the green solids are dissolved in solution (e.g. CDCI3), only the five-coordinate complex zraw5-RuCl2(P-N)(PPh3) (6a) is 156 References on page 169 Chapter 4 I I 3 0.80 0.40 + 0.00 4--0.40 -0.80 -1.20 -1.60 50 L = EtSH, 21 L AH° (kJ/mol) H2S 85 ± 2 MeSH 94 + 2 EtSH 64 + 3 i 1— 70 1 90 L = H2S, 18a 110 130 Temperature °C L = MeSH, 20 — I 1— 150 170 Figure 4.32 DSC curves for c/s-RuCl2(P-N)(PPh3)(L) complexes. Samples are heated in an N 2 atmosphere (flow rate = 40 cc/min) at a rate of 5°C/min to 200°C. observed by NMR spectroscopy. It is reasonable to assume that the air-sensitive, green solid is c/s-RuCl2(P-N)(PPh3) and that it rearranges to the trans isomer in solution. A proposed scheme for the chemistry is shown in Figure 4.33. Differences in the AH° values determined by the solution and solid state methods are then attributed to the enthalpy change on converting this cis- to trans-isomer in the solid state. Thus, by comparison of the AH° values obtained from solution (ignoring any solvation effects on the 5- and 6-coordinate species) and those obtained by solid state DSC, AH° for the conversion of the cis to the more thermodynamically stable trans-chloro RuCl2(P-N)(PPh3) isomer is in the range -39 to -66 kJ/mol. These values are of the same order of magnitude as those for the solid phase 157 References on page 169 Chapter 4 isomerizations of rraws-RuCl2(CO)(RP)3 to czs-RuCl2(CO)(RP)3 (R = Ph2Me, PhMe2, Me3; AH° values are -15, -21 and -48 kJ/mol, respectively);43 P h 2 p \ ...NMe 2 a—p*!£r—ci Phsl Ph2?' Cl—pBHf L P h s P ^ CI L = H2S, MeSH or EtSH yellow PteP' ,...NMe2 CI—— ?Ru" P h a P ^ CI proposed "cis" structure green in solution. in air 6a green decomposition Figure 4.33 Proposed reaction scheme for the loss of L from solid m-RuCl2(P-N)(PPh3)(L). 4.8 The Acidity of RuCI2(P-N)(PPh3)(H2S): Proton Abstraction with Proton Sponge R 2N NR 2 R = alkyl or aryl Figure 4.34 Structure of a typical proton sponge. Proton sponges are strong bases containing a naphthalene structure with amine groups in the 1- and 8- positions (Figure 4.34). Because of their high basicity, non-coordinating behaviour towards metal ions (as a consequence of its steric bulk), and the favourable formation of strong N—H—N hydrogen bonds upon proton transfer, proton sponges abstract protons effectively from acidic moieties.44 In fact, reactions via coordination of proton sponges to metal centres have appeared infrequently in the literature.45 In this thesis work, l,8-bis(dimethylamino)naphthalene (pK» of conjugate acid = 12.3 in H20), herein referred to 158 References on page 169 Chapter 4 as PS, was used. No reaction was observed spectroscopically, when PS is added to a solution of RuCl2(P-N)(PPh3) (6a) in CDC13. In accord with the reaction of RuCl2(PPh3)3 and H 2 in the presence of added base to produce Ru(H)Cl(PPh3)3 (Figure 4.35(a)),46 Mudalige et al. have shown that the reaction of RuCl2(P-N)(PR3) and H 2 in the presence of PS affords the hydride Ru(H)Cl(P-N)(PR3) via the r| 2-H 2 intermediate (Figure 4.35(b)).27 The use of external bases to deprotonate dihydrogen complexes has been primarily aimed at studying the thermodynamic acidity or p K a values of such systems. Common bases used in the literature for such experiments include alkoxides (MeO', EtO', 'BuO), phosphines (P'Bu3, P"Bu3, PCy3), amines (NEt3), and metal hydrides (Ru(H)Cp(PPh3)2, Ru(H)Cp(dppm)).47 Analogously, in the present study, it would be beneficial to obtain Ru(SH) species (Figure 4.35(c)) in order to determine the acidity of RuCl2(P-N)(PPh3)(SH2) and, in turn, evaluate the strength of the S-H bonds in the coordinated H2S complex. (a) RuClzfPPhj^  + H 2 + base +» Ru(H)Cl(PPh3)3 + baseH+Cl" base = NMe 3 or D M A (b) RuCl2(P-N)(PPh3)(rr-H2) + PS „ Ru(H)Cl(P-N)(PPh3) + PSH+Cf Ru(SH)Cl(P-N)(PPh3) + PSH+C1" (c) RuCl2(P-N)(PPh3)(SH2) + PS e q - or [Rud2(SH)(P-N)(PPh3)]"PSH+ Figure 4.35 (a), (b) Dihydrogen activation by Ru(II) complexes in the presence of added base, and (c) abstraction of proton from RuCl2(P-N)(PPh3)(SH2). In organic solvents such as CDC13, CD2CI2, C6D 6 , or d6-acetone, there is no reaction observed between H2S and PS, implying that H2S ( p K a = 7 (in aqueous media)) is not a strong acid in these solvents. Similarly, PS does not deprotonate CH3COOH ( p K a = 4.7 (in aqueous media)) in CDC13. Although a direct comparison of acidity cannot be made between values 159 References on page 169 Chapter 4 obtained in organic and aqueous solutions, studies have shown that p K a values are related linearly.48'49 For example, the p K a values of hydride complexes are related by the expression pKa(H 2 0) = pKa(MeCN) - 7.5.48 In the present study, CD2C12 was chosen as solvent because it dissolves all the species in equlibrium (Figure 4.35(c)) and is noncoordinating. In theory, the p K a value of c/s:-RuCl2(P-N)(PPh3)(SH2) may be obtained by evaluating the equilbrium constant (Figure 4.35(c)) and applying the following equation: p K a = pK*, + pKPsH+, where p K a for the H2S complex and pK P S H + are on the same acidity scale.47'50 For ease of comparison, all values are discussed on the aqueous scale. At 20°C, the addition of 1 atm H2S to RuCl2(P-N)(PPh3) (6a) in the presence of 3 equivalents PS in CD2C12 generated in situ a new species observed as an AX pattern at 8 82.25 and 8 57.88 ( 2JP P = 34.05 Hz) in the ^Pl/H} NMR spectrum (Figure 4.36 (b)), different from that of cw-RuCl2(P-N)(PPh3)(SH2) (18a) (Figure 4.36 (a)). However, this new, yellow species, 30, is only stable within 10 min of H2S addition; after this time, the 31P{1H} NMR signals are no longer observed. 30 decomposed rapidly to a dark brown solution with formation of a white precipitate. The dark brown solid isolated from the filtrate did not give any 31P{1H} NMR signals, while broad peaks (8 6.5 - 8.2, phenyl region and 8 1.5 - 3.8) in the ! H NMR spectrum are indicative of a paramagnetic Ru(III) species. This observation perhaps resembles the decomposition of [Ru(NH3)5(SH2)][BF4]2 to [Ru(NH3)5(SH)][BF4]2 and H 2 (Section 4.1.1),2 although in the current system no H 2 was observed. The *H NMR spectrum of the white precipitate in CDC13 is that of PSIfCf. The *H NMR spectra of PS (8 7.35, 6.92 (6H, m, phenyl); 8 2.80 (12H, s, NMe)) and PSlTCf (8 12.2 (1H, br, PS/T); 8 7.95, 7.80, 7.65 (6H, m, phenyl); 8 3.38 (12H, s, NMe)) in CDC13 are shown in Figure 4.37. Evidently, PS does abstract proton from H2S with concomitant decomposition of the Ru complex. 160 References on page 169 Chapter 4 (a) 30 (c) J l v (d) 18a 1 18a (e) v. I I I I I I I I I I I I I I I I I I I I I I I I I I I I M I I I I I I I I I I I M I 1 I I I I I I I I I I I I I I I I I i I 1 I I I I 1 I 90 80 70 60 50 40 30 ppm Figure 4.36 31P{*H} NMR (300 MHz, CD2C12) spectra for various Ru(II) complexes containing sulfur ligands: (a) RuCl2(P-N)(PPh3)(SH2) at 20°C; RuCl2(P-N)(PPh3) + 3PS + 1 atm H2S at (b) 20°C, (c) -25°C, (d) -60°C and (e) -70°C (There is slow decomposition of 27a and 30 even at low temperatures). *Broadening of the P A peak of 18a is only observed with the Varian XL300 spectrometer and not with the Bruker AMX500 spectrometer (Figure 4.12). 161 References on page 169 Chapter 4 phenyl region NMe 1 (a) CHCh \ PS/T phenyl region NMe (b) 12.0 10.0 8.0 6.0 ppm 4.0 2.0 Figure 4.37 X H NMR spectra (200 MHz, CDC13, r.t.) of (a) PS and (b) PSlfCT. Attempts to isolate 30 were carried out at -78°C. On addition of 1 atm of H2S to a stirring solution of RuCl2(P-N)(PPh3) (6a) and 1 or 3 equivalents PS in CD2C12, a bright yellow solution formed. Addition of hexanes at -78°C resulted in the precipitation of a dark yellow-brown solid. When the suspension was filtered at ~ -20°C, the yellow solid thermally decomposed to a dark brown powder. Of note, the 3IP{1H} NMR spectrum of the above reaction in situ at -30°C or lower denotes the presence of three species (Figure 4.36 (c)-(e)). The three sets of AX signals indicate the presence of 18a, 30, and an unknown 27a [8 54. (PA); 8 46.06 (Px); 2 J P P = 30.96 Hz]. To rationalize the 31P{1H} NMR data, a proposed reaction scheme is shown in Figure 4.38; this suggests the formation of Ru(SH)Cl(P-N)(PPh3) (27a) as an intermediate en route 52 162 References on page 169 Chapter 4 a—pRii—ci + H 2S 6a 2 ^ . N Rii'- -SH, a 18a (a) ph3pr . N R l i ' - -SH, a 18a + PS Ph3PjT . N RH'- SH + PSH TQ" 27a (b) . N Q — ^ R u — S H + H2S Ph 3pr 27a C I -ph3pr . N R u — S H SH2 30' (c) , N Ru" SH SH2 30' PS , .N "** HS——; Ru'—— SH + PSH + a (d) Ph3PjT 30 Figure 4.38 (a) Equilibrium for formation of RuCl2(P-N)(PPh3)(SH2) (18a); (b), (c), (d) are subsequent equilibria en route to the formation of Ru(SH)2(P-N)(PPh3) (30) in the presence of added PS. Note: the speculative species 30' was not observed by NMR. 163 References on page 169 Chapter 4 to a bis(mercapto) species Ru(SH)2(P-N)(PPh3) (30). This scheme is supported by other in situ NMR data (see below). The presence of excess H2S ensures the complete formation of RuCl2(P-N)(PPh3)(SH2) (18a). K i has already been discussed in detail in Section 4.6 . The *H NMR signals of 27a in CD2C12 or de-acetone could not be assigned at -70 to -25°C because of overlapping peaks due to PS, PSrTCl' and NMe2 protons (from 18a and 30) in the region 5 2.5 - 3.5. Warming a d6-acetone solution of the low temperature samples to 20°C leads to complete formation of 30 and assignment of its J H NMR signals. A sharp singlet at 8 3.20 due to the NMe2 protons suggests a symmetrical square pyramidal structure similar to that of 6a. The SH signals were not observed even when the temperature was lowered to -70°C. Similarly, the reaction of RuBr2(P-N)(PPh3) (6b), PS and H 2S gives Ru(SH)Br(P-N)(PPh3) (27b) and 30. Further evidence for the formation of 30 was provided by reaction of RuCl2(P:N)(PPh3) (6a) or RuBr2(P-N)(PPh3) (6b) with excess NaSH-xH20 in dVacetone at 20°C. The fact that the same product was formed regardless of the halogen involved is significant; i.e., both halogens from 6a and 6b are displaced by SH. The initial formation of Ru(SH)Cl(P-N)(PPh3) (27a) and Ru(SH)Br(P-N)(PPh3) (27b) was also evident when 6a or 6b was reacted with excess NaSH-xH20 at-70°C. The^Pl/H} NMR chemical shifts of 27a are shifted marginally downfield from those of 27b (Table 4.13). For these in situ reactions, assignment of *H NMR signals of 27a (5 3.27, 3.18 (6H, s, NMe) and 8-2.08 (2H, s, Ru-S#)) and 27b (8 3.56, 3.17 (6H, s, NMe) and 8-1.63 (2H, s, Ru-S#)) were possible because of the absences of overlapping peaks due to PS and free H2S. Although there is no evidence to indicate the existence of 30' as an intermediate, the initial coordination of an H2S molecule to 27a followed by deprotonation seems a logical route to the formation of 30. The initial exchange of CI' for SH" is less likely because there is no 164 References on page 169 Chapter 4 reaction between PS and H2S in the absence of the metal complex. Table 4.13 summarizes the 31P{1H} NMR chemicals shifts for 27a, 27b and 30 in d6-acetone; data for 27a and 30 in CD2CI2 are very similar (Figure 4.36). All the NMR experiments using hydrosulfide were carried out in ck-acetone because NaSH-xtbO is slightly soluble in d6-acetone and insoluble in CD2CI2. Table 4.13 31P{ *H} NMR chemicals shifts of Ru(U) mercapto complexes in d6-acetone. Complex T ( ° C ) 5 PA(P-N) 5 P B (PPh3) 2 JPP (Hz) RuCl(SH)(P-N)(PPh3) (27a) -70 55.70 45.79 31.93 RuBr(SH)(P-N)(PPh3) (27b) -70 56.62 46.16 30.48 Ru(SH)2(P-N)(PPh3) (30) 20 82.88 59.19 34.11 A variable temperature NMR study indicates that the formation of 27a is reversible while the formation of 30 is not. The integration ratio (31P{XH} NMR spectroscopy) of 27a and 18a decreases when the temperature is raised from -70°C to -50°C, but the same ratio re-appears when the temperature returns to -70°C. At 20°C, 30 is fully formed, and lowering the temperature gives no indications of the reversible formation of 18a or 27a. Repeated attempts to measure accurate equilibrium concentrations of 18a and 27a en route to calculating the equilibrium constant (K2) of formation were unsuccessful. Because 27a and 30 are thermally unstable and only observed in situ, their concentrations can only be measured by integrations in the 31P{1H} spectra at temperatures between -70 to -25°C. However, even at these temperatures, decomposition occurs (see Figure 4.36), resulting in broadened XH NMR shifts and very 'noisy' 31P{1H} NMR spectra. Even with long delay acquisition times of 4 s, there are discrepancies between 31P{1H} NMR integrations for repeated experiments. 165 References on page 169 Chapter 4 This matter was further complicated by the decrease in solubilities of the species involved at low temperatures. Because of these difficulties, the pKa of c/s-RuCi2(P-N)(PPh3)(SH2) (18a) could not be ascertained. However, it can be predicted and concluded that the acidity of H2S increases upon coordination to 6. In fact, the Ru complex seems to promote the reaction between H2S and PS; For example, the in situ reaction of RuCl2(P-N)(PPh3) (6a) with excess added H2S (100 equivalents) and PS (10 equivalents) in CD2C12 after 1 h resulted in the formation of 100 % PSH* (*H NMR singlet at 5 3.38 due to NMe groups; no *H NMR signal at 5 2.80 due to PS was observed) and decomposition of the Ru complex. The counter anion for PSFf is most likely to be CI" and SH"; there is a maximum of 2 equivs of CI" available for the 10 equivs PStT, although no SH" signal was observed in the *H NMR spectrum. Other bases such as triethylamine and 2,6-lutidine were used for attempted proton abstraction from 18a. However, the same results as described above were obtained. No reactions were observed when PS was added to solutions containing cw-RuCl2(P-N)(PPh3)(MeSH) (20) and czs-RuCl2(P-N)(PPh3)(EtSH) (21). The p K a values of uncoordinated MeSH (10.3)51 and EtSH (10.5)52 in aqueous solutions are larger than that of H2S (7)53. It thus appears that the acidities of MeSH and EtSH upon coordination to Ru are not affected to the extent required for reaction with PS. A stronger base than PS is perhaps required to deprotonate 20 and 21; the resulting thiolate species are likely to be more stable than the corresponding mercapto species. 4.9 Reaction of RuCl2(P-N)(PPh3) with S0 2 Previous work in this laboratory has shown that 6a reacts with S0 2 in CH2C12 to form c/s-RuCl2(P-N)(PPh3)(S02), isolable as a yellow-orange solid.2700 The "Pf/H} NMR chemical shifts (in CDC13) are at 6 39.02 (PA) and 8 37.88 (Px) ( 2 J p p = 24.77 Hz), while the *H 166 References on page 169 Chapter 4 NMR data show two signals at 8 3.50 and 8 3.28 for the NMe2 protons indicating a cis orientation of the CI ligands. Unlike previous small molecule binding reactions discussed in this Chapter, the S0 2 reaction is irreversible; this, coupled with IR data for the vSo bands (1287 and 1122 cm'1), suggests a co-planar bonding mode (r^-S) for the S0 2 ligand with the Ru. 5 4 4.10 Decompositon of as-RuCl2(P-N)(PPh3)(SH2) The H2S systems are very sensitive to 0 2 in solution. When 0 2 is added to a bright yellow CDC13 solution of c/5-RuCl2(P-N)(PPh3)(SH2) (18a) under 1 atm H2S, a dark green solution results. Precipitation with hexanes resulted in a green-brown solid that gave very 'noisy' 31P{1H) and J H NMR spectra. From the filtrate, a white solid was isolated by slow evaporation of the solvents; microanalysis was consistent with the formulation S=PPh3, and the 31P(1H> NMR spectrum (in CDC13) showed a singlet at 8 44.8. S=PPh3 was also isolated from the reaction of PPh3 with S8 5 5 and gave a 31P{1H} NMR signal, identical to that of the above species. Of interest, when a mixture of 0 2 and H2S (1:1 by volume injection) is added to a CH2C12 solution containing 18a and excess PPh3, the Ru complex catalytically converts all the PPh3 to S=PPh3 and then decomposes. The role that 0 2 plays is equivocal at this point, but the following reaction is envisioned: Ru H2S + PPh3 + V2 0 2 • SPPh3+H20. 167 References on page 169 Chapter 4 4.11 Summary In this Chapter, it was shown that Ru(II) H2S and thiol complexes can be formed and these are stable under ambient conditions. Thermodynamic parameters indicate that Ru-S bonds are weak. Sterically hindered S-ligands do not coordinate to RuCl2(P-N)(PPh3). Although the pKa of c/s-RuCl2(P-N)(PPh3)(SH2) was not determined, the acidity of H2S does apparently increase upon coordination as shown by reactions occurring in the presence of proton sponge. Deprotonation of the coordinated thiol groups does not occur. 168 References on page 169 Chapter 4 4.12 References 1. James, B. R. Pure Appl. Chem. 1997, 69, 2213. 2. Kuehn, C. G ; Taube, H. J. Amer. Chem. Soc. 1976, 98, 689. 3. (a) Sellmann, D.; Lechner, P.; Knoch, F. Angew. Chem.Int. Ed Engl. 1991, 30, 552. (b) Sellmann, D.; Lechner, P.; Knoch, F.; Moll, M. J. Am. Chem. Soc. 1992,114, 922. 4. Edwards, T. H.; Moncur, N. K.; Snyder, L. E. J. Chem. Phys. 1967, 46, 2139. 5. Ugo, R.; La Monica, G. Cenini, S.; Segre, A.; Conti, F. J. Chem. Soc. (A) 1971,522. 6. (a) Herberhold, M.; Suss, G. Angew. Chem. Int. Ed. Engl. 1976,15, 366. (b) Herberhold, M.; Suss, G. J. Chem. Res. (S), 1977, 246; J. Chem. Res. (M) 1977, 2720. 7. Vahrenkamp, H. In Sulfur - Its Significance for Chemistry, for the Geo-, Bio- and Cosmosphere and Technology, Muller, A.; Krebs, B., Eds.; Elsevier: Amsterdam, 1984, p. 121. 8. Harris, P. J.; Knox, S. A. R.; McKinney, R. J.; Stone, F. G. A. J. Chem. Soc. Dalton Trans. 1978, 1009. 9. Strohmeier, W.; Guttenberger, J. F. Chem. Ber. 1964, 97, 1871. 10. Raab, K.; Beck, W. Chem. Ber. 1985,118, 3830. 11. Urban, G ; Sunkel, K.; Beck, W. J. Organomet. Chem, 1985, 290, 329. 12. Crabtree, R. H.; Davis, M. W.; Mellea, M. F.; Mihelcic, J. M. Inorg. Chim. Acta 1983, 72, 223. 13. Amarasekera, J.; Rauchfiiss, T. B. Inorg. Chem. 1989, 28, 3875. 14. Kroener, R.; Heeg, M. J.; Deutsch, E. Inorg. Chem. 1988, 27, 558. 15. Park, H.; Minick, D.; Draganjac, M.; Cordes, A. W.; Hallford, R. L.; Eggleton, G.; Inorg. Chim. Acta 1993, 204, 195. 16. Conroy-Lewis, F. M.; Simpson, S. J. J. Chem. Soc, Chem. Commun. 1991, 388. 169 Chapter 4 17. Treichel, P. M.; Crane, R. A.; Haller, K. N . J. Organomet. Chem, 1991, 401, 173. 18. Treichel, P. M.; Schmidt, M. S.; Crane, R. A. Inorg. Chem. 1991, 30, 379. 19. Belchem, G.; Steed, J. W.; Tocher, D. A. J. Chem. Soc. Dalton Trans. 1994, 1949. 20. Darensbourg, M. Y.; Longridge, E. M.; Payne, V.; Reibenspies, J.; Riordan, C. G.; Springs, J. J.; Calabrese, J. C. Inorg. Chem. 1990, 29, 2721. 21. Winter, C. H.; Lewkebandara, T. S.; Proscia, J. W.; Rheingold, A. L. Inorg. Chem. 1993, 32, 3807. 22. (a) Collman, J. P.; Sorrell, T. N . ; Hoffman, B. M. J. Am. Chem. Soc. 1975, 97, 913. (b) Collman, J. P.; Sorrell, T. N . ; Hodgson, K. O.; Kulshrestha, A. K.; Strouse, C. E. J. Am. Chem. Soc. 1977, 99, 5180. (c) Collman, J. P.; Sorrell, T. N . In Concepts in Drug Metabolism; Jerina, D. M., Ed.; Am. Chem. Soc. Symp. Series, A. C. S., Washington, D. C , 1977, p. 27. 23. Byrn, M. P.; Katz, B. A.; Keder, N . L.; Levari, K. R; Magurany, C. J.; Miller, K. M.; Pritt, J. W.; Strouse, C. E. J. Am. Chem. Soc. 1983,105, 4916. 24. Stephan, D. W. Inorg. Chem. 1984, 23, 2207. 25. (a) Schlaf, M.; Morris, R. H. J. Chem. Soc, Chem. Commun. 1995, 625. (b) Schlaf, M.; Lough, A. J.; Morris, R. H. Organometallics 1996, 75, 4423. 26. Bartucz, T. Y.; Golombek, A.; Lough, A. J.; Maltby, P. A.; Morris, R. H.; Ramachandran, R; Schlaf, M. Inorg. Chem. 1998, 37, 1555. 27. (a) Mudalige, D. C ; Rettig, S. I; James, B. R.; Cullen, W. R. J. Chem. Soc, Chem. Commun. 1993, 830. (b) Mudalige, D. C. Ph.D. Thesis, The University of British Columbia, 1994. 28. Mudalige, D. C ; Ma, E. S.; Rettig, S. J.; James, B. R.; Cullen, W. R. Inorg. Chem. 1997, 36, 5426. 29. Osakada, K.; Yamamoto, T.; Yamamoto, A. Inorg. Chim. Acta 1985,105, L9. 30. Jessop, P. G.; Lee, C.-L.; Rastar, G.; James, B. R; Lock, C. J. L.; Faggiani, R. Inorg. Chem. 1992, 31, 4601. 31. Csizmadia, I. G. In The Chemistry of the Thiol Group, Parti; Patai, S., Ed.; John Wiley & Sons: Toronto, 1974, p. 7. 170 Chapter 4 32. Pauling, L. The Nature of the Chemical Bond; 3rd Ed.; Cornell University Press: Ithaca, N.Y. 1960. 33. Shaka, A. J.; Barker, P. B.; Freeman, R. J. Mag. Res. 1985, 64, 547. 34. Jessop, P. G.; Rettig, S. J.; Lee, C.-L.; James, B. R. Inorg. Chem. 1991, 30, 4617. 35. Jessop, P. G. Ph.D. Thesis, The University of British Columbia, 1991. 36. (a) Karplus, M. J. Chem. Phys. 1959, 30, 11. (b) Karplus, M. J. Am. Chem. Soc. 1963, 85, 2870. 37. Bentrude, W. G ; Setzer, W. N. In Phosphorus-31 NMR Spectroscopy in Stereochemical Analysis; Verkade, J. G ; Quin, L. D., Eds.; VCH Publishers, Inc.: Florida, 1987, p. 365, and references therein. 38. (a) Lipsch, J. M. J. G ; Schuit, G. C. J. Catal. 1969, 75, 179. (b) Angelici, R. Acc. Chem. Res. 1988, 21, 387. 39. Wong, T. Y. H.; Barnabas, A. F.; Sallin D.; James, B. R. Inorg. Chem. 1995, 34, 2278. 40. James, B. R.; Pacheco, A.; Rettig, S. J.; Ibers, J. A. Inorg. Chem. 1988, 27, 2414, and references therein. 41. (a) Allen, H. C; Blaine, L. R.; Plyler, E. K. J. Chem. Phys. 1956, 24, 35. (b) Allen, H. C; Plyler, E. K. J. Chem. Phys. 1956, 25, 1132. 42. West, A. R. Solid State Chemistry and its Applications; John Wiley & Sons: New York, 1984, p. 102. 43 . (a) Krassowski, D. W.; Nelson, J. H ; Brower, K. R.; Hauenstein, D.; Jacobson, R. A. Inorg. Chem. 1988, 27, 4294. (b) Krassowski, D. W.; Reimer, K.; LeMay, Jr., H. E.; Nelson, J. H. Inorg. Chem. 1988, 27, 4307. 44. (a) Hibbert, F. J. Chem. Soc. Perkin Trans. II1974, 857. (b) Alder, R. W.; Goode, N. C ; Miller, N. J. Chem. Soc, Chem. Commun. 1978, 89. (c) Hibbert, F.; Hunte, K. P. P. J. Chem. Soc. Perkin Trans. II1983, 1895. (d) Benoit, R. L.; Lefebvre, D.; Frechette, M. Can. J. Chem. 1987, 65, 996. (e) Staab, H. A.; Saupe, T. Angew. Chem.Int. Ed. Engl. 1988, 27, 865. 171 Chapter 4 (f) Brzezinski, B.; Grech, E.; Malarski, Z.; Sobczyk, L. J. Chem. Soc. Perkin Trans. II1991, 857. 45. (a) Gamage, S. N.; Morris, R. H ; Rettig, S. J.; Thackray, D. C ; Thorburn, I. S.; James, B. R. J. Chem. Soc, Chem. Commun. 1987, 894. (b) Joshi, A. M. Ph.D. Thesis, The University of British Columbia, 1990. 46. (a) Hallman, P. S.; McGarvey, B. R; Wilkinson, G. J. Chem. Soc (A) 1968, 3143. (b) James, B. R. Adv. Organomet. Chem. 1979, 77, 319. (c) James, B. R. In Comprehensive Organometallic Chemistry, Vol, 8; Wilkinson, G.; Stone, F. G. A ; Abel, E. W., Eds.; Pergamon Press: Oxford, 1982, Chapter 51. 47. Jessop, P. G.; Morris, R. H. Coord. Chem. Rev. 1992,121, 155, and references therein. 48. Kristjansdottir, S. S.; Norton, J. R. In Transition Metal Hydrides: Recent Advances in Theory and Experiment, Dedieu, A , Ed.; VCH, New York, 1991, Chapter 10. 49. Streuli, C. A. Anal. Chem. 1960, 32, 985. 50. (a) Guochen, J.; Morris, R. H. Inorg. Chem. 1990, 29, 582. (b) Guochen, J.; Morris, R. H. J. Am. Chem. Soc. 1991,113, 875. (c) Guochen, J.; Lough, A. J.; Morris, R. H. Organometallics 1992, 11, 161. 51. Kreevoy, M. M.; Harper, E. T.; Stary, F. E.; Katz, E. A.; Sellstedt, J. H. J. Org. Chem. 1964, 29, 1641. 52. Danehy, J. P.; Noel, C. J. J. Am. Chem. Soc. 1960, 82, 2511. 53. Subcommittee on Hydrogen Sulfide, Committee on Medical and Biologic Effects of Environmental Pollutants, Division of Medical Services, Assembly of Life Sciences, National Research Council in 'Hydrogen Sulfide,' Univeristy Park Press, Baltimore, 1979. 54. (a) Mingos, D. M. P. Transition Met. Chem. 1978, 3, 1, and references therein, (b) Kubas, G. J. Inorg. Chem. 1979,18, 182. 55. (a) Olah, G. A ; Berrier, A ; Ohannesian, L. Nouv. J. Chim. 1986,10, 253. (b) Wong, T. Y. H. Ph.D. Thesis, The University of British Columbia, 1996. 172 Chapter 5 Coordination of H 2 0 and Alcohols to RuCl2(P-N)(PR3) The coordination chemistry of H 20 has been extensively studied and is ubiquitous compared to that of H2S, in part because it is more pleasant and tractable to work with. In addition, the more weakly acidic H 20 is more stable with respect to the formation of hydroxides and oxides. In homogeneous catalytic systems, weakly coordinating ligands such as H 20, alcohols and other solvent molecules stabilize the vacant coordination sites of catalytic complexes prior to exchange with desired substrates.1 The reaction of H 2 0 with RuCl2(P-N)(PR3) (R = Ph, />tolyl) produces the stable H 2 0 adducts, fraws-RuCl2(P-N)(PR3)(OH2).2 From a structural point of view, the major difference between RuCl2(P-N)(PR3)(SH2) and RuCl2(P-N)(PR3)(OH2) is that the former contains cis Cl-atoms while the Cl-atoms of the latter are trans. In this Chapter, the aquo complexes are reported, characterized and compared to those of the complexes containing S-ligands discussed in Chapter 4. A probable mechanism for the coordination of H2S to RuCl2(P-N)(PR3) is deduced from these comparisons. 5.1 Preparation of 7rans-RuCl2(P-N)(PR3)(OH2) The aquo complexes, fraws-RuCl2(P-N)(PR3)(OH2) (R = Ph (33a), p-to\y\ (33b)), were initially prepared by Mudalige, previously of this laboratory, and she reported the X-ray structure of the R = />tolyl complex.2 Mudalige had formed in situ samples of 33a and 33b in CDC13 solutions of RuCl2(P-N)(PPh3) (6a) or RuCl2(P-N)(P(p-tolyl)3) (7a), respectively, and crystals of 33b formed in the NMR tube.2 During the course of this present thesis work, it was noted that crystals of 33a and 33b form easily in the presence of minute amounts of 173 References on page 202 Chapter 5 moisture in solutions and the complexes were further investigated. The aquo complexes are most conveniently prepared by stirring 6a or 7a in a mixture of acetone/H20 (4:1) under Ar (Sections 2.10.1 and 2.10.2). The precipitated and isolated pink solids analyse for the solvated species RuCl2(P-N)(PR3)(OH2)-(acetone). Heating these solids in vacuo at 80°C results in the removal of acetone and H 2 0 and formation of the green, unsaturated five-coordinate precursors 6a and 7a. The loss of H 2 0 is also demonstrated by the thermogravimetric analysis (TGA) of 33a (Figure 5.1). A weight loss of 11% between 80 to 110°C prior to thermal decomposition is a good approximation to the theoretical combined 9 % weight of acetone and H 2 0 present. 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0 Temperature °C Figure 5.1 TGA spectrum of 33a, depicting the loss of acetone and H 2 0 between 80° to 110°C. The sample was heated in a N 2 atm at a flow rate of 100 cc/min. 174 References on page 202 Chapter 5 The vi, v 2 and V3 vibrational bands for gaseous H 2 0 appear at 3657, 1595 and 3756 cm-1, respectively.3 Upon coordination of H 2 0, these vibrations emerge as sharp and intense bands at 3295, 1605 and 3556 cm-1 in the IR spectrum of 33a in the solid state (KBr). [These values differ from those of 3470 and 1739 cm-1 obtained by Mudalige for a CHC13 solution of 33a (KBr);2 perhaps she may have not recognized the extreme air-sensitivity of 33a in solution.] In the solid state, 33a and 33b can be formed reversibly by placing 6a or 7a in a moist atmosphere. However, the rate at which 33b forms is approximately three times faster than that of 33a, although this could well depend on particle size. Nevertheless, when green, powdered samples of 7a and 6a are placed in air, the pink solid 33b forms in < 3 min whereas formation of 33a takes > 15 min. The X-ray crystal structure of 7a indicates no agostic interactions between the Ru-atom and any ortho-phenyl hydrogen atoms from the P(/?-tolyl)3 ligand, and thus the species has an accessible, vacant sixth coordination site.2'4 Although many attempts to grow crystals of 6a were unsuccessful, the observation that 33a takes longer to form in the solid state perhaps infers that the sixth coordination site of 6a is occupied by an ort/70-phenyl hydrogen of the PPhj ligand. This type of agostic interaction has been observed in the very similar square pyramidal complexes RuCl2(PPli3)35, RuBr2(PPh3)3,6'7 RuCl2(dppb)(PPh3)6'7 and RuCl2(isoPFA)(PPh3).8 5.2 X-Ray Crystal Structures of rra»s-RuCl2(P-N)(PPh3)(OH2) (33a) Pink needle shaped crystals with a monoclinic unit cell, and yellow-brown prism shaped crystals with a triclinic unit cell, were isolated from a solution of 6a in CeHg under Ar. X-ray crystallographic analysis revealed the respective molecular formulas as rraw5-RuCl2(P-N)(PPh3)(OH2)-2C6H5 (I) and f7-a«5-RuCl2(P-N)(PPh3)(OH2)-1.5C6H6 (Tt). 175 References on page 202 Chapter 5 The PLUTO plots for the two structures are shown in Figure 5.2. Both types of crystals yielded very similar structures for the Ru moiety, and both of these are associated with two CeHe solvate molecules. The crystals of II were of superior X-ray quality than those of I and both H-atoms on the coordinated H 2 0 were isotropically refined in the former. While no interactions between the solvated CeHe molecules and the Ru moiety in I were found, a distance of 2.77(3) A between H(2) and C(40) in II indicates a probable OH/71 phenyl ring interaction. II Figure 5.2 PLUTO plots: orientations of CeHe molecules in the structures of 33a (fr-am-RuCl2(P-N)(PPh3)(OH2)-2C6H6 (I) and fra«s-RuCl 2(P-N)(PPh 3)(OH 2)-1.50^ (II)). The ORTEP plot of H, which is very similar to that of I, is shown in Figure 5.3 and reveals a pseudooctahedral geometry around the Ru with trans-chloro ligands and the H 2 0 176 References on page 202 Chapter 5 C(33) Figure 5.3 The ORTEP plot of RuCl2(P-N)(PPh3)(OH2)-1.5C6H6(33a (II)). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some of the phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix VIII. 177 References on page 202 Chapter 5 trans to the P-atom of the P-N ligand. Selected bond lengths and angles of I and II are shown and compared with those of frara-RuCl2(P-N)(PG>tolyl)3(OH2) (33b)2 in Tables 5.1 and 5.2, respectively. The Ru-O(l) bond of II is significantly shorter (2.187 A) than those of I (2.238 A) and 33b (2.252 A), but is intermediate between those weakly bound aquo ligand complexes (e.g. fra«5-[Ru(H20)(PEt3)2(trpy)][C104]2 (2.218 A, trpy - 2,2',2"-terpyridine)9 and [Ru(Ti6-MeC6H4Pr':p)(H20)(L)][C104] (2.203 A, HL = (S)-(a-methylbenzyl)salicylald-imine)10) and strongly coordinated aquo complexes (e.g. [RuH(H20)(CO)2(PPh3)2]X (2.15 A) , 1 1 [Ru(ti6-C6H6)(H20)3][S04] (2.127 A) , 1 2 R u C r l a O M V C O ^ C C C ' ) -OCOCH2CH=CHCH3)2 (2.141 and 2.115 A) , 1 3 [Ru(H20)6][OTs]2 (2.122 A, OTs = />toluenesulfonate),14 and [(cod)Ru(H20)4][OTs]2 (2.158 and 2.095 A) 1 5). Evidently, the close approach of the solvated benzene rings to the coordinated H 2 0 ligand of II results in the contraction of the Ru-0 bond. This shorter Ru-0 bond of II imposes the following structural consequences: (i) Strong intramolecular hydrogen bonds between the H 2 0 ligand and the trans-Cl-atoms are formed. The H(1)-CI(1) and H(2)-C1(2) bonds are 2.43 A (2.79 A for 33b) and 2.76 A (2.84 A for 33b), respectively, (ii) The coordinated O-H bonds are 0.74 and 0.81 A, significantly shorter than those of free H 2 0 (0.956 A) and the H-O-H angle contracts from 105° (free H 20) to 97.5°; this is perhaps because of volume restrictions imposed by the close proximity of the Cl-atoms and the solvated benzene rings, (iii) Mutual repulsion of the O and Cl(l) atoms results in a larger Cl(l)-Ru-0 angle of 85.40° (82.47° for I and 81.6° for 33b) and a smaller Cl(2)-Ru-0 angle of 80.63° (83.87° for I and 82.2° for 33b); as a result, the Cl(l)-Ru-P(l) angle is substantially smaller at 88.02° compared to 104.11° of I and 104.30° of 33b. Repulsion between Cl(2) and O also results in a smaller Cl(2)-Ru(l)-P(2) angle of 86.97° (98.88° for I and 96.26° for 33b). 178 References on page 202 Chapter 5 Table 5.1 Selected bond lengths (A) for /ra«5-RuCl2(P-N)(PPh3)(OH2)-2C6H6 (I), trans-RuCbCP-^CPP^XOH^-LSCeHs (tt) and ?ra«5-RuCl2(P-N)(P(p-tolyl)3(OH2) (33b) with estimated standard deviations in parentheses. Bond 33a (I) Length (A) 33a (tt) 33b Ru(l)-0(1) 2.238(3) 2.187(2) 2.252(4) Ru(l)-P(l) 2.2281(11) 2.2344(8) 2.220(1) Ru(l)-P(2) 2.3147(12) 2.3085(7) 2.284(1) Ru(l)-N(l) 2.308(3) 2.311(2) 2.326(4) Ru(l)-Cl(l) 2.3941(11) 2.3976(6) 2.385(1) Ru(l)-Cl(2) 2.4173(10) 2.4298(6) 2.418(1) 0(1)-H(1) N/A 0.74(2) 0.69(6) 0(1)-H(2) N/A 0.81(3) 0.96(6) H(1)-C1(1) N/A 2.43(3) 2.79(7) H(2)-C1(2) N/A 2.76(3) 2.84(6) 179 References on page 202 Chapter 5 Table 5.2 Selected bond angles (°) for 7ro«5-RuCl2(P-N)(PPh3)(OH2)-2C6H6 (I), trans-RuCl2(P-N)(PPh3)(OH2)-1.5C6H6 (H) and fra«5-RuCl2(P-N)(P(p-tolyl)3(OH2) (33b) with estimated standard deviations in parentheses. Bond 33a (I) Angle (°) 33a (II) 33b H(l)-0(1)-H(2) N / A 97.5(28) N / A Ru(l)-0(1)-H(l) N / A 126.6(23) N / A Ru(l)-0(1)-H(2) N / A 116.4(25) N / A Cl(l)-Ru(l)-0(1) 82.47(7) 85.40(6) 81.6(1) Cl(2)-Ru(l)-0(1) 83.87(7) 80.63(6) 82.2(1) Cl(l)-Ru(l)-P(l) 104.11(4) 88.02(2) 104.30(5) Cl(l)-Ru(l)-P(2) 87.05(4) 96.30(2) 89.74(5) Cl(l)-Ru(l)-N(l) 91.01(9) 84.09(5) 90.8(1) Cl(l)-Ru(l)-Cl(2) 165.18(4) 165.58(2) 162.91(4) 0(1)-Ru(l)-P(l) 168.33(7) 169.95(6) 168.8(1) 0(1)-Ru(l)-P(2) 90.94(8) 88.57(6) 91.4(1) 0(1)-Ru(l)-N(l) 88.85(11) 90.30(8) 90.3(1) Cl(2)-Ru(l)-P(l) 88.45(4) 105.32(3) 90.73(4) Cl(2)-Ru(l)-P(2) 98.88(4) 86.97(2) 96.26(5) Cl(2)-Ru(l)-N(l) 83.01(9) 92.37(5) 83.7(1) P(l)-Ru(l)-P(2) 98.94(4) 99.70(3) 98.04(5) P(l)-Ru(l)-N(l) 81.48(9) 81.46(6) 80.20(9) P(2)-Ru(l)-N(l) 178.06(9) 178.77(6) 178.24(9) 180 References on page 202 Chapter 5 The notable structural difference between the aquo complexes and the complexes containing sulfur ligands (Chapter 4) is that the Cl-atoms in the former are mutually trans but are cis in the latter. Consequently, the P(l) (of the P-N ligand) is trans to H 20 ligand in the former and trans to a Cl-atom in the latter (see Chapter 1, Figure 1.18). The observation that the Ru-P(l) bonds in I, II and 33b (2.2281, 2.2344 and 2.220 A) are shorter than those in the complexes containing S ligands (2.27 A on average) indicates that the Cl-atom has a stronger trans influence than that of H 20 toward phosphines. This is in agreement with ab initio calculations,16 and ^ NMR data obtained for trans- [Pt(H20)(CH3)(dppe)]BF4 and /ra«5-[Pt(Cl)(CH3)(dppe)].17 The correlation between 3 1P NMR data and trans influence will be discussed in Section 5.3. 5.3 NMR Spectra of 7>ans-RuCl2(P-N)(PPh3)(OH2) (33a) The 3 1P NMR spectrum of a sample of isolated 33a shows a characteristic AX coupling pattern. The resolution and chemical shifts of these resonances, however, are dependent on the solvent, temperature and concentration of added H20. In solution, 33a is in a rapid equilibrium with 6a (Figure 5.4) and resonances of the individual species are unresolved and indistinguishable on the NMR timescale. While the chemical shifts due to Px (sharp doublets at 8 ~ 48) are relatively constant in different temperatures and solvents in the 31P{1H} NMR spectra of 33a, the P A signals appear from 8 68 to 8 80 as broad peaks or doublets (e.g. see Figure 5.5). Table 5.3 compares the P A and Px chemical shifts of isolated samples of 33a with those of 6a in various solvents. Weakly coordinating solvent molecules compete with H 20 for the vacant sixth site on the Ru. For example, d6-acetone is weakly coordinated to 6a, trans to PA, as indicated by the broad P A signal at 8 70.5 (Figure 5.6(a)). A sharp doublet due to P A emerges as the concentration of H 20 is increased and equilibrium 181 References on page 202 Chapter 5 favours the formation of 33a (Figure 5.6(b)-(e)). Coordinative competition from acetone is negligible upon addition of > 300 equiv of H20. a-N Ru—a _H20 a-. N RU—a 6a 33a Figure 5.4 Rapid equilibrium between 6a and 33a. Table 5.3 P A and P x chemical shifts for RuCl2(P-N)(PPh3) (6a) and frtf«s-RuCl2(P-N)(PPh3)(OH2) (33a) in various solvents at 20°C. Solvent 5 P A 8Px 2JPP (Hz) 6a 33a 6a 33a 6a 33a n CD2C12 80.51 80.1(br)b 47.00 48.40" 36.54 37.39" CDC13 83.23 68.5(br)b 48.41 45.70b 34.82 37.76b CeDe 83.69 73.52b 48.87 49.3 l b 36.54 38.00" de-acetone 70.5(br) 61.78c 47.27 48.03c 38.36 38.12° aAll chemical shifts above are doublets unless otherwise specified by (br) to indicate a broad signal. "The spectra are for isolated samples of 33a, i.e. in the absence of added H20. cSpectra refer to fully formed 33a in the presence of added H20. 182 References on page 202 Chapter 5 25° PA -20° -50°C Figure 5.5 3 1P{'Hj NMR spectra (202.47 MHz) of /rara-RuCl2(P-N)(PPh3)(OH2) (33a) in CD2C12 at various temperatures. A new, unidentified species appeared between -50° and -80°C as indicated by signals at 5 49. 8 and 5 59.0. 183 References on page 202 Chapter 5 80 70 60 ppm Figure 5.6 "P^H} NMR spectra (121.4 MHz, 20°C) of RuCl2(P-N)(PPh3) (6a) in de-acetone with various H 20 concentrations. 184 References on page 202 Chapter 5 The 31P{1H} NMR spectra of samples of 33a in CD2C12 at various temperatures are shown in Figure 5.5. The rapid coordination and dissociation of the aquo ligand trans to the P A atom of the aminophosphine ligands are apparent from the downfield broad signal. This type of NMR coalescence is a consequence of the trans effect of P A on the H 2 0 ligand. Examples of this behaviour have been demonstrated by the weakly bonded H 2 0 complexes, fraw5,/wer-[MCl2(H20)(PMe2Ph)3][C104] (M = Rh 1 9 or lr20). At 25°C, equilibrium favours 6a as indicated by the P A chemical shift at 6 80.1. As the temperature is lowered to -50°C, concentrations of both species become equivalent and the PA resonances coalese into the base line. Finally, at -80°C, the P A signal reappears at 5 62.3 due to the dominance of the aquo complex. The 'H NMR spectra of 33a also agree with the above observation although the distinction between the resonances of 6a and 33a is not as obvious. That is, the -NMe2 signals of both complexes overlap as seen in Figure 5.7. Of note, when the temperature is lowered from 25° to -80°C, the resonances due to the coordinated H 2 0 shift downfield from 6 2.18 to 3.42 while the -NMe2 resonances shift upfield from 5 3.20 to 2.85. The "P^H} and 'H NMR spectra of the 6a/33a equilibrium system are in marked contrast to those of the 6a/18a (cw-RuCl2(P-N)(PPh3)(SH2)) system where both species are distinguished. The coalescence of the resonances of 6a and 33a on the NMR-timescale indicate that the aquo system is much more labile; i.e. the reversible formation of the aquo complex is faster than the H2S species. 185 References on page 202 Chapter 5 25°C phenyl region -NMe2 for 6a and 33a CH 2C1 2 Ru-OHj 6a -50°C RU-OH2 -NMe2 -80°C Ru-OH 2 -NMe2 ' I ' I " " 2.5 1.5 0.5 ppm 8.5 l ' ' 1 ' 1' ' " 1 " " 1 '1 " 11 1 1 1 l 1 " ' l " 1 1 I ' ' " l " ' ' I " 7.5 6.5 5.5 4.5 3.5 Figure 5.7 *H NMR spectra (500 MHz) of *raw5-RuCl2(P-N)(PPh3)(OH2) (33a) in CD2CI2 at various temperatures. 5.4 Trans Influence of Ligands and its Effect on 3 1 P NMR Chemical Shifts The trans effect of the P-atom of the P-N ligand on the H 2 0 ligand leads to the rapid and reversible coordination of H 20. Conversely, the trans influence of H 2 0 on P-N must weaken the Ru-PA bond relative to its strength in the five-coordinate complex 6a. The frawj-influence of the ligand trans to the P A atoms is exemplified by the 31P{1H} NMR spectra of the RuCl2(P-N)(PR3)(L) (L = small molecule) complexes. For example, the ligand trans to P A is CI for m-RuCl2(PA-N)(PxR3)(H2S), and H 2 0 for fra«s-RuCl2(PA-N)(PxR3)(H20). In both cases the N-atom of the P-N ligand is trans to PPh3 and the chemical shift of P x is 186 References on page 202 Chapter 5 relatively insensitive to the incoming ligand L or the orientation of the Cl-atoms (Table 5.4). The negligible confluence of ligands on phosphines is also demonstrated by 3 1P NMR chemical shifts and 'Jpt-p coupling constants of platinum(II) phosphine systems.21'22 The chemical shifts of P A, however, are dependent on the ligand at the trans position. A more downfield P A signal corresponds to a higher trans influence of the trans ligand because trans influence is determined by the ability of this ligand to deshield P A 2 3 , 2 4 That is, the trans influence is determined by the ligands effectiveness in competing for the metal orbital's s-character.25'26 Alternatively, the trans influence is also dependent on the a-donating ability of the ligands as demonstrated by the ^ M - P NMR data obtained for M = Rh(I)25 and Pt(II)23'27 systems. A large J value indicates a weak influence by the trans ligand because large NMR coupling constants reflect strong a-bonds.25'28 Table 5.4 Comparison of 3 !P {'H} NMR chemical shifts and Ru-P bond lengths. Complex (in CDC13) 5P A Ru-PA (A) 5P X Ru-PX(A) 2JPP (Hz) fro»s-RuCl2(P-N)(P(p-tolyl)3) (7a)a 81.46 2.170(1) 47.64 2.290(1) 37.15 rra«5-RuCl2(P-N)(P(p-tolyl)3)(OH2)(33b)b 71.80 2.220(1) 47.62 2.284(1) 38.12 7ram-RuCl2(P-N)(PPh3)(OH2) (33a, I (II))b 68.50 2.2281(11) (2.2344(8)) 47.70 2.3147(12) (2.3085(7)) 37.76 m-RuCl2(P-N)(P(p-tolyl)3)(SH2)(19a)c 51.91 2.2560(4) 42.58 2.3040(3) 30.41 czs-RuCl2(P-N)(PPh3)(SH2) (18a)c 50.60 2.2712(6) 44.48 2.3110(7) 30.23 cw-RuBr2(P-N)(PPh3)(SH2) (18b)c 53.41 2.2617(10) 44.36 2.5540(4) 29.20 c/5-RuCl2(P-N)(PPh3)(MeSH) (20)c 51.43 2.2803(7) 42.37 2.3100(7) 29.87 cz5-RuCl2(P-N)(PPh3)(EtSH) (21)c 50.97 2.2753(5) 42.48 2.3100(6) 30.05 c/5-RuCl2(P-N)(PPh3)(H2) (36)d 49.30 2.2884(7) 45.48 2.3098(6) 26.83 C/5-RuCl2(P-N)(PPh3)(=C=C(H)Ph)(45)d 37.85 2.332(2) 36.40 - h 2.346(2) 26.50 C/-11 _ i „ 4, and dChapter 6. 187 References on page 202 Chapter 5 2.3400 4-• 45 2.3200 + 2.1800 R2 = 0.94 • 7a 2.1600 2.1400 30.00 40.00 50.00 60.00 70.00 80.00 90.00 31 P N M R Chemical Shifts (ppm) Figure 5.8 The relationship between Ru-PA bond length (A) and 8 P A (in CDC13) for the complexes containing the Ru(P-N) moiety. (Structures of 7a, 19a, 33b and 4 5 were measured at 21°C, 18a, 18b, 20, 21 and 33a were determined at -93°C, and 36 was determined at -100°C; 3 lP{ lH) NMR chemical shifts of P A for all the complexes were determined at 20°C.) Table 5.4 also compares the 3 1P{1H) NMR chemical shifts and Ru-P bond lengths for Ru(P-N) complexes related to this thesis work. With the exception of 4 5 , the 8 Px shifts for the chloro complexes are consistently at ca. 5 45 and the Ru-Px bond lengths are ca. 2.31 A. The inverse dependence of 8 P A on Ru-PA is plotted in Figure 5.8, a trend that has also been observed for Ru(II) complexes containing PPh 3 2 9 , 3 0 and DPPB (Ph2P(CH2)4PPh2)31'32 ligands. In fact, the plot for the P-N system (slope = -3.2 x 10'3 A ppm"1, intercept = 2.44 A) is similar to that of the PPh3 (slope = -2.9. x 10-3 A ppm"1, intercept = 2.47 A) and DPPB (slope = -2.9 X 10"3 A ppm"1, intercept = 2.42 A) systems. 188 References on page 202 Chapter 5 From the plot shown in Figure 5.8, the ligands can be listed in order of decreasing trans influence: CI ~ Br > H20. In accord, halides are better a- and 7t-donors than H20. Of note, 2JPP values for the trans complexes (~ 37.7 Hz) are larger than those of the cis complexes (~ 29.0 Hz). Tables 5.5 and 5.6 list the Ru-Cl bond distances when the Cl-atoms are mutally trans and cis, respectively. From the comparisons of the average trans Ru-Cl bond distances in Table 5.5 and Ru-C1A bond distances in Table 5.6, it can be stated that S-ligands have a stronger trans influence than that of CI. Further, the S-ligands (average Ru-C1A = 2.42 A) perhaps have a slightly greater trans influence than that of H 2 (Ru-C1A = 2.41). The PA-atom of the P-N ligand has a greater trans influence than that of CI as indicated by the relatively long Ru-C1B bonds in Table 5.6. Greater trans influence of phosphine ligands over CI has been previously observed for P^JI)23 and Rh(I)25 complexes. Using the above observations and assuming that the cis effects are negligible, a trans influence order is derived as: P A > SH2 ~ thiols > H 2 > CI ~ Br > H20. Table 5.5 Ru-Cl bond lengths (A) for *rara-RuCl2(P-N)(PR3)(L). *raro-RuCl2(P-N)(PR3)(L) Bond Lengths (A) Ru-C1A RU-C1B R = Ph, L = vacant (7a) 2.387(1) 2.379(1) R = Ph,L = H20(33a,I) 2.3941(11) 2.4173(10) R = Ph,L = H20(33a,n) 2.3976(6) 2.4298(6) R=/7-tolyl,L = H20(33b) 2.385(1) 2.418(1) _,,N Q A — P J i — C t ph3p«r 189 References on page 202 Chapter 5 Table 5.6 Ru-Cl bond lengths (A) for cw-RuCl2(P-N)(PR3)(L). cw-RuCl2(P-N)(PR3)(L) Bond Lengths (A) Ru-CU R U - C 1 B R = Ph,L = H2S (18a) 2 . 4 2 3 8 ( 6 ) 2 . 4 7 2 1 ( 5 ) R = p-Xo\y\, L = H2S (19a) 2 . 4 2 9 ( 3 ) 2 . 4 6 9 ( 4 ) R = Ph, L = MeSH (20) 2 . 4 2 4 1 ( 7 ) 2 . 4 4 7 2 ( 7 ) R = Ph,L = EtSH(21) 2 . 4 2 0 4 ( 6 ) 2 . 4 6 7 4 ( 5 ) R = Ph,L = Ti2-H2(36) 2 . 4 0 9 0 ( 6 ) 2 . 4 5 4 3 ( 7 ) Ph3PT N Ru L O B Reaction of RuCl2(P-N)(PPh3) (6a) with L = H2S and thiols (Chapter 4 ) , H 2 (Chapter 6 ) , and HCCPh (Chapter 6 ) results in the exclusive formation of the cis isomers, i.e., having L trans to the apical P A atom is disfavoured. A plausible mechanism for the ?* ,.N a—^Ril'—ci Ph3Pj 6a -H2S +H2S a- i 1 U ";RU—N a 6a' -H 2S| +H,S a Ph,P, ,N Ru" CI H 18a' .N CI——;Ru-ph3pr | Cl -SH, 18a Figure 5.9 Proposed mechanism for the formation of cw-RuCl2(P-N)(PPh3)(SH2) (18a). 1 9 0 References on page 202 Chapter 5 formation of c/s-RuCl2(P-N)(PPh3)(SH2) and other cis isomers is shown in Figure 5.9, involving an equilibrium between the square pyramidal 6a and minute amounts of trigonal bipyramidal 6a' structures. The approach of the H2S ligand towards 6a to give the trans species 18a' is perhaps disfavoured because of the mutual trans influences of PA and H2S. The approach of H2S toward 6a' at the equatorial position between P x and N, presumably results in the favourable formation of the preferred cis isomer 18a. The rearrangement of square pyramidal structures to trigonal bipyramidal has also been shown to exist when H 20 dissociates from trans, roer-[MCl2(H20)(PMe2Ph)3][C104] (M = Rh 1 9 or Ir33). Other routes involving initial dissociation of CF cannot be ruled out at this stage. 5.5 UV-Vis Spectral Studies of the RuCl2(P-N)(PPh3)/H20 System The UV-Vis spectra of 6a with increasing concentrations of H 20 in CD2C12, C<>D6, acetone and THF are shown in Figures 11-14, respectively. Three isosbestic points at 414, 498 and 552 nm (s in CH2C12 (and CeHe) = 560 (600), 395 (380) and 145 (115) M" 1 an1) are observed in CH2C12 and solutions, while only one distinct isosbestic point at 404 nm (e in acetone (and THF) = 545 (655) JVT1 cm-1) is observed in solutions of the more coordinating solvents acetone and THF. The differences in spectra changes suggest that coordinating solvents such as acetone and THF compete with H 20 for the vacant site in the coordination sphere of 6a as shown in Figure 5.10. O f 0 * +H,0 P Ph 3 P^J " s P h 3 P ^ - H * ° Ph 3 p^J H S = acetone or THF 6a 33a Figure 5.10 Species in equilibrium when 6a is dissolved in a coordinating solvent in the presence of H20. 191 References on page 202 Chapter 5 3.00 T 2.50 2.00 1.50 4-1.00 0.50 0.00 454 nm(s= 1100 M"1 cm-1) \ 678 nm (e = 480 M1 cm'1) 320 370 420 470 520 570 620 Wavelength (nm) 670 720 770 820 Figure 5 11 Spectral changes observed upon addition of Ff 20 to RuCl2(P-N)(PPh3) (6a) (1 04 X lO"3 M) in CH2C12 at 25°C. Added [H 20] = (a) 0.0, (b) 0.0056, (c) 0.0111, (d) 0.0333, (e) 0.0500, (f) 0.0666, (g) 0.0999, (h) 0.1110 M. 3.00 2.50 2.00 1.50 + 1.00 0.50 + 452 nm (e = 1000 M1 cm'1) 0.00 682 nm (s = 400 MT1 cm-1) 320 370 420 470 520 570 620 Wavelength (nm) 670 720 770 820 Figure 5.12 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) (1.21 X lO'3 M) in CeHe at 25°C. Added [H 20] = (a) 0.0, (b) 0.0056, (c) 0.0111, (d) 0.0222, (e) 0.0333, (f) 0.0444, (g) 0.0776 M. 192 References on page 202 Chapter 5 1.20 1.00 0.80 0.60 0.40 + 0.20 0.00 H h 380 430 480 530 580 630 Wavelength (nm) 680 730 780 Figure 5.13 Spectral changes observed upon addition of H 2 0 to RuCi2(?-N)(PPh3) (6a) (1.12 X 10"3 M) in acetone at 25°C. Added [H 2 0] = (a) 0.0, (b) 0.0089, (c) 0.2652, (d) 0.9171, (e) 1.9702, (f) 3.9591 M. 1.60 -r 1.40 \ 1.20 1.00 0.80 0.60 0.40 4-0.20 0.00 380 430 480 530 580 630 Wavelength (nm) 680 730 780 Figure 5.14 Spectral changes observed upon addition of H 2 0 to RuCl2(P-N)(PPh3) (6a) (1.19 X lO"3 M) in THF at 25°C. Added [H 2 0] = (a) 0.0, (b) 0.0444, (c) 0.1110, (d) 0.2220, (e) 0.9992, (f) 4.330 M. 193 References on page 202 Chapter 5 - r 0.80 -- 0.60 -2.00 -1.80 -1.60 -1.40 -1.20 -1.00 -0.80 log [H20] Figure 5.15 Solving K for the addition of H 20 to 6a at 25°C. The equihbrium concentrations were obtained by monitoring the absorbance at 678 nm (Figure 5.11). Data points at higher H 20 concentrations have been omitted due to the insolubility of H 2 0 in C H 2 C 1 2 ; solubility of H 2 0 in C H 2 C 1 2 is 0.128 M at 25°C. 3 4 From the equation log {[33a]/[6a]} = log K + log [H20], the equilibrium constant K for the formation of 33a in CH2C12 is obtained by plotting log {[33a]/[6a]} versus log [H20] (Figure 5.15). K = 37±2M* at 25°C is calculated from the intercept of the plot, the estimated error being based on repeat experiments (see Appendix XII. 1 for raw data). The slope of 1.06 is in agreement with the unity dependence on the concentration of H 20. A value of the same order of magnitude (K = 28 JVT1, see Appendix XII.2) was obtained for the reaction in C£k, implying that both these solvents are non-coordinating in the equilibrium system. Of note, K = ~ 10 M"1 was estimated from the XH NMR spectra of 33a in CD2C12 (at 25°C). Comparison of K = 37 M 1 with those obtained for H2S and thiols (discussed in Section 4.6) insinuates that equilibrium favours the formation of RuCl2(P-N)(PPh3)(L) in the 194 References on page 202 Chapter 5 order L = MeSH > EtSH ~ H2S > H 2 0 at 25°C in CH2C12 solutions, with K decreasing from 296 to 37 M" 1. K values in CH2C12 were measured from 10 to 38°C, but reproducible values at the extreme temperatures could not be obtained. AH°, AS° and AG 0 for the coordination of H 2 0 to 6a are nevertheless estimated to be -50 ± 20 kJ/mol, -140 ±40 J/mol K and -8.9 ±0.2 kJ/mol (at 25°C, based on K = 37 ± 2 M 1 ) (see Appendix XII. 1). Kinetic studies of ligand substitution on 33a were attempted. Thus, H2S or H 2 at 1 atm total pressure was added to solutions of 33a (1.0 x 10_3M) in acetone or CH2C12 containing excess H 2 0 (> 1.0 M in acetone, > 0.13 M in CH2C12) to insure complete formation of 33a. However, the substitution reactions were too rapid to be measured by UV-Vis spectroscopy; for example, upon addition of 1 atm H2S to 33a in CH2C12, the solution 'instantaneously' changed from a pink colour to bright yellow, the UV-Vis spectrum showing complete formation of the H2S adduct. 5.6 The Preparation of rra«s-RuCI2(P-N)(PPh3)(L) (L = MeOH (34) and EtOH (35)) The preparations of the MeOH and EtOH complexes proved to be difficult as trace moisture led to the formation of the aquo complex 33a. rra«5-RuCl2(P-N)(PPh3)(MeOH) (34) was previously observed in situ by Mudalige from NMR experiments.2 In this thesis work, 34 was isolated by stirring RuCl2(PPh3)3 and P - N in a mixture of vigorously dried MeOH and acetone; addition of hexanes led to the precipitation of a pink solid that analysed for 34 (Section 2.10.3). The 31P{1H} NMR spectrum (in CD2C12) of an isolated sample of 34, similar to that of 33a, shows a broad signal at 8 77 due to PA and a resolved doublet due to Px at 8 47.14 ( 2Jpp = 36.66 Hz); upon addition of 50 equiv of MeOH to the solution, the signal due to PA is resolved into a doublet (8 77.46, 36.66 Hz). The *H NMR spectrum of an 195 References on page 202 Chapter 5 isolated sample of 34 is shown in Figure 5.16. The singlet at 5 3.16 is due to the NMe2 resonances, the equivalence of the Me groups implying the trans structure. The doublet at 8 3.30 ( 3JHH= 5.3 Hz) is assigned to the CH 3 group while the quartet at 8 1.34 ( 3 JHH = 5.3 Hz) is assigned to the OH group of the coordinated MeOH. The small singlet at 8 3.19 happens to be at the position of the resonances for the NMe2 group of 6a, which is in equilibrium with 34, but the 31P{1H} NMR data imply a rapid equilibrium on the NMR-timescale. phenyl region Ru-(HOCif 3) JL Ru-(M)CH 3 ) acetone J I l I i l i i | i i i i | l i i i | l i i i | l i i i | i i i l l I I l l I | I I I I | I I I I | I l I i | I I i I | i I M | I I I I | I I I i | I I I 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 ppm Figure 5.16 ! H NMR spectrum (300 MHz) of *raws-RuCl2(P->0(PPh3)(MeOH) (34) in CD2C12. 196 References on page 202 Chapter 5 -N(C/f 3 ) 2 Ru(HOCH 2 CZf 3 ) Ru(HOCtf 2 CH 3 ) R u ( M ) C H 2 C H 3 ) JU I i i i i I i i i i i i i i i | i i i i i i i i i | i i i i i i i i i | i i i i i i i i i | i i i i i i i i i | i i i i i i t • . i 5.0 4.0 3.0 2.0 1.0 8.0 7.0 6.0 ppm Figure 5.17 J H N M R spectrum (300 M H z ) of /ra«5-RuCl2(P-N)(PPri3)(EtOH) (35) in CD 2C1 2. The preparation o f /raw5-RuCl2(P-N)(PPh3)(EtOH) (35) required stirring a suspension o f R u C l 2 ( P P h 3 ) 3 and P-N in neat E t O H for 1 week (Section 2.10.4), when work-up o f this reaction mixture resulted in two products. Firstly, a precipitated brown solid was not characterized because o f its insolubility in acetone, C 6D 6, CDC1 3 or CD 2C1 2. A second work-up o f the filtrate resulted in a pink solid characterized as 35, although an analytically pure sample could not be isolated even after several repeated preparations. The 3 1P{ XH} N M R (in CD 2C1 2) spectrum o f 35 is similar to that o f 34, and consists o f a broad P A signal at 8 80 and a doublet at 8 46.90 ( 2 J P P = 36.24 Hz) due to P x. The P A signal is again resolved into a sharp doublet at 8 79.79 ( 2 J P P = 36.24 Hz) after the addition o f 50 equiv o f E t O H to the above solution. The *H N M R spectrum o f isolated 35 is shown in Figure 5.17. In addition to the singlet at 8 3.18 due to the N M e 2 group, well resolved peaks due to the 197 References on page 202 Chapter 5 coordinated EtOH group are also depicted. The assignments are as follows: 8 3.61 (doublet of quartets) due to CH3C#2OH; 8 1.40 (triplet) due to Ci73CH2OH; and 8 1.16 (triplet) due to CH 3CH 20#. The solution properties of 34 and 35 are very similar to those of the aquo complex 33a. That is, rapid coordination and dissociation of the alcohol ligands are apparent from the broad P A signals in the 31P{1H} NMR spectra of 34 and 35. Furthermore, variable temperature NMR studies also display similar trends which resemble those of 33a. In conclusion, 34 and 35 are isolated only under absolutely anhydrous conditions. In the solid state, the complexes lose the solvent molecules rapidly even under 1 atm of Ar to regenerate the five-coordinate, green solid 6a. Weakly coordinating solvent molecules play an important role in stabilizing complexes such as RuCl2(EtOH)(PMe2Ph)3, [RuH(PPh3)2(H20)2(MeOH)][BF4],36 [Ru(Y)Cl2(MeOH)(PPh3)2] (Y = CO or CS) [RuH(PMe2Ph)4(MeOH)][PF6], and [RuH(dppe)2(EtOH)][PF6].38 Dissociation of the solvent molecules can create vacant coordination sites for substrate binding in highly reactive catalysts. For example, Ru(BINAP)(acac)(MNAA)(MeOH) (MNAA 2-(6'-methoxynaphth-2'-yl) acrylate anion)) plays a role in the homogeneous asymmetric hydrogenation of 2-arylacrylic acids to give high e.e. of chiral 2-arylpropionic acids, which are used as anti-inflammatory drugs.39 The high activity of this species is attributed to the dissociation of the highly labile MeOH ligand as an intermediate in the catalytic cycle. 5.7 DSC Data for Complexes Containing O-Donor ligands The enthalpy values, AH°, for the loss of L = H 20, MeOH and EtOH from their corresponding complexes, 33a, 34 and 35 are obtained from DSC experiments, the data being shown in Figure 5.18. When these endothermic values are compared with those of complexes 35 37 198 References on page 202 Chapter 5 containing S-ligands (Section 4.7), the dissociation energy o f L decreases in the order M e S H > M e O H > H 2 S > H 2 0 > E t S H > EtOH. Thus, in the solid state, the S-ligand containing complexes have a higher dissociation energy than the corresponding O-ligand containing species, which is likely attributed to the higher thermal stability o f the c/s-chloro S-containing molecules. A s previously discussed (Section 5.4), the apical P A atom o f the P-N ligand exerts a strong trans influence on the mutually trans ligand ( H 2 0 , MeOH, EtOH). The H 2S, M e S H and E t S H ligands, however, do not experience such a strong trans influence from the Cl-atom. The M e S H and M e O H adducts are noticeably more thermally stable than the other complexes; perhaps the methyl mercaptan and methanol molecules are o f the most compatible size and electronic structure to occupy the vacant site o f the five-coordinate complex 6a. 1.20 -0.80 A 1 " 1 1 1 1 ^ 50 70 90 110 130 150 170 Temperature °C Figure 5.18 D S C curves for fram-RuCl2(P-N)(PPh3)(L). Samples are heated in a N 2 atmosphere (flow rate = 40 cc/min) at a rate o f 5°C/min to 200°C. A more accurate A H ° for 35 ( L = E t O H ) could not be determined because o f the inability o f obtaining an analytically pure sample. 199 References on page 202 Chapter 5 If solution effects are negligible, the magnitude of AH° from solution and solid state studies should be eventually the same, as the chemistry in both cases involves no trans to cis rearrangement of the Cl-atoms. In Section 5.5, AH° = -50 ± 20 kJ/mol was obtained for the coordination of H 2 0 to 6a to give 33a in CH2C12, while for the dissociation of H 2 0 from 33a in the solid state AH° = 75 ± 4 kJ/mol. DSC is also used to differentiate the Ru-0 bond strengths between rraws-RuCl2(P-N)(PPh3)(H20) (33a) and rra«5-RuCl2(P-N)(P(p-tolyl)3)(H20) (33b). From the DSC curves shown in Figure 5.19, AH° values for the loss of H 2 0 are 75 ± 4 and 62 ± 2 kJ/mol for 33a and 33b, respectively; i.e., the Ru-0 bond in 33a is stronger than that in 33b which is in agreement with the shorter Ru-0 bond lengths of 33a (2.238 A (I), 2.187 A(II)) versus that of 33b (2.252 A). 0.90 j -0.70 - : 0.50 --f 0.30 --g 1 <+* 0.10 -08 tS -0.10 ---0.30 -0.50 50 33b. AH° = 62 ± 2 kJ/mol 33a. AH° = 75 ± 4 kJ/mol 70 —I 1— 1— 90 110 130 Temperature °C 150 170 Figure 5.19 DSC curves for /raws-RuCl2(P-N)(?Ph3)(H20) (33a) and rra«5-RuCl2(P-N)(P(p-tolyl)3)(H20) (33b). Samples are heated in a N 2 atmosphere (flow rate = 40 cc/min) at a rate of 5°C/min to 200°C. 200 References on page 202 Chapter 5 5.8 Summary In this Chapter, the apical phosphine (PA of P-N) of the five-coordinate complex RuCl2(P-N)(PPh3) is seen to play a significant role in directing incoming monodentate ligands in a position either trans or cis to itself. The trans effect of P A induces /raws-RuCl2(P-N)(PPh3)(L) complexes (L = H 20, MeOH and EtOH) into a rapid equilibrium with RuCl2(P-N)(PPh3). The S-containing ligands (H2S, MeSH and EtSH), on the other hand, appear to have a stronger trans influence (than the O-donors) toward P A and the c/j-RuCl2(P-N)(PPh3)(L) structures are more favourable. 201 References on page 202 Chapter 5 5.9 References 1. (a) Stang, P. J.; Song, L.; Huang, Y.-H; Arif, A. M . J. Organomet Chem., 1991, 405, 403. (b) Collman, J.P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemsitry, University Science Books: Mill Valley, CA, 1987. 2. Mudalige, D. C. Ph.D. Thesis, The University of British Columbia, 1994. 3. Benedict, W. S.; Gailar, N.; Plyler, E. K. J. Chem. Phys. 1956, 24, 1139. 4. Mudalige, D. C; Rettig, S. J.; James, B. R.; Cullen, W. R. J. Chem. Soc, Chem. Commun., 1993, 830. 5. LaPlaca, S. J.; Ibers, J. A. Inorg. Chem. 1965, 4, 778. 6. MacFarlane, K. S.; Joshi, A. M.; Rettig, S. J.; James, B. R. Inorg. Chem. 1996, 35, 7304. 7. MacFarlane, K. S. Ph.D. Thesis, The University of British Columbia, 1995. 8. Hampton, C. R. S. M.; Butler, I. R.; Cullen, W. R.; James, B. R.; Charland, J.-P.; Simpson, J. Inorg. Chem. 1992, 31, 5509. 9. Lawson, H. J.; Janik, T. S.; Churchill, M. R.; Takeuchi, K. J. Inorg. Chim. Acta, 1990, 174, 197. 10. Mandal, S. K.; Chakravarty, A. R. Inorg. Chem. 1993, 32, 3851. 11. Boniface, S. M.; Clark, G. R.; Collins, T. J.; Roper, W. R. J. Organomet. Chem., 1981, 206, 109. 12. Rothlisberger, M. S.; Hummel, W., Pittet, P.-A; Burgi, H.-B.; Ludi, A.; Merbach, A. E. Inorg. Chem. 1988, 27, 1358. 13. McGrath, D. V.; Grubbs, R. H. J. Am. Chem. Soc. 1991,113, 3611. 14. Bernhard, P.; Burgi, H.-B.; Hauser, J.; Lehmann, H.; Ludi, A. Inorg. Chem. 1982, 21, 3936. 15. Kolle, U.; Flunkert, G. Gorissen., R. Schmidt, M. U.; Englert, U. Angew. Chem., Int. Ed. Engl. 1992, 31, 440. 202 Chapter 5 16. Basch, H.; Krauss, M.; Stevens, W. J.; Cohen, D. Inorg. Chem. 1985, 24, 3313. 17. Shinoda, S.; Koie, Y. Saito, Y. Bull. Chem. Soc. Jpn. 1986, 59, 2938. 19. Deeming, A. J.; Proud, G. P. Inorg. Chim. Acta 1985,100, 223. 20. Deeming, A. J.; Proud, G. P.; Dawes, H. M ; Hursthouse, M. B. J. Chem. Soc, Dalton Trans. 1986, 2545. 21. Malito, J.; Alyea, E. C. Transition Met. Chem. 1992, 77, 481. 22. Anderson, G. K.; Kumar, R. J. Chem. Research (S) 1998, 48; J. Chem. Research (M) 1988, 432. 23. Bruggeller, P. Inorg. Chem. 1987, 26, 4125. 24. Grimley, E.; Meek, D. W. Inorg. Chem. 1986, 25, 2049. 25. Gambaro, J. J.; Hohman, W. H.; Meek, D. W. Inorg. Chem. 1989, 28, 4154. 26. Pidcock, A.; Richards, R. E.; Venanzi, L. M. J. Chem. Soc. (A) 1966, 1707. 27. Tau, K. D.; Meek, D. W. Inorg. Chem. 1979,18, 3574. 28. Keiter, R. L.; Verkade, J. G. Inorg. Chem. 1969, 8, 2115. 29. Jessop, P. G.; Rettig, S. J.; Lee, C.-L.; James, B. R. Inorg. Chem. 1991, 30, 4617. 30. Dekleva, T. W. Ph.D. Thesis, The University of British Columbia, 1983. 31. (a) MacFarlane, K. S. Ph.D. Thesis, The University of British Columbia, 1995. (b) MacFarlane, K. S.; Joshi, A. M.; Rettig, S. J.; James, B. R. Inorg. Chem. 1996, 35, 7304. 32. Queiroz, S. L.; Batista, A. A ; Oliva, G.; Gambardella, M. T. do P.; Santos, R. H. A.; MacFarlane, K. S.; Rettig, S. J.; James, B. R. Inorg. Chim. Acta 1998, 267, 209. 33. Deeming, A. J. Doherty, S.; Marshall, J. E.; Powell, J. L.; Senior, A. M. J. Chem. Soc, Dalton Trans. 1993, 1093. 34. IUPAC Solubility Data Series, Volume 60, Halogenated Methanes with Water; Horvath, A. L.; Getzen, F. W., Eds.; Oxford University Press: Oxford, 1995, p. 153. 203 Chapter 5 Young, R. J.; Wilkinson, G. J. Chem. Soc, Dalton Trans. 1976, 719. Chart, J.; Leigh, G. J.; Paske, R. J. J. Chem. Soc.(A) 1969, 854. Armit, P. W.; Sime, W. J.; Stephenson, T. A. J. Chem. Soc, Dalton Trans. 1976, 2121. Ashworth, T. V.; Singleton, E. J. Chem. Soc, Chem. Commun. 1976, 706. Chen, C.-C; Huang, T.-T.; Lin, C.-W.; Cao, R.; Chan, A. S. C. Inorg. Chim. Acta 1998, 270, 247. 204 Chapter 6 Reactions of RuCl2(P-N)(PPh3) with Dihyd rogen, Ammonia, Nitrous Oxide, Alkynes, and Hydrogen Chloride In this Chapter, the coordination chemistry of RuCl2(P-N)(PPh 3) is extended to small molecules other than H2S, H2O, thiols and alcohols, leading to greater insight into the reactivity of the compound. The potential of this five-coordinate complex as a catalyst for hydrogenation of imines is also briefly examined. 6.1 The Structure and Reactivity of Cis-RuCl2(P-N)(PPh3)(r|2-H2) (36) The formation of c/5-RuCl2(P-N)(PPh3)(ri 2-H2) (36) has been described by Mudalige et al. 1' 2 However, this species was only observed in situ and its formulation established by NMR studies, including experiments to determine T i , the spin-lattice relaxation time of the hydrogen nuclei. The temperature dependence of T i gives a predicted3'4 V-shaped plot, and from the minimum T i value of 13.4 ± 0.2 ms, an intramolecular H-H bond distance of 0.87 + 0.03 A was calculated.1'2 In the present thesis work, 36 was isolated (Section 2.11.1) by reacting a suspension of RuCi2(PPh3)3 and P-N in acetone under 1 atm H 2 gas. The microanalysis of the isolated pale yellow solid is consistent with the formulation of 36. This solid is stable under H2 and reasonably so under Ar, but slowly loses H2 in air and decomposition occurs. The IR spectrum of 36 in the solid state (KBr plate) shows a band of medium intensity at 2149 cm"1 due to the V R U . ( H 2 ) stretching, while V H - H is not observed. Generally, V H - H bands of r|2-H2 complexes are very weak and are only rarely located (in the 2400 to 2700 cm'1 range).3'5 205 References on page 248 Chapter 6 6.1.1 The Crystal Structure Cw-RuCl2(P-N)(PPh3)(ri2-H2) (36) X-ray quality yellow crystals were crystallized from a saturated acetone solution of 36 under 1 atm H 2 . The ORTEP plot of 36, reveals a distorted octahedral structure and is shown in Figure 6.1. The dihydrogen was isotropically refined as a double-occupancy hydrogen atom, and consequently the intramolecular H-H distance was not determined. Selected bond lengths and angles of 36 are presented in Tables 6.1 and 6.2. The bond distances of Ru to the P(l), P(2), Cl(l), Cl(2) and N(l) atoms are normal, and are comparable to those of the complexes discussed in Chapters 4 and 5. Similarly, there are no significant differences between the angles around the Ru atom for 36 and those of the other c/s-dichloro complexes containing H2S or thiol ligands. The relatively short Ru(l)-H(l*) distance of 1.60 A is consistent with reasonable stablility with respect to loss of H 2 in the solid state. This distance is slightly longer than the Ru-(r|2-H2) distance (1.50 and 1.47A for the two Ru-H distances) reported for the dinuclear complex (isoPFA)(Ti2-H2)Ru(u,-Cl)2(|j,-H)RuH(PPh3)2,6 but is much shorter than 1.81 A (Ru-(r|2-H2)) of the labile complex /ra«5-[RuH(ri2-H2)(dppe)2][BPh4].7 The observation that the Ru-(r)2-H2) distance in 36 is comparable to Ru-H distances within classical monohydrides such as RuH(SC6H4pCH3)(CO)2(PPh3)2 (1.58 A),8 trans-[RuH(ri2-H2)(dppe)2][BPh4] (1.64 A),7 RuH(Cl)(diop)2 (1.65 A; diop = 4,5-bis((diphenyl phosphino)methyl)-2,2-dimethyl-1,3 -dioxolane)),9 RuH(dmpe)2(naphthyl) (1.67 A),10 RuH(PPh 3) 3(0 2CCH 3) (1.68 A),11 and RuH(Cl)(PPh3)3 (1.70 A)12 is consistent with a Ru-H complex. However, NMR spectroscopic evidence and reversible solution behaviour (see Section 6.1.2) clearly show 36 to be the Ru(II)-(ri2-H2) adduct. 206 References on page 248 Chapter 6 C16 C30 Figure 6.1 The ORTEP plot of c/s-RuCl2(P-N)(PPh3)(r|2-H2) (36). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability. Full experimental parameters and details are given in Appendix IX. 207 References on page 248 Chapter 6 Table 6.1 Selected bond lengths (A) for c/5-RuCl2(P-N)(PPh3)(r|2-H2) (36) with estimated standard deviations in parentheses. The H(l*) atomic site represents the double-occupancy hydrogen atom refined isotropically. Bond Length (A) Bond Length (A) Ru(l)-H(l*) 1.60(2) Ru(l)-N(l) 2.306(2) Ru(l)-P(l) 2.2884(7) Ru(l)-Cl(l) 2.4543(7) Ru(l)-P(2) 2.3098(6) Ru(l)-Cl(2) 2.4090(6) Table 6.2 Selected bond angles (°) for cw-RuCl2(P-N)(PPh3)(r|2-H2) (36) with estimated standard deviations in parentheses. Bonds Angle (°) Bonds Angle (°) P(l)-Ru(l)-N(l) 80.34(6) Cl(l)-Ru(l)-N(l) 92.20(6) P(l)-Ru(l)-Cl(l) 172.22(2) Cl(2)-Ru(l)-N(l) 86.78(6) P(l)-Ru(l)-Cl(2) 88.52(2) P(l)-Ru(l)-H(l*) 93.6(8) P(l)-Ru(l)-P(2) 105.27(3) P(2)-Ru(l)-H(l*) 87.3(8) P(2)-Ru(l)-N(l) 172.78(6) N(l)-Ru(l)-H(l*) 87.8(8) P(2)-Ru(l)-Cl(l) 82.34(3) Cl(l)-Ru(l)-H(l*) 88.3(8) P(2)-Ru(l)-Cl(2) 97.79(2) Cl(2)-Ru(l)-H(l*) 173.8(8) Cl(l)-Ru(l)-Cl(2) 88.86(2) 6.1.2 Thermodynamic Studies of Cw-RuCI2(P-N)(PPh3)(T|2-H2) (36) in Solution and in the Solid State When 36 is dissolved in solution, the r| 2-H 2 moiety quickly dissociates to form some 6a, and the ^P^H) and *H NMR spectra clearly show the equilibrium between the two species (Figures 6.2 and 6.3, respectively). The ^PI^ H} NMR chemical shifts of 36 are located at 8 47.14 (PA) and 8 45.33 (Px), 2Jpp = 26.49 Hz, in accord with similar structures 208 References on page 248 Chapter 6 containing cis Cl-atoms (see Table 4.9, p. 146). In the ! H NMR spectrum, inequivalent NMe chemical shifts for 36 are located at 5 3.78 and 2.79, and the coordinated H 2 at 5 -10.6. At 25°C, the equihbrium constant, K, for the formation of 36 is determined to be 261 ± 20 M"1, a value comparable to those of corresponding complexes containing S-ligands (K = 51 to 296 M"1, Section 4.6). From variable temperature NMR studies, the AH 0 , AS°, and AG° (at 25°C, calculated from AG° = -RTlnK) values are determined to be -26±4kJ/mol, -40 ± 15 J/mol K and -13.8 ± 0.2 kJ/mol, respectively. The raw data for the calculations of these data are given in Appendix XIII. The AH° value for the binding of r | 2 -H2 to Ru(U) is comparable to those of (ri2-H2)(dppb)(u-Cl)3RuCl(dppb) (-60 kJ/mol)13 and Ru(H2)(H)Cl(CO)(PiPr3)2 (-32 kJ/mol).14 The relatively labile nature of the r)2-H2 is also apparent in the solid state as shown by DSC experiments. The enthalpy, AH°, for the loss of H 2 in the solid state was found to be 50 ± 3 kJ/mol (Figure 6.4), and thus, ~ -24 kJ/mol is attributed to the enthalpy change for the cis to trans rearrangement of RuCl2(P-N)(PPh3); values of -39 to -66 kJ/mol were obtained from similar data for the complexes containing H2S or RSH (see Section 4.7). 209 References on page 248 Chapter 6 Figure 6.2 31P{*H} NMR spectrum (81.0 MHz) of 36 in equilibrium with 6a in C e D 6 at 20°C, established by dissolution of a solid sample of 36; although the signal due to P A of 6a is less intense than that of P x , their integrations are the same. Figure 6.3 *H NMR spectrum (200 MHz) of 36 in equilibrium with 6a in CeDe at 20°C, established by dissolution of a solid sample of 36; inset shows the upfield chemical shift due to Ru-(r|2-H2) at 8 -10.6. The signal for free H 2 (at 8 4.44) is not seen because of the low [H2]. 210 References on page 248 Chapter 6 0.90 0.40 4-0.30 4 1 1 1 1 1 1 1 40 60 80 100 120 140 160 180 Temperature °C Figure 6.4 DSC curve for c/'5-RuCl2(P-N)(PPh3)(r|2-H2) (36). The sample is heated in a N 2 atmosphere (flow rate = 40 cc/min) at a rate of 5°C/min to 200°C. 6.1.3 The pK a of Cis-RuCl2(P-N)(PPh3)(r|2-H2) (36) Determination of the acidity of dihydrogen complexes leads to a better understanding of homolytic or heterolytic cleavage of dihydrogen in catalytic hydrogenation reactions. The nature of the ancillary ligands has a dramatic influence on the reactivity of r | 2 -H 2 ; 1 5 for example, [RuH(ri2-H2)(dppe)2]+ is more electron-rich and therefore less acidic ( p K a = 15.0)15b than [CpRu(r|2-H2)(dppe)]+ ( p K a = 7.2).16 Furthermore, the structure of a complex is also correlated to acidity; for example, within the complexes fr-flr«5-[RuX(rj2-H2)(dppe)2]+ (X = CI, H), 1 7 the chloro complex is more acidic ( p K a = 6.0) than the hydrido complex ( p K a =15.0) because of the p7c(Cl)-d7t(Ru) repulsions which enhance the d7c(Ru)-»a*(H 2) back-bonding and thus weaken the H-H bond. 211 References on page 248 Chapter 6 The reaction of 36 with PS (proton sponge) gives the monohydride complex Ru(H)Cl(P-N)(PPh 3) (29) and PSrfCr (Section 4.8):1 .1,2 RuChCP-KKPPhs)^ 2 -^) + PS .. K g l > Ru(H)Cl(P-N)(PPh3) + PStTCT 36 29 Accordingly, the p K a of 36 can be determined by measuring the equilibrium concentrations of the above species. As discussed in Section 4.7, the p K a for 36 is obtained by solving the equation p K a = p K e q + p K p s i ^ (where p K P S H + = 12.3). For a typical experiment, a sample of 6a along with 0.75 to 3.0 equiv PS are dissolved in CD 2C1 2; the addition of 1 atm H 2 then produces a dark yellow-brown solution. Unlike the reaction of PS with cw-RuCl 2(P-N)(PPh 3)(SH 2) (18a) where the products, Ru(SH)Cl(P-N)(PPh 3) (27a) and Ru(SH) 2 (P-N)(PPh 3) (30) are unstable at r. t., the hydride complex Ru(H)Cl(P-N)(PPh 3) (29) is stable indefinitely under inert atmospheres. The "Pl/H} and XH NMR spectra (Figures 6.5 and 6.6, respectively) indicate that three species, 6a, 29, and 36, are in equilibrium. [The broadness of the P A chemical shift of 6a is due to minute amounts of H 2 0 in the system, (see Section 5.3)1. From the above equilibrium equation, Keq = P9][PSH ] ^ n 4 4 , 1 [36][PS] concentrations are readily obtained, for example, from the peak integrations of the *H NMR (Figure 6.6); the actual concentrations are not required as only the concentration ratios are relevant. The data give K e q = 15 ± 5 and consequently, the p K a of 36 is determined to be approximately 11. This value falls within a wide range of p K a values (0 to 16) for complexes of the type [M(H 2)Cp(P-P)] + (M = Ru, Os; P-P = diphosphine ligand) previously reported.3'15"19 In order to establish a trend in the acidity of Ru(P-N)-type r) 2-H 2 complexes, more studies on species with variations of the phosphines and halogens are required. 212 References on page 248 Chapter 6 6a P* 29 PA 29 P„ 6a PA 36 PA 36 Px T I I I I ll I I I I I I I I I I [ I I I I I 1 I I I I 90 80 70 I I | l l i l | 60 I I I I I I I | I I f I I I l l I 50 40 PPM Figure 6.5 3lV{lU} NMR (121.4 MHz, 20°C, CD2C12) spectrum of the in situ reaction of RuCl2(P-N)(PPh3) (6a) with 1.5 equiv PS under 1 atm H2. (NMe2)2 PSrf N M e 29 N M e 36, NMe2 6a NMe | 36 NMe 29 * / / (NMe,), PS •I 11 I 111 | 111111II111111 111111 II11 | I 11 11 11 11111111 11 11 11 11| I | | \ 1111| | I 111| [ 11| 11 11111 | | 111 11 11111 11 I ! 3 .8 3 . 6 3 . 4 3 . 2 3 .0 2 . 8 2 . 6 2 . 4 2 . 2 PPM 2 . 0 Figure 6.6 *H NMR (121.4 MHz, 20°C, CD2C12) spectrum in the region 8 2.0 to 4.0 of the in situ reaction of RuCl2(P-N)(PPh3) (6a) with 1.5 equiv PS under 1 atm H2. 213 References on page 248 Chapter 6 6.2 Reactions of RuX2(P-N)(PPh3) (X = CI, Br) with NH 3 The reactions of NH 3 with the five-coordinate complexes RuCl2(dppb)(PPh3) and RuCl2(PPh3)3 in solution are reported to result in the dissociation of one PPh3 molecule and the coordination of two molecules of NH 3 , with formation of the six-coordinate species, RuCl2(dppb)(NH3)220'21 and RuCl2(PPh3)2(NH3)2,22 respectively. The reactions of NH 3 with RuX2(P-N)(PPh3) (X = CI (6a) or Br (6b)), however, do not result in the dissociation of PPh3 as indicated by 31P{1H} NMR spectroscopy. With an equimolar concentration of NH 3 , only one NH 3 is coordinated to the vacant site of RuX2(P-N)(PPh3), with formation of /ra«5-RuX2(P-N)(PPh3)(NH3), this then rearranging to the more stable cis isomer. In the presence of 1 atm NH 3 , a second NH 3 displaces an X atom with formation of the complexes [RuX(P-N)(PPh3)(NH3)2---X] (see below). All experimental details for the reactions with NH 3 or with the NH 3 complexes may be found in Section 2.11.2. 6.2.1 Isolation of [RuX(P-N)(PPh3)(NH3)2-X] (37) in the Presence of Excess NH 3 When NH 3 gas is passed through a solution of RuCl2(P-N)(PPh3) (6a) in CH2C12, a dark blue-green solution formed. Microanalysis of the isolated green solid corresponds to the formulation of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a), with the suggested structure shown in Figure 6.7; remarkably 37a is non-conducting in acetone or CH2CI2 solutions (see Section 6.2.4), implying a "strongly associated ion-pair" formulation, possibly with the X associated via H-bonding to the NH 3 ligands as shown. In CDC13 solution under 1 atm NH 3 , 37a is fully formed as indicated by the 31P{1H} NMR and *H NMR spectra. The *H NMR spectrum (Figure 6.8) shows two singlets due to Ru-N(Cff3)2, 8 3.19, 3.00 and two singlets due to Ru-(N//3)2, 8 3.72, 1.70, data consistent with a cis orientation of the NH 3 groups. The presence of doublets at 8 57.20 (PA-N) and 8 53.24 (PxPhs), 2 J P P = 32.05 Hz, in the 31P{1H} 214 References on page 248 Chapter 6 NMR spectrum reveals an AX coupling pattern (Figure 6.9(a)), meaning the PPh3 ligand remains coordinated. fT\-Me ..•N--"Me X — R U — N H 3 P h 3 P / | NH3-_4 X = CI or Br Figure 6.7 Proposed structure of [RuX(P-N)(PPh3)(NH3)2-X] (37); the nature of the "associated" X remain uncertain (see text). freeNH3 I i i i i | i i i i | i i i i | i i i i | i i i i \ i » i i i i i i i I i i i i I i i » ' I i ' • ' I 8.0 6.0 4.0 2.0 0.0 ppm Figure 6.8 *H NMR spectrum (CDC13, 300 MHz) of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) under 1 atm NH 3 at 20°C. 215 References on page 248 Chapter 6 Similar observations were found for the reaction of 1 atm NH 3 with a solution of RuBr2(P-N)(PPh3) (6b). The "Pf/H} NMR spectrum for [RuBr(P-N)(PPh3)(NH3)2--Br] (37b) consists of doublets at 8 57.40 (PA) and 8 56.08 (Px), 2 J P P = 31.81 Hz, while the *H NMR resonances for NMe2 are found at 8 3.34 and 2.78, and for (NH3)2 at 8 3.64 and 1.75. (Tables 6.3 and 6.4). 6.2.2 The Solution Chemistry of [RuX(P-N)(PPh 3)(NH 3) 2»X] (37) When solid [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) is dissolved in CDC13 in the absence of excess NH 3 , three species are observed in the NMR spectra (Tables 6.3 and 6.4). The starting material, [RuCl(P-N)(PPh3)(NH3)2—Cl] (37a), is present in a relatively small amount compared to the other two species, identified as fra«s-RuCl2(P-N)(PPh3)(NH3) (38a), and c/5-RuCl2(P-N)(PPh3)(NH3) (39a). The 31P{!H} spectrum is shown in Figure 6.9(b); the presence of two doublets each for each of 38a and 39a shows that both P-N and PPh3 ligands remain coordinated; the doublets at 8 53.86 and 50.79 ( 2JP P = 36.48 Hz) are assigned to the trans isomer 38a because of the comparable coupling constant to that of trans-Cl isomers 6a (36.54 Hz) and 33a (37.76 Hz). The *H NMR singlets due to the two symmetrical NMe groups and the NH 3 are found at 8 2.72 and 1.64, respectively. For the cis isomer (39a), the 31P{1H} NMR peaks are found at 8 59.27 and 51.45 ( 2JP P = 32.29 Hz); inequivalent NMe groups are indicated by singlets at 8 3.61 and 2.94, while the NH 3 is detected at 8 0.38 in the ! H NMR spectrum. 216 References on page 248 Chapter 6 39a 38a (a) (b) • » f | i i i t | i i f i | i i i i | i i i i | « i i i | » t i i | i i i i | i i « i | t i i n i n i | i i i i | i i n | i i i m m i n i i | n n | m » I * » " l " " l " " l ' " » l " l | I M H | i m | 64 58 52 46 40 ppm Figure 6.9 3 1P{ 1H} spectra (121.4 MHz, 20°C, CDCI3) for [RuCl(P-N)(PPh 3)(NH 3)2-Cl] (37a): (a) with 1 atm NH 3 and (b) absence of excess NH 3. Table 6.3 3 *P {1H} NMR data for Ru(II) ammonia complexes in CDC13. Complex 5 P-N 8PPh 3 2Jpp(Hz) [RuCl(P-N)(PPh 3)(NH 3) 2-Cl] (37a) 57.20 53.24 32.05 [RuBr(P-N)(PPh 3)(NH 3) 2-Br] (37b) 57.40 56.08 31.81 *ra«s-RuCl2(P-N)(PPh3)(NH3) (38a) 53.86 50.79 36.48 frows-RuBr2(P-N)(PPh3)(NH3) (38b) 55.25 50.65 36.66 c/5-RuCl 2(P-N)(PPh 3)(NH 3) (39a) 59.27 51.45 32.29 cw-RuBr 2(P-N)(PPh 3)(NH 3) (39b) 62.86 51.85 31.75 217 References on page 248 Chapter 6 Table 6.4 X H NMR data for Ru(II) ammonia complexes in CDCI3. Complex 5 Ru-N(CH3)2 8 Ru-NH3 [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) 3.19, 3.00 3.72, 1.70 [RuBr(P-N)(PPh3)(NH3)2-Br] (37b) 3.34, 2.78 3.64, 1.75 fraws-RuCl2(P-N)(PPh3)(NH3) (38a) 2.72 1.64 ^/w-RuBr2(P-N)(PPh3)(NH3) (38b) 3.01 1.58 c/5-RuCl2(P-N)(PPh3)(NH3) (39a) 3.61,2.94 0.38 m-RuBr2(P-N)(PPh3)(NH3) (39b) 3.97, 2.74 0.48 The presence of the three complexes can be explained by the equation shown in Figure 6.10. In the absence of excess NH 3 , the NH 3 trans to the coordinated CI is replaced by the "associated CI" to form the neutral fra«s-RuCl2(P-N)(PPh3)(NH3) (38a), which then rearranges to the more stable cis isomer 39a. The concentrations of the three species are time-dependent, those of 37a and 38a diminishing significantly within 10 min. After 1 week, [38a] is zero, while there are 10 % 37a and 90 % 39a; addition of 1 atm of NH 3 completely regenerates 37a. ci P h a P ^ NMe 2 Ru^  N H 3 --a 37a - NH 3 NMe 2 CI ; R i i - —C I P h j P ^ Cl -PhjP' NMe 2 RU^—NHj NH3 38a CI 39a 1 atmNH3 Figure 6.10 Reversible conversion of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) to cw-RuCl2(P-N)(PPh3)(NH3) (39a). 218 References on page 248 Chapter 6 The solution chemistry of the Br analogue 37b is identical to that of 37a. The change of halide is reflected in changes in the chemical shifts in the NMR spectra (Tables 6.3 and 6.4). 6.2.3 The Solid State Reaction of RuX2(P-N)(PPh3) with NH 3 When a solid sample of RuCl2(P-N)(PPh3) (6a) is exposed to 1 atm NH 3 , a colour change from green to pink occurs in 5 min, and the microanalysis of the solid product corresponds to RuCl2(P-N)(PPh3)(NH3). A green solution formed when this solid was dissolved in CDC13, and the resulting "Pf/H} and J H NMR spectra (within 5 min of dissolution) indicated the presence of 37a, 38a and 39a in similar concentrations (Figures 6.11 and 6.12). After 30 min, the concentrations of 37a and 38a significantly diminish while that of 39a increases. The initial presence of 37a must be due to a slight excess of NH 3 present in the solid. The data lead to the conclusion that *ra«s-RuCl2(P-N)(PPh3)(NH3) (38a) is initially formed in the solid state and then, in solution, it rearranges to the more stable cis isomer 39a. The trans to cis rearrangement supports indirectly the formation of *raws-RuCl2(P-N)(PPh3)(SH2) (18a') en route to cw-RuCl2(P-N)(PPh3)(SH2) (18a) (Figure 5.9); that is, the NH 3 ligand likely initially dissociates to form the square pyramidal complex that rearranges to a trigonal bipyramidal structure prior to attack by NH 3 at the position cis to PA-The solid state reaction of RuBr2(P-N)(PPh3) (6b) with NH 3 produced fraws-RuBr2(P-N)(PPh3)(NH3) (38b) which also rearranges to the more stable cis isomer 39b in solution. 219 References on page 248 Chapter 6 39a 39a 38a j M iifi m^ i 11111111 11111111 i M | ill ijf 11 tfi i 1111111 I^I 111111 I ^ I 11 • I'' njj • • • I •' • ijg HIM • • Figure 6.11 31P{XH} NMR spectrum (121.4 MHz) of *raws-RuCl2(P-N)(PPh3)(MJ.3) (38a) 5 min after dissolution in CDC13 at 20°C. 37a 39a • i i i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — i — 4.0 S .B 3 .0 2 . B 2 .0 l . B 1—I—I—I—I I I—I—I 1.0 1—I—I—I—I—I—I O.B PPM 0.0 Figure 6.12 *H NMR spectrum (300 MHz) of /raw5-RuCl2(P-N)(PPh3)(NH3) (38a) (5 min after dissolution in CDC13 at 20°C) in the region 8 0.0 to 4.0. 6.2.4 The Preparation of [RuCl(P-N)(PPh3)(NH3)2]PF6 (41) Conductivity measurements, performed on acetone or CH2C12 solutions of [RuX(P-N)(PPh3)(NH3)2"-X] (37) in the absence or presence of 1 atm NH 3 , showed surprisingly that the solution species are non-conducting. Thus, these complexes are "close ion pairs" in solution, and Figure 6.7 shows a plausible formulation with H-bonding of the X-atom. 220 References on page 248 Chapter 6 The reaction of rRuCl(P-N)(PPh3)(NH3)2---Cl] (37a) with NH4PF6, under 1 atm of NH 3 , resulted in the displacement of the associated chlorine as CI" anion, and formation of a yellow solid, formulated as [RuCl(P-N)(PPh3)(NH3)2][PF6] (41); the conductivity of 41 in acetone (with or without the presence of excess NH3) was 140 + 5 ohm"1 cm2 mol'1, consistent with a 1:1 electrolyte.23 In the absence of excess NH 3 , the 31P{1H} NMR spectrum (in de-acetone, Figure 6.13(a)) shows two doublets at 8 58.87 and 8 51.70 ( 2J P P = 31.40 Hz), comparable to those of [RuCl(P-N)(PPh3)(NH3)2-Cl] (37a) [8 57.87 and 8 52.60 ( 2JP P = 31.93 Hz, de-acetone, Figure 6.13(b))]; some trace signals at ~ 8 55.4 in Figure 6.13(a) were not identified. When the sample containing 41 is placed under 1 atm NH 3 , the only signals present are at 8 54.94 and 8 51.47 ( 2JP P = 32.05 Hz, Figure 6.14), and are attributed to [Ru(P-N)(PPh3)(NH3)3-Cl][PF6] (40a), where the coordinated Cl-atom of 41 has been replaced by another NH 3 ligand. The formation of such a tris-ammine complex was confirmed by reacting RuCl2(P-N)(PPh3) (6a) with 2 equiv of NH4PF6 under 1 atm NH 3; the 31P{1H} NMR chemical shifts at 8 55.26 and 8 51.67 ( 2JP P = 32.05 Hz), which are similar to those of 40a, are attributed to in situ formation of |^u(P-N)(PPh3)(Ml3)3][PF6]2 (40b). Repeated attempts to isolate 40b yielded only dark yellow oily residues. The conductivity of 40b, prepared in situ in acetone after removal of NH4CI, was 288 ohm"1 cm2 mol"1, in the range for a 1:2 electrolyte.23 A tentative reaction scheme for the formation of the PF6" salts is shown in Figure 6.15. It is likely that 41 is formed by the direct reaction of 37a with NH4PF6 in the absence of excess NH 3; however, this is difficult to demonstrate directly because in the absence of excess NH 3 , 37a isomerizes to czs-RuCl2(P-N)(PPh3)(NH3) (39a). 221 References on page 248 Chapter 6 P P M 4 . 4 I l l l | l l I l l l l • I I • l I • I l l l l I l l • • | • • • • I 1 1 1 1 I ' 1 1 . I I I l I I I l l I • • I l I l eb S B s o Figure 6.13 31P{XH} NMR spectra (121.4 MHz) of (a) [RuCl(P-N)(PPh3)(NH3)2][PF6] (41) (a septet due to PF6 is located at 5 -143.4) and (b) [RuCl(P-N)(PPh3)(NH3)2"-Cl] (37a) in de-acetone at 20°C. y i I i | i i i l y i i • I i ' " i ^ i ' • ' I • r,%J±' Figure 6.14 31P{1H) NMR spectrum (121.4 MHz) for the in situ formation of [Ru(P-N)(PPh3)(NH3)3-Cl][PF6] (40a) from the reaction of [RuCl(P-N)(PPh3)(NH3)2][PFe] (41) and 1 atmNH3 in d6-actone at 20°C (septet due to PF6 is located at 5 -143.4). 222 References on page 248 Chapter 6 ...NMej C I — ; R u — N H 3 42 air-sensitive green solid PF* heat, vacuum -NH3 ...NMej CI -Rpf Ph,P' " N H 3 N H 3 c i 37a 1 equiv NH,FF6 latmNHa ) -NH4Q H 3 N P^P' ...NMe2 R u - — N H 3 N H 3 Q ] 40a PF f i ^ ^ N M e 2 CI ~Z$~~—NH3 Ph,P' PF f i 41 C I — PhjP' , . . - N M e 2 ZequivNHiPFj — C I latmNH, 6a ,..NMe2 UJl—tif—NH3 P h j P ^ N H 3 40b 1 equiv NH,PF6 latmM^ Figure 6.15 Reaction scheme for the preparation of NH 3 complexes containing PF6" ions. Unfortunately, the microanalysis of 41, a yellow solid, is not consistent (especially the high N content, see Section 2.11.2.5, p. 68) with the formulation [RuCl(P-N)(PPh3)(NH3)2][PF6], in part because of the presence of unidentified species, which have lH NMR signals in the region 8 0.8 to 2.4 (Figure 6.16). Drying 41 in vacuo at 80°C resulted in a dark green solid with a microanalysis indicating the loss of an NH 3 molecule, and formation of [RuCl(P-N)(PPh3)(NH3)][PF6] (42). This solid in de-acetone gave new broad doublets in the ^Pl/H} NMR spectrum at 8 48.64 and 8 47.85. Upon exposure to air, a solid 223 References on page 248 Chapter 6 sample of 42 decomposed into a black powder. The reactive nature of this complex is consistent with the presence of a vacant coordination site. When the isolated yellow solid (41) was dissolved in CDC13, all three species, 40a, 41, 42, were observed in the "Pf/H} NMR spectrum (cf. Figure 6.15). N H 3 phenyl region Ru-NMe 2 A I 1 1 1 1 1 I I I I I 11 I I I I I I I • • ' J 1 1 1 11 ' ^ 1 1 1 I I I 1 1 1 ^ 1 1 1 1 11 1 1 I j I I I 11 I 1 1 1 ^ I I I I I 1 1 1 1 j I I 1 1 I I 1 1 n 1 1 1 1 1 1 I I 1 ^ I ' 1 1 I I ' ' Figure 6.16 *H NMR spectrum of (300 MHz) of [RuCl(P-N)(PPh3)(NH3)2][PF6] (41) in de-acetone at 20°C; *, unidentified, but (5 3.4, 1.2) and •acetone (5 2.0) are present. The conductivities of species 40a and 41 are identical, indicating 1:1 electrolytes in both cases, and implying again that in 40a the Cl-atom is associated strongly with the cationic complex. Perhaps hydrogen-bonding plays a role as in 37a (Figure 6.7). Several attempts to grow crystals of 37a and 41 were unsuccessful. 224 References on page 248 Chapter 6 6.3 The Coordination Chemistry of N 2 0 6.3.1 N 2 0 as a Potential Oxidant Nitrous oxide, also known as "laughing gas" is a colourless, odourless, non-flammable, and non-toxic gas. At room temperature, it exists as a liquid at pressures of > 50 atm. Commercial manufacture is from the thermal decomposition of ammonium nitrate at ~ 270°C: NH4NO3 h e a t > N 2 0 + 2H 20 N 2 0 is primarily used as an inhalation anaesthetic in medicine and dentistry, and as a dispersing agent in cream whippers. N 2 0 is a linear molecule as expected by the following resonance forms:24 :N=N—6:~ *- ":N=N=6: At temperatures above 600°C, N 2 0 is thermodynamically unstable and decomposes into its elements:25 2N20 2N, + 0 9 - ^Urno!"1 Interest in the inorganic chemistry of N 2 0 has advanced partly because of its potential use as an oxidant in catalytic systems. N 2 0 only reacts slowly with oxidizing and reducing agents and is relatively inert towards metal complexes, but is an attractive oxidant because of the following advantages: (i) Its oxidizing power is comparable to those of hydrogen peroxide and perbromate owing to the large thermodynamic driving force for the loss of N 2 . (ii) In the absence of activating reagents such as metal complexes or surfaces, N 2 0 is kinetically inert toward organic molecules, implying oxidation by N 2 0 could have conceivable selectively upon activation by catalysts, (iii) N 2 0 is inexpensive and non-toxic, (iv) The by-product of any potential catalytic systems involving N 2 0 is N 2 (Figure 6.17). 2 6" 3 0 225 References on page 248 Chapter 6 N,0 M = metal catalyst; sub = organic substrate M(sub)(N20) sub(0) Figure 6.17 Potential catalytic cycle for the oxidation of organic substrates using N 20. Previous to this work, only one coordinated N 2 0 complex, [Ru(NH3)5(N20)]2+, has been reported with definite characterization.31'33 The complex was first prepared by Armor and Taube by adding N 2 0 to an aqueous solution of [Ru(NH3)5(H20)]2+.31a Whilst this route did not give a high purity product, an indirect route discovered by Bottomley and co-workers gave good yields of [Ru(NH3)5(N20)]2+:33 [Ru(NH3)3(NO)]3+ + NH 2OH + OH • [RuCNH3)5(N20)]2+ + 2H20 Although numerous studies have been carried out to ascertain the bonding mode of N 2 0 in this complex, no definitive evidence has supported either the possible Ru-N-N-0 3 1 b' 3 3 e or Ru-0-N-N3 2 c'd bonding modes. However, circumstantial evidence such as IR data, force constants, and the similarity of the electronic spectra of [Ru(NH3)5(N20)]2+ and [Ru(NH3)5(N2)]2+, strongly suggests bonding through the N-atom;33c theoretical studies by Tuan and Hoffmann also indicate that N-linkage complexes are more stable than the O-linkage complexes.34 226 References on page 248 Chapter 6 Interest in the reactivity of N 20 has also involved oxygen-atom transfer from N 20 into a transition metal-ligand bond (cf. Figure 6.17). The ligand may range from hydrogen to organic substrates. The catalytic reduction of N 20 to N 2 with concomitant oxidation of PPh3 to OPPh3 by CoH(N2)(PPh3)3 has been studied by Yamamoto and co-workers,35 and of interest because a ligand, rather than the metal centre, was oxidized. Consequently, the N20-oxidation of other ligands and substrates coordinated to metal centres is worth investigation. Hillhouse and co-workers have studied the reactions of group 4 transition-metal (Ti, Zr and Hf) complexes with N 20 that result in the oxidation of a coordinated ligand.36 For example, the reaction with the diphenylacetylene zirconocene complex Cp*2Zr(C2Ph2), with subsequent treatment with HC1, leads to the formation of Cp*2ZrCl2 and deoxybenzoin, PhCH2C(0)Ph (Figure 6.18).36b The high strength of the group 4 M-0 bonds, however, places limitations on the potential applications of the use of such metal systems with N 20 in catalytic cycles, and it is certainly of interest to study late transition metal systems as they form weaker bonds with heteroatoms (N, S, O). Ph Ph I 0" Figure 6.18 Stoichiometric formation of PhCH2C(0)Ph utilizing N 20. N 20 reacts with cyclic and acyclic nickel alkyls to give stable nickel alkoxide complexes, with regiospecific insertion of the O-atom into the Ni-C bond (Figure 6.19).28'37 227 References on page 248 Chapter 6 Elimination of the organic moieties to form an alcohol, cyclic ether or lactone occurs via addition of HC1,12 and CO, respectively.28 HCl N \ Ni N 7 0 - N 2 CO Figure 6.19 Transfer of the O-atom of N 2 0 into a Ni-C bond. Monomeric late transition metal hydroxo complexes are important in catalytic processes such as hydration of olefins to alcohols, nitriles to carboxamides and the Wacker process (see Section 3.3.2, p. 88); however the synthesis and isolation of such complexes may be difficult because elevated temperatures and extended reaction times are often required.27'38"40 Kaplan and Bergman have shown recently that N 2 0 can be used to insert an O-atom into one or two Ru-H bonds of (dmpe)2Ru(H)2 (dmpe = l,2-bis(dimethylphosphino)ethane) under mild conditions to form (dmpe)2Ru(H)(0H) and (dmpe)2Ru(OH)2 (Figure 6.20).39'40 ^ X P M e 2 Me2 OH Me2 M 6 2 OH Me2 J H 1 eqvdvN,Q, 2 5 ° C ^ f P J . *S 1 ataN 2Q, 25°C f F J P > L^PMea M E 2 H Me2 Me2 6H Me2 Figure 6.20 Formation of Ru-OH complexes by O-atom insertion from N 20. 228 References on page 248 Chapter 6 For the reactions with N2O with the Ni and Ru complexes described above, no intermediates were observed to suggest any mechanistic pathway for O-atom insertion. However, the researchers suggest coordination of N 20 prior to N2 loss and O-atom transfer in both cases. For the former case, a five-coordinate Ni intermediate was insinuated,29 while for the Ru hydride complex, initial N 20 coordination to the Ru either via an O- or N-atom with subsequent rearrangement was suggested (Figure 6.21)40 Despite these suggestions, the direct N 2 0 insertion pathway as observed for the Zr complex (Figure 6.18) cannot be ruled out. .H (dmpe)2(H)RuQ N (dmpe)2(H)RuC N.v •N Figure 6.21 Possible coordination modes of N 20 to (dmpe)2Ru(H)2. 6.3.2 The Reaction of RuCl2(P-N)(PPh3) with N 2 0 When 1 atmN20 is added to a solution of RuCl2(P-N)(PPh3) (6a) in CD2Cl2at 20°C, no immediate reaction is noted by NMR spectroscopy. After 2 days, decomposition of the Ru(U) species occurs, with identifiable species in the ^ Pf^ H} NMR spectrum (Figure 6.22(e)) being the Ru(m) oxo complex, (u-0)(u-Cl)[RuCl(P-N)]2 (17) (5 39.35, 38.21 (d, 4 J P P = 10.08 Hz)), 0=PPh3 (s, 8 27.22) and 0=P-N (s, 5 25.33; signal is assigned following the preparation of 0=P-N from P-N and H2O2).1 Assignment of the chemical shifts in the *H NMR spectra proved to be difficult because the 8 2.0 - 4.0 region contains overlapping signals due to NMe resonances of the above species. As discussed in Chapter 3, 17 is formed by the oxidation of 6a in an 0 2 atmosphere, and evidently there is a slow oxidation reaction between 229 References on page 248 Chapter 6 6a and N20. When the N 20 pressure was increased to 6 atm, the ^Pl/H} NMR spectrum, measured within 5 min of N 20 addition, became very noisy and the chemical shifts due to 6a became broad Figure 6.22(b). This behaviour is characteristic of the presence of a paramagnetic species, and perhaps formation of diamagnetic 17 occurs via a paramagnetic Ru(III) intermediate. The reaction of 6a with ~ 6 atm N 20 in CD2C12 between -90 and -40°C surprisingly produced a bright yellow solution. Two species are identified by two sets of AX doublets at 8 49.52 (PA) and 8 40.06 (Px), 2 J P P = 27.93 Hz, and at 8 47.54 (PA) and 8 37.91 (Px), 2 J p p = 27.01 Hz in the 31P{1H} NMR spectra (Figure 6.22(c) and (d)). From previous work in this laboratory, the latter species was identified as the dinitrogen complex cw-RuClztP-N^PhsXV-NO (43).u As indicated by 31P{1H} NMR data (Figure 6.23(a)), 43 is formed when 6a is placed under 6 atm N 2 . Furthermore, 43 is in a dynamic equilibrium with 6a and much higher pressures of N 2 are required for complete product formation. The assignment of a cis structure for 43 is based on the two singlets at 8 3.63 and 3.04 due to NMe2 observed in the *H NMR spectrum. A direct comparison of the reactions of 6a with N 20 and N 2 is shown in Figure 6.23. The new species, 44 is tentatively ascribed as the coordinated N 20 complex cw-RuCl2(P-N)(PPh3)(N20). The assignment of a cis structure for 44 is based on the similar positions of the chemical shifts and coupling constants for 43 and 44 in the 31P{1H} NMR spectra, and the presence of two singlets at 8 3.60 and 2.85 due to the NMe 2 of 44 in the *H NMR spectrum (at -88°C). The N 20 complex is only observed and stable at temperatures at or below -40°C. 230 References on page 248 Chapter 6 0=PPh3 17 (e) 20°C u u 0=P-N 44 44 (d) -90°C 43 6a 6a 43 0=PPh3 44 (c) -40°C 44 43 43 (b) 20°C 6a + 6 atm N 20 (a) 20°C P I ..N a—^Ril—ci 6a 90 I 11 i 11 n i i i u i i | 11 11 I i i 111 | 11 11 | 11 i i | ; i t i | SO 70 60 50 4-0 111111111II III1111 1111 1111 30 PPM 20 Figure 6.22 nV{lH} NMR spectrum (121.4 MHz, CD2C12) of (a) 6a, and the reaction of 6a with 6 atm N 20 at (b) 20°C, (c) -40°C, (d) -90°C and (e) 20°C after reaction time of 2 days. The spectra at low temperatures are time-independent; trace 0=PPh3 is formed during transfer of the NMR sample from the cold temperature bath to the spectrometer probe. 231 References on page 248 Chapter 6 44 6a + 6atmN20 (b) -40°C 43 6a + 6 atm N 2 (a) 20°C |T1 I I | I I I I | i I I I [ I I I I J i I I I | I M I | I 1 I 9 0 8 0 7 0 60 5 0 4 0 3 0 P P M 2 C Figure 6.23 31P{1H} NMR spectra (121.4 MHz, CD2C12) for the reaction of 6a with (a) 6 atm N 2 at 20°C and (b) 6 atm N 20 at -40°C. Although 31P{1H} NMR data are consistent with formation of a coordinated N 20 species 44, the coordination mode of N 20 is not identifiable, although coordination via the N-atom seems most likely because of the formation of the r j 1 - ^ adduct. The initial coordination of N20, followed by the cleavage of the O atom to form 43 and 02, seems plausible (Figure 6.24). At temperatures below -40°C, the species 6a, 43 and 44 are stable ^definitely, and 0 2 is ineffective in oxidizing the Ru(II) complexes; trace 0=PPh3 (as seen in Figure 6.22 (c) and (d)) is formed during transfer of the NMR sample from the cold temperature bath to the spectrometer probe. This was verified when a sample of 6a was placed under latm 0 2 at -40°C; no reaction was indicated by the 31P(1H} NMR spectrum. In 232 References on page 248 Chapter 6 both systems involving N 2 0 and 0 2, the formation of 17 and 0=PPh3 is observed when the temperature is slowly raised to room temperature. The mechanistic aspects involving the 02-oxidation, however, has not been ascertained. CI PhsP; , N i i — N = N = 0 ..N Ru- Cl-PhsP; Rir N = N + 1/2 0 2 CI 44 CI 43 N 2 0 +N 2 +N 2 0 Ct PhaP: . N Ru" CI 6a o 2 T > - 4 0 C 0=PPh3 (u-0)(u-Cl)2[RuCl(P-N)]2 17 Figure 6.24 Proposed reaction scheme for the formation of 17 and 0-PPh3, if N 2 0 is initially coordinated to 6a via the terminal N atom. If the N 2 0 is coordinated to 6a via the O-atom, the direct migratory insertion of O into the Ru-PPh3 bond is conceivable. This correlates with one mechanism proposed in Chapter 3 (Section 3.2.1) where the formation of 0=PPh3 and 17 occurs via the initial coordination of 0 2 to the Ru. Of note, the oxidation of PPh3 is catalytic. When an excess of 2 equiv of PPh3 is added to the reaction of 6a with N 20, all the PPh3 is converted to 0=PPh3 (Figure 6.25) and, only when all the PPh3 has reacted, is the Ru(II) species oxidized to 17. 233 References on page 248 , N a—^Ril— a N , 0 2W P h , F -N 2 0 6a - O P P h , .+PPh3 Chapter 6 C I -Ph3Pr . N R i l — O — N = N a 44 - N 2 . N I ' a—^Rii P V x =cr a Figure 6.25 The catalytic oxidation of PPh3 by N 20. The potential use of 6a as an oxidation catalyst is promising because N 2 0 preferentially oxidizes PPh3 rather than the Ru centre. However, attempts to oxidize organic substrates such as ethylene, styrene or cyclooctene at ambient conditions were unsuccessful. Even with 3 to 6 atm N 2 0 added to a CH2C12 or CeHs solution containing 6a and 10 equiv substrates (at -80 to 60°C), only 17 and 0=PPh3 were observed to form while the organic substrates remained unchanged. Of note, the substrates studied do not coordinate to 6a, while in order for N 2 0 to be an effective oxidant, it is likely that the substrate in question must bind to the Ru. Furthermore, insertion of the O-atom into a Ru-substrate bond must be preferred over that of the Ru-PPh3 bond. Fine tuning of the Ru complex is perhaps required to obtain an effective catalytic cycle using N 2 0 as the oxidant. These modifications may include incorporation of an alkyl ligand or the replacement of the PPh3 with a more strongly basic phosphine. 234 References on page 248 Chapter 6 6.4 Ruthenium Carbene Complexes: The Synthesis and Reactivity of as-RuCl2(P-N)(PR3)(=C=C(H)R') (R, R' = Ph,/Molyl) Carbenes are formed when monohapto, two-electron alkylidene ligands of the type CH 2 , CHR and CR 2 (R = alkyl or aryl group) form M=C d-p double bonds within metal complexes. The first carbene complex, (CO)5W=C(OMe)Me, was reported by Fischer and Maasbol in 1964.41 Two efficient tools for the characterization of metal carbenes are X-ray crystallography and 1 3 C NMR spectroscopy. A short M-C(carbene) bond distance and a downfield shift of the carbene-carbon resonance is indicative of a M=C bond. Metal carbene complexes constitute an important area of research in organometallic and catalytic reactions,42 and new organic compounds of well-defined stereochemistry have been accessed from complexes with functionalized carbenes 4 3 6.4.1 Characterization of Cw-RuCl2(P-N)(PR3)(=C=C(H)R) Dark orange solutions were obtained when a mixture of 10 equiv of HCCPh or HCC(/?-tolyl) and 6a or 7a in CH2C12 was refluxed at 40°C, and work-up yielded dark orange powders, that were identified as cw-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45), cw-RuCl2(P-N)(P(p-tolyl)3)(=C=C(H)Ph) (46), and cw-RuCl2(P-N)(PPh3)(=C=C(H)(/7-tolyl)) (47). The formation of the vinylidene moiety is thought to occur via an t|2- to V-alkyne slippage followed by an a,P-hydrogen shift (Figure 6.26); a repulsive 4e interaction between a d„ orbital of the Ru d6 system and the perpendicular filled TC orbital of the alkyne destabilizes the metal r|2-alkyne bond and, by localization of electron density on the Ru centre, the vinylidene complex is relatively more stable than the r|2-alkyne complex.44 235 References on page 248 Chapter 6 H H / H L*Ru—il l 9P \ Ph Ph Ph Figure 6.26 Formation of a vinylidene complex from a 1 -alkyne ligand. L„ represents X-ray quality, red-orange crystals of 4 5 were obtained from the slow evaporation of a CDC13 solution of the complex in an NMR tube. The ORTEP plot, selected bond lengths and bond angles are shown in Figure 6.27, and Tables 6.5 and 6.6, respectively. The pseudo-octahedral structure contains two c/s-Cl-atoms [Cl(l)-Ru-Cl(2) 91.50°], with the P-atom of the P-N trans to one Cl-atom, and the vinylidene (=C=C(H)Ph) trans to the second Cl-atom [Cl(2)-Ru-C(l) 172.7°]. The bond length of 1.814 A is indicative of a Ru=C double bond, and is comparable to those observed for other Ru vinylidene complexes (1.823 to 1.86 A):45 e.g. [Ru{=C=C(Me)R}(Ti5-C9H7)(PPh3)2][CF3S03] (1.838 A, R = 1-cyclohexenyl)46 and [Ru(=C=C(H)Me}(PMe3)2(Ti5-C5H5)][PF6] (1.845 A).47 The C(l)-C(2) distance of 1.329A is in the normal range (1.25 to 1.41 A)45 for a C=C bond, while the Ru-C(l)-C(2) angle of 176.4° indicates the linearity of the Ru=C=C moiety. All the other bonds with the exception of the Ru-P(l) bond are within the range found for the other cis-RuCl2(P-N)(PPh3)(L) complexes. The distance of 2.332 A for Ru-P(l) is slightly longer than the 2.2617 - 2.2884 A for analogous complexes previously discussed (Sections 4.2, 4.3 and 6.1), and this is attributed to the distribution of more electron density to the d-p bonding of Ru=C. auxiliary ligands of the Ru complex. 236 References on page 248 Chapter 6 C(13) Figure 6.27 The ORTEP plot of c/s-RuCi2(P-N)(PPh3)(=C=C(H)Ph) (45). Thermal ellipsoids for non-hydrogen atoms are drawn at 33 % probability (some phenyl carbons have been omitted for clarity). Full experimental parameters and details are given in Appendix X. 237 References on page 248 Chapter 6 Table 6.5 Selected bond lengths (A) for cw-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) with estimated standard deviations in parentheses. Bond Length (A) Bond Length (A) Ru(l)-Cl(l) 2.434(2) Ru(l)-N(l) 2.308(7) Ru(l)-Cl(2) 2.495(2) RuO)-C(l) 1.814(8) Ru(l)-P(l) 2.332(2) C(l)-C(2) 1.329(12) Ru(l)-P(2) 2.346(2) C(2)-C(3) 1.455(13) Table 6.6 Selected bond angles (°) for cw-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) with estimated standard deviations in parentheses. Bonds Angle (°) Bonds Angle (°) Cl(l)-Ru(l)-Cl(2) 91.50(9) P(l)-Ru(l)-P(2) 106.94(8) Cl(l)-Ru(l)-P(l) 169.56(8) P(l)-Ru(l)-N(l) 82.2(2) Cl(l)-Ru(l)-P(2) 83.15(8) P(l)-Ru(l)-C(l) 87.3(3) Cl(l)-Ru(l)-N(l) 87.8(2) P(2)-Ru(l)-N(l) 170.9(2) Cl(l)-Ru(l)-C(l) 95.6(3) P(2)-Ru(l)-C(l) 89.9(3) Cl(2)-Ru(l)-P(l) 85.45(8) N(l)-Ru(l)-C(l) 89.9(3) Cl(2)-Ru(l)-P(2) 92.61(9) Ru(l)-C(l)-C(2) 176.4(8) Cl(2)-Ru(l)-N(l) 88.7(2) C(l)-C(2)-C(3) 124.3(9) Cl(2)-Ru(l)-C(l) 172.7(3) The IR spectrum of 45 depicts a strong band at 1615 cm"1 which is typical of the vc=c stretching of vinylidene ligands.45'48 The ^P^HJand *H NMR spectra of 45 are shown in Figures 6.28 and 6.29, respectively. The P A and P x chemical shifts are found at 8 37.85 and 36.40,2JPP = 26.50 Hz, 238 References on page 248 Chapter 6 while the inequivalent NMe groups are seen as singlets at 5 3.60 and 3.11 in the *H NMR spectrum. The Cp-proton is coupled to the or/to-protons of the phenyl ring giving a doublet of doublets at 6 2.43 (4JHH = 6 Hz). The ^Pl/HJand *H NMR chemicals shifts for RuCl2(P-N)(P(p-tolyl)3)(=C=C(H)Ph) (46) and RuCl2(P-N)(PPh3)(=C=C(H)(p-tolyl)) (47) are nearly identical to those of 45 with the exception of an additional singlet due to the Me of the /?-tolyl group at 8 2.16 in the *H NMR spectra (see Sections 2.12.2 and 2.12.3). Characteristic 1 3 C NMR data pertaining to the resonances of the four C-atoms of the RuC a C p and of the N(CyH 3 ) 2 units were obtained for 45: the strongly deshielded C a resonates at 8 358.2 (t, 2JCP = 18.6 Hz); Cp at 8 111.0 (s); and inequivalent CY signals at 8 57.26 and 52.52 (s). Figure 6.28 31P{*H} NMR spectrum (81.0 MHz, 20°C) of c/5-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) in CDC13. 239 References on page 248 Chapter 6 Phenyl region Ll NMe NMe Cp-H T—1—1—f 3.5 2.5 ppm 8.5 7.5 6.5 5.5 4.5 Figure 6.29 *H NMR spectrum (200 MHz, 20°C) of c/5-RuCl2(P-N)(PPh3)(=Ca=Cp(H)Ph) 6.4.2 The Reactivity of Cis-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) As a result of localization of electron density in the Ru=C« bond and on the Cp atom, there is electron deficiency at the C a atom of vinylidene complexes.49 Consequently, electrophiles are attracted to both the Ru=Ca bond and the Cp atom, while nucleophiles react at the C a atom. Bianchini and co-workers reported the reaction of H2S with fac,cis-[(PNP)RuCl2{=C=C(H)Ph}] (PNP = CH3CH2CH2N(CH2CH2PPh2)2) to give an r\l-2-phenylethanethial complex, /ac,cw-[(PNP)RuCl2{S=C(H)CH2Ph}].50 To investigate the reactivity of 45, an analogous reaction with H2S was carried out in this thesis work. A colour change from orange to brown resulted when H2S was passed through a refluxing CH2C12 solution of 45, and a dark brown solid was isolated after work-up with hexanes. The 3 1P{1H) and *H NMR spectra of this solid in CDC13 are consistent with the formation of a single new (45) in CDC13. 240 References on page 248 Chapter 6 product, cw-RuCl2(P-N)(PPh3)(S=C(H)CH2Ph) (48) [3lP{1H}: doublets at 8 59.61 (PA) and 8 42.36 (Px) 2 J P P = 28.22 Hz; ! H: 8 3.04, 2.52 (s, NMe2), 8 3.18 (t, =CH, 3 J H H = 15 Hz), 8 1.30 (d, CH2, 3 J H H =15 Hz)]. However, an analytically pure solid could not be isolated even after several attempts with varying times (3 - 16 h). Figure 6.30 shows the proposed mechanism for the formation of 48. Initially, the nucleophilic Cp is protonated by the acidic hydrogen of H2S leading to the formation of a cationic carbyne complex (which can be observed by 31P{1H} NMR spectroscopy [5 62.80 (PA), 8 38.36 (Px) 2 J P P = 22.82 Hz] in the in situ reaction of 45 with excess HBF 4-Et 20 in CDC13; the *H NMR spectrum could not be assigned because of overlapping peaks due to excess Et20). The electrophilic C a is then attacked by the SH", and a S,Ca-hydrogen shift is followed by S-atom insertion into the Ru-C a bond. . N H i r 45 | | a. a H , S a — ; i i t l ' = c t t = c B / Ph3Pr | ^ if ph a , . . N H R P h 3 P ^ \ a Ph S H . . . N H C l - ^ R l i ' = C _ < H Ph3Pj \ Ph CI H a Ph,P, I " N R U — s = c ; H CI 48 \ h ph 3 PjT I \ ' ci 3 V Ph Figure 6.30 Proposed mechanism for the formation of czs-RuCl2(P-N)(PPh3)(S-C(H)-CH2Ph) (48) from 45 and H2S. 241 References on page 248 Chapter 6 THF and CH2CI2 solutions of 45 also react with H2O under reflux conditions as implicated by changes in NMR spectra. The brown solid isolated from this reaction consists of many products as indicated by ~ 15 peaks in the 31P{XH} NMR spectrum (CDCU), while the ! H NMR spectrum is uninformative because of many overlapping broad peaks in the region 8 1.2-3.5. Repeated attempts to isolate a pure product were unsuccessful. Two major products in a 1:1 ratio were identified by two sets of broad peaks at 8 44.57, 38.28 (49) and 8 50.55, 18.74 (50) in the 31P{1H} NMR spectrum. By analogy to the reaction offac,cis-[(PNP)RuCl2{S=C(H)CH2Ph}] with H 2 0 where /ac-(PNP)RuCl(CO)(CH2Ph) and fac,cis-(PNP)RuCl2(CO) are formed,51 49 and 50 are tentatively identified as RuCl(P-N)(PPh3)(CH2Ph)(CO) and RuCl2(P-N)(PPh3)(CO), respectively (Figure 6.31). The IR spectrum for a mixture containing 49 and 50 showed two strong bands at 2046 and 1990 cm"1, attributed to v c o . Previously in this laboratory, RuCl2(P-N)(PPh3)(CO) (50) has been observed when CO was added to a solid state sample or a solution of 6a at < -20°C (while at higher temperatures, the bis-CO adducts, trans,cis-RuCl2(CO)2(Ti-1>f) and cw,cw-RuCl2(CO)2(P-N) are formed).1 The 31P{1H} NMR data (8 51.68 and 18.56, 2 J P P = 25.74 Hz) for the in situ reaction at -20°C 1 correspond well with the data assigned (8 50.55 and 18.74) in the current work to 50, although the 2 J P P coupling constants could not be obtained for 49 and 50 because the peaks were broad and the baseline noisy. The Vco value obtained by Mudalige was 1962 cm"1 (Nujol mull of the solid sample). Upon addition of 1 atm HC1 to a mixture containing 49 and 50, the concentration of 49 significantly diminished while that of 50 increased. This observation implies that 49 is initially formed with elimination of HC1 when H 2 0 is reacted with 45, while the HC1 can also react with 49 to form 50 with the 242 References on page 248 Chapter 6 elimination of toluene. The signals due to toluene could not be identified in the X H NMR spectrum because of the presence of other species. O - M e P T ^ H 2 0 HC1 P - T ^ P7~^ . N . . .N A I N H C l - ^ R u = C a = C p T H F , 8 0 ° C , 2 0 h ' C I — ^ R u - C = 0 + C 1 CI CH 2 Ph CO 49 50 VQO = 2046 c m 1 voo = 1990 c m 1 45 Figure 6.31 The reaction of cw-RuCl2(P-N)(PPh3)(=C=C(H)Ph) (45) with H 2 0 at 80°C in THF. Of note, the carbene complexes 45 - 47 are stable indefinitely in air and, at ambient conditions, they do not react with H 2 , HC1, H2S, H 2 0 or NEt3. 6.5 The Reaction of RuCl2(P-N)(PPh3) (6a) with HC1 When 1 atm of anhydrous HC1 gas was bubbled through a dark green CeH6 solution of 6a at r.t., a deep red solution formed immediately, and the isolated bright red solid had a microanalysis and UV-Vis spectrum corresponding to those of the paramagnetic RuCl3(P-N)(PPh3) (15a) (see Section 2.7.1). Figure 6.32 suggests the formation of 15a via a coordinated HC1 intermediate. The 31P{1H} NMR spectrum observed during the in situ reaction in is dependent on the concentration of H Q added (Figure 6.33) and, similar to the reaction of 6a with H 2 0 (Section 5.3, Figure 5.5), an upfield shift of the P A chemical shift is observed as the concentration of HC1 is increased from 1 to 5 equiv; eventually, the P A and P x signals vanish when more than 10 equiv of HC1 are added. The formation of dihydrogen seems rational because no hydride species are observed; however, no *H NMR signal due to 243 References on page 248 Chapter 6 H 2 was observed presumably because of the low concentration of H 2 formed in the reaction. Of note, evidence for H C l complexes of Pt has been reported recently.52 C h — ^ R i r 01 phsPr 6a HCl ,..N C I — CI C l - H Ph3P : , N - C I 1/2 H 2 CI ISa Figure 6.32 Reaction of RuCl 2(P-N)(PPh 3) (6a) with HCl to form RuCl 3(P-N)(PPh 3) (15a). (a) [ 1 l 1 I | I I I I ) I I I I | I I I I | I I I I | I l I I [ I I l I | I I I I | 80 75 70 65 60 55! 50 45 PPM 40 Figure 6.33  31V{ lH} NMR spectra (121.4 MHz, 20°C) for the reaction of RuCl 2(P-N)(PPh 3) (6a) with (a) 1 equiv H C l and (b) 5 equiv H C l in CeD6; spectra measured within 10 min of addition of HCl. 6.6 The Catalytic Hydrogenation of PhC(H)=NPh Using Complexes Containing the Ru(P-N) Moiety The necessity to acquire chiral amines as precursors for the synthesis of pharmaceutical and agrochemical substances has led to accelerated interest in the homogeneous hydrogenation of imines, 5 3 , 5 4 and much work has concentrated on Rh 5 5 and Ir 5 6 systems. Recently, Ru complexes containing phosphine ligands have also been found to hydrogenate imines effectively to the corresponding amines.21'53'57'58 The catalytic ability of 244 References on page 248 Chapter 6 Ru complexes containing aminophosphine ligands to hydrogenate iV-benzyhdeneaniline to N-benzylaniline was briefly investigated, and is described in this section: PhC(H)=NPh H 2 , [catalyst] > PhCH 2 -NHPh Conditions for each hydrogenation experiment were as follows. While under the flow of Ar, the catalyst and imine, in a 1:200 ratio along with 10 mL MeOH, were placed in a glass liner equipped with a magnetic stirrer. The glass liner and its contents were then quickly placed in a machined-steel autoclave which had been previously evacuated, filled with N 2 , and equipped with a high-pressure regulator connected to an H 2 cylinder. The reaction mixture was evacuated and flushed with N 2 three times before a final evacuation. The autoclave was then pressurized with 400 psi H 2 and evacuated three times before a final pressure of 1000 psi H 2 was introduced. With the stirrer turned on, the hydrogenation was allowed to proceed for 3 h. Percentage conversion was then analyzed by gas chromatography using an HP-20M (Carbowax 20M) column. The results for the conversion of PhC(H)=NPh to PhCH2-N(H)Ph by ruthenium aminophosphines are presented in Table 6.7. The specific substrate PhC(H)=NPh, and the chosen conditions, were used to allow for comparison between % conversions by the complexes in the present study and those by Ru phosphine complexes previously studied in this laboratory.21'57 The % conversions by complexes 6a, 7a, 15a and 15b are comparable to those for the most effective Ru species found to date: Ru2Cl5(dppb)2 (98 % after 1 h) and Ru2Cl4(dppb)2 (89 % after 1 h) (dppb = l,4-bis(diphenylphosphino)butane).21'57 The Ru(II) or Ru(ffl) complexes which contain chlorine ligands, one P-N ligand, and a monodentate phosphine (PPI13 or P(p-tolyl)3), are comparable in effectiveness, while the complexes containing the P(p-tolyl)3 ligand are somewhat better catalysts. Contrary to findings for 245 References on page 248 Chapter 6 systems containing dppb,21 the chloro-containing complexes in the present study are more effective than the bromo analogue. Not surprisingly, the "less reactive" complexes containing BPN or two P-N ligands gave relatively low conversions. Table 6.7 Hydrogenation of PhC(H)=NPh using ruthenium aminophosphine complexes. Conditions: 1000 psi H 2 ; [imine] = 0.153 M; [catalyst] = 0.77 mM; 20°C; 3 h; in MeOH. Catalyst % Conversion RuCl2(P-N)(PPh3) (6a) 91 RuCl2(P-N)(P(p-tolyl)3) (7a) 96 RuBr2(P-N)(PPh3) (6b) 57 RuCl3(P-N)(PPh3) (15a) 82 RuCl3(P-N)(P(p-tolyl)3) (15b) 100 RuCl2(P-N)2 (8) 25 RuCl2(BPN)(PPh3) (13) 56 RuCl3(BPN) (16) 54 In order to evaluate further the complexes in Table 6.7 as useful catalysts, conditions for the hydrogenation such as pressure of H 2 , temperature, solvent, and reaction time must be optimized. Mechanistic and kinetic studies might be of value. 6.7 Summary RuCl2(P-N)(PPh3) (6a) forms six-coordinate complexes with H 2 , NH 3 , N 2 , N 2 0 and alkynes. The r| 2 -H 2 complex 36 is characterized crystallographically and its pKa of ~ 11 is determined by NMR spectroscopy. Depending on the concentration of NH 3 and whether 6a is in solution or the solid state, three products (37, 38 and 39) containing NH 3 ligands are 246 References on page 248 Chapter 6 identified, and salts of these complexes may be obtained by reaction with NH4PF6. The formation of a coordinated N 2 0 complex 44 at low temperatures (below -40°C) is especially rare as only one such complex has been reported previous to this work. At higher temperatures, oxidation of 6a by N 2 0 results in the formation of 0=PPh3 and the dinuclear species (ii-0)(|i-Cl)2[RuCl(P-N)]2 (17). Vinylidene complexes, obtained from the reaction of 6a with 1-alkynes, react with H2S and H 20. Finally, 6a can be oxidized by HC1 to form RuCl3(P-N)(PPh3) (15a). It has been shown in this Chapter that a wide range of small molecules binds and reacts with 6a. Preliminary work (not documented here) has also shown that 6a reacts with CH 3CN, NOBF4, NO, CH 3COOH, CH3COSH, NaSEt, SMe2 and C 5 H 5 N without decomposition or oxidation; however because of the many products formed as observed by complex ^Pl/H} NMR spectra, detailed investigation into these reactions was not pursued. Full characterization of the products formed would lead to even greater insight into the reactivity of 6a. 247 References on page 248 Chapter 6 6.8 References 1. Mudalige, D. C. Ph.D. Thesis, The University of British Columbia, 1994. 2. Mudalige, D. C ; Rettig, S. J.; James, B. R.; Cullen, W. R. J. Chem. Soc, Chem. Commun. 1993, 830. 3. (a) Jessop, P. G.; Morris, R H. Coord. Chem. Rev. 1992,121, 155. (b) Heinekey, D. M.; Oldham, W. J., Jr.; Chem. Rev. 1993, 93, 913. (c) Esteruelas, M. A.; Oro, L. A. Chem. Rev. 1998, 98, 577. 4. Hamilton, D. G ; Crabtree, R. H. J. Am. Chem. Soc 1988,110, 4126. 5. (a) Crabtree, R. H ; Hamiltion, D. G. Adv. Organomet. Chem. 1988, 28, 299. 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Tetrahedron Lett. 57,4117. 252 Chapter 7 General Conclusions and Recommendations for Future Research This thesis describes for the main part the reactivity of the five-coordinate, square pyramidal complexes RuCl2(P-N)(PR3) (P-N = [o-(iV,iV-dimethylamino)phenyl]-diphenylphosphine; R = Ph or /?-tolyl) which were successfully synthesized by the reaction of RuCl2(PR3)3 with P-N. The RuCl2(P-N)(PR3) complexes are air-stable in the solid state, but in solution in the presence of 0 2 are oxidized to 0=PPh3 and the crystallographically characterized, dinuclear complex (p.-0)(p.-Cl)2[RuCl(P-N)2]2. Reactions of RuCl2(P-N)(PPh3) with L give c/s-RuCl2(P-N)(PPh3)(L) (L = H2S, alkanethiols, H 2 , N 2 and N20), fr-aw5-RuCl2(P-N)(PPh3)(L) (L = H 20, MeOH and EtOH), or both isomers (L = NH3). The H-atoms bonded to the S-ligands of the cw-RuX2(P-N)(PPh3)(L) type complexes (X = CI, L = H2S, MeSH, EtSH; X = Br, L = H2S) were located isotropically in crystal structures and detected in *H NMR spectra. In particular, the *H NMR spectra of c/5-RuX2(P-N)(PPh3)(SH2) at -50°C show that one H-atom of the coordinated H2S is coupled to the P-atom the P-N ligand, this being explained by the Karplus relationship. Solution thermodynamic parameters for the reversible formation of the H2S and thiol complexes were obtained by variable temperature NMR measurements of equilibrated systems, and show that the Ru-S bonds are weak. Heating a solid sample of c/s-RuCl2(P-N)(PPh3)(SH2) results in the evolution of H2S and suggested formation of cw-RuCl2(P-N)(PPh3); further characterization (e.g. by far-infrared spectroscopy) is needed to confirm this. rraws-RuCl2(P-N)(PR3)(OH2) was formed by the reaction of RuCl2(P-N)(PR3) in acetone solution or in the solid state with H 20. The crystal structures of 253 References on page 256 Chapter 7 fraw5-RuCl2(P-N)(PPh3)(OH2)-(2C6H6) and rraw5-RuCl2(P-N)(PPh3)(OH2)-(1.5C6H6) revealed that the Ru-O distance is shortened when a H-atom of the coordinated H 2 0 interacts with the 7t ring of a benzene solvate molecule. An order for the trans influence of the L ligands is proposed by comparison of the Ru-Cl bond lengths in the X-ray crystal structures of rra«5-RuCl2(P-N)(PPh3)(L) and c/5-RuCl2(P-N)(PPh3)(L): P-N > H2S ~ thiols > H 2 > CI ~ Br >H 20. RuCl2(P-N)(PPh3) also binds H 2 reversibly, and the crystal structure of cw-RuCl2(P-N)(PPh3)(ri2-H2) was determined. Reaction of the dihydrogen complex with proton sponge resulted in the formation of the five-coordinate, monohydride complex Ru(H)Cl(P-N)(PPh3), while the pKa of c/5-RuCl2(P-N)(PPh3)(ri2-H2) was estimated to be ~ 11 by in situ NMR experiments. The reaction of RuCl2(P-N)(PPh3) in the solid state and in solution with excess NH 3 gave fram-RuCl2(P-N)(PPh3)(NH3) and [RuCl(P-N)(PPh3)(NH3)2-Cl], respectively. Both species dissolve in CDC13 solution in the absence of added NH 3 and equilibrate to the more stable c/5-RuCl2(P-N)(PPh3)(NH3). The [RuCl(P-N)(PPh3)(NH3)2-Cl] formulation implies a strongly associated chlorine (possibly H-bonded to the ammine ligands), as indicated by non-conductivity of the complex. Reaction of this complex with NH4PF6 resulted in the expected pRuCl(P-N)(PPh3)(NH3)2]PF6 which, when subjected to vacuum and heat, subsequently gave an air-sensitive, five-coordinate species tentatively formulated [RuCl(P-N)(PPh3)(NH3)]PF6. The formulation of this species requires confirmation, but in any case the species is a good candidate for study of reactions with small molecules. At temperatures ranging from -90 to -40°C, RuCl2(P-N)(PPh3) reacts in situ with 6 atm N 2 0 to give apparently c/s-RuCl2(P-N)(PPh3)(N20) which subsequently forms 254 References on page 256 Chapter 7 cw-RuC^CP-NXPPhsXri1^) and 02; at temperatures above -40°C, 02-oxidation processes yield 0=PPh3 and (|a-0)(ji-Cl)2[RuCl(P-N)2]2. The formulation of the coordinated N 2 0 complex is based on the similarity of the 31P{1H} NMR signals to those of the previously characterized r) 1 -^ complex. More positive confirmation of N2O coordination could be realized if RuCl2(P-N)(PPh3) is reacted with N 2 0 enriched with 1 5 N (I = V4, natural abundance = 0.365 %), and the reaction monitored by 1 5 N NMR spectroscopy. Further, such data should distinguish between N- or O-atom coordination. The potential to use N 2 0 as an O-atom donor to organic substrates should be further investigated. The synthesis and reactivities of Ru(II) complexes containing aminophosphines (BPN, TPN, AMPHOS, PAN and ALAPHOS) other than P-N were also examined. While Ru complexes containing BPN, AMPHOS, PAN and ALAPHOS were either formed in situ or isolated, TPN did not coordinate to Ru(II). The isolated species, RuCl2(BPN)(PPh3) and RuCl2(PAN)(PPh3), are relatively 'robust' and do not react with the small molecules disscussed in this thesis. The electronics of the P-N ligand should be "fine-tuned" by modification of substituents on the N- or P-atom (see Figure 7.1), and/or the aromatic moiety. (ref. 2) (ref. 1) (ref. 2) Figure 7.1 Examples for the modification of P-N. 255 References on page 256 Chapter 7 7.1 References 1. (a) Cooper, M. K.; Dowries, J. M. Inorg. Chem. 1978, 77, 880. (b) Cooper, M. K.; Dowries, J. M.; Duckworth, P. A. Inorg. Synth. 1989, 25, 129. 2. Cooper, M. K.; Dowries, J. M.; Duckworth, P. A ; Tiekink, E. R. T. Aust. J. Chem. 1992, 45, 595. 256 APPENDICES 257 Appendix I APPENDIX I X-Ray Crystallographic Analysis of Bis [o-A7^V-dimethylamino)phenyl] phenylphosphine, BPN Figure 1.1 Stereoview of the molecular structure of BPN. 258 Appendix I E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type No. of Reflections Used for Unit Cell Determination (20 range) Omega Scan Peak Width at Half-height Lattice Parameters Space Group Z value D ^ c Fooo H(CuKa) C22H25N2P 348.43 colourless, plate 0.04X0.25X0.30 mm monoclinic C-centred 25 (43.7 - 55.3°) 0.39° a = 9.026(1) A b = 14.859(2) A c = 15.677(1) A 3 = 106.119(7)° V = 2019.9(4) A3 Cc (#9) 4 1.146 g/cm3 744 12.33 cm 1 B. Intensity Measurements Diflractometer Radiation Take-off Angle Detector Aperture Crystal to Detector Distance Temperature Scan Type Scan Rate Scan Width 29max No. of Reflections Measured Corrections Rigaku AFC6S CuKa (X = 1.54178 A) graphite monochromated 6.0° 6.0 mm horizontal 6.0 mm vertical 285 mm 21.0° 0-20 16°/min (in a) (up to 9 scans) (1.10+ 0.20 tan 9 ) ° 155° Total: 2271 Unique: 2124 (Rjllt = 0.024) Lorentz-polarization Absorption (trans. Factors: 0.692-1.000) Secondary Extinction (coefficient: 1.3(3) x 10"°) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations (I>3o(I)) No. Variables Reflection/Parameter Ratio Residuals: R; Rw Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Direct Methods (SIR92) Full-matrix least-squares 2>(|Fo| - |Fc | ) 2 a> = 1 0.0000 All non-hydrogen atoms 1667 225 7.41 0.053; 0.056 1.11 0.003 0.20 e'/A3 -0.19 e'/A3 259 Appendix I Table L l Atomic coordinates and B e q atom X y z B e q 3.73(3) atom X y z Beq P(l) 0.6306 0.2026(1) 0.3869 C(ll) 0.8168 10) -0.0365(5) 0.5054(5) 5.9(2) N<1) 0.5193(7) 0.3356(4) 0.2539(4) 5.4(1) C(12) 0.7961(8) 0.0432(5) 0.4605(4) 4.6(2) N(2) 0.4057(7) 0.1126(4) 0.4645(4) 4.8(1) C(13) 0.8025(7) 0.2120(4) 0.3452(4) 4.1(1) C(l) 0.4887(7) 0.1789(4) 0.2810(4) 3.6(1) C(14) 0.9056(8) 0.2794(5) 0.3777(4) 4.8(2) C(2) 0.4463(7) 0.2512(4) 0.2217(5) 4.1(1) C(15) 1.0344(10) 0.2911(7) 0.3490(6) 7.0(2) C(3) 0.3469(8) 0.2390(5) 0.1408(5) 4.9(2) C(16) 1.0579(9) 0.2393(6) 0.2809(5) 6.1(2) C(4) 0.2791(9) 0.1578(5) 0.1141(4) 4.9(2) C(17) 0.9557(9) 0.1707(6) 0.2488(5) 5.6(2) C(5) 0.3131(9) 0.0859(5) 0.1714(4) 4.9(2) C(18) 0.8265(8) 0.1572(5) 0.2787(4) 4.4(2) C(6) 0.4172(8) 0.0965(4) 0.2545(4) 4.2(1) C(19) 0.418(1) 0.3960(7) 0.287(1) 12.3(4) CO) 0.6609(8) 0.0918(4) 0.4429(4) 3.9(1) C(20) 0.594(2) 0.3789(8) 0.1949(8) 11.8(4) C<8) 0.5442(8) 0.0604(4) 0.4782(4) 4.4(2) C(21) 0.410(1) 0.1765(7) 0.5341(7) 7.7(3) C(9) 0.5665(9) -0.0181(5) 0.5266(4) 5.1(2) C(22) 0.2645(10) 0.0618(6) 0.4420(6) 6.6(2) C(10) 0.700(1) -0.0665(5) 0.5409(4) 5.5(2) 8 Beq = — Jt j (t /„(aa*) 2 + t / 2 2 (bb*) 2 + C/33(cc*)2 + 2C/i2aa*bb*cos y + 2t/naa*cc*cos p + 2C/23bb*cc*cos a) Table 1.2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance P(l) C(l) 1.828(6) P(l) C(7) 1.849(6) P(l) C(13) 1.849(6) N(l) C(2) 1.441(8) N(l) C(19) 1.48(1) N(l) C(20) 1.44(1) N(2) C(8) 1.435(9) N(2) C(21) 1.44(1) N(2) C(22) 1.438(10) C(l) C(2) 1.402(8) C(l) C(6) 1.393(8) C(2) C(3) 1.347(9) C(3) C(4) 1.37(1) C(4) C(5) 1.375(10) C(5) C(6) 1.387(9) C(7) C(8) 1.400(8) C(7) C(12) 1.378(9) C(8) C(9) 1.377(9) C(9) C(10) 1.37(1) C(10) C(ll) 1.40(1) C(l l ) C(12) 1.365(10) C(13) C(14) 1.366(8) C(13) C(18) 1.387(8) C(14) C(15) 1.368(10) C(15) C(16) 1.38(1) C(16) C(17) 1.37(1) C(17) C(18) 1.386(9) Table 1.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle C(l) P(l) C(7) 103.5(3) C(l) P(l) C(13) 97.9(3) C(7) P(l) C(13) 101.9(3) C(2) N(l) C(19) 112.6(6) C(2) N(l) C(20) 114.5(7) C(19) N(l) C(20) 113.8(9) C(8) N(2) C(21) 113.7(6) C(8) N(2) C(22) 115.5(6) C(21) N(2) C(22) 111.6(7) P(l) C(l) C(2) 116.6(4) P(l) C(l) C(6) 126.1(4) C(2) C(l) C(6) 117.2(5) N(l) C(2) C(l) 114.9(6) N(l) C(2) C(3) 124.5(6) C(l) C(2) C(3) 120.6(6) C(2) C(3) C(4) 122.2(6) C(3) C(4) C(5) 119.1(6) C(4) C(5) C(6) 119.7(7) C(l) C(6) C(5) 121.1(6) P(l) C(7) C(8) 117.1(5) P(l) C(7) C(12) 124.6(5) C(8) C(7) C(12) 117.9(6) N(2) C(8) C(7) 118.8(6) N(2) C(8) C(9) 121.9(6) C(7) C(8) C(9) 119.3(7) C(8) C(9) C(10) 121.6(7) C(9) C(10) C(ll) 119.8(7) C(10) C(ll) C(12) 118.2(7) C(7) C(12) C(ll) 123.0(7) P(l) C(13) C(14) 118.4(5) P(l) C(13) C(18) 122.9(5) C(14) C(13) C(18) 118.6(6) C(13) C(14) C(15) 121.6(7) C(14) C(15) C(16) 120.7(7) C(15) C(16) C(17) 117.8(6) C(16) C(17) C(18) 121.7(7) C(13) C(18) C(17) 119.4(6) 260 APPENDIX II X-Ray Crystallographic Analysis of #ner-RuCl3(BPN) (16) Appendix II 261 Appendix II 262 Appendix II E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type No. of Reflections Used for Unit Cell Determination (28 range) Omega Scan Peak Width at Half-height Lattice Parameters Space Group Z value Dole Fooo H(CuKa) C23H26CUN2PRU 675.23 orange, plate 0.03X0.25X0.25 mm monoclinic Primitive 25(45 .3 -72 .1° ) 0.36° a = 13.027(3) A b = 14.859(2) A c = 21.221(3) A p = 106.92(1)° V = 2769.1(9) A3 P2i/n(#14) 4 1.620 g/cm3 1356.00 105.87 cm-1 B. Intensity Measurements Diffractometer Radiation Take-off Angle Detector Aperture Crystal to Detector Distance Temperature Scan Type Scan Rate Scan Width 29nux No. of Reflections Measured Corrections Rigaku AFC6S CuKa (X = 1.54178 A) graphite monochromated 6.0° 6.0 mm horizontal 6.0 mm vertical 285 mm 21.0° a>-29 16°/min (in a>) (up to 9 scans) (0.94+ 0.20 tan 9)° 155.4° Total: 6028 Unique: 5753 (Rj* = 0.033) Lorentz-polarization Absorption (trans. Factors: 0.2193-1.0000) Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations (I>3.00a(I)) No. Variables Reflection/Parameter Ratio Residuals: R;Rw Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map C. Structure Solution and Refinement Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares 2o(|Fo| - |Fc | ) 2 2 P 2 - 1 m= —2 = [er (Fo) + i 7 -Fo ] CT (Fo) c 4 0.0000 All non-hydrogen atoms 3934 310 12.69 0.049; 0.055 2.78 0.00 0.78 eVA3 -0.63 e"/A3 263 Appendix II Table n.l Atomic coordinates and B, a t o m X y z Beq a t o m X y z Beq Ru(l) 0.47670(4) 0.56766(4) 0.20235(2) 2.585(9) C(19) 0.2594(6) 0.6858(7) 0.2040(4) 5.2(2) Cl(l) 0.6126(1) 0.7186(2) 0.22839(9) 4.24(4) C(20) 0.4112(7) 0.7855(6) 0.2800(4) 5.2(2) Cl(2) 0.3373(1) 0.4158(1) 0.17122(7) 3.29(3) C(21) 0.5261(7) 0.3975(7) 0.0964(3) 4.8(2) Cl(3) 0.4035(2) 0.6788(2) 0.09533(9) 5.08(4) C(22) 0.6835(5) 0.4507(7) 0.1843(4) 4.1(2) Cl(4a) 0.099(2) 0.398(2) 0.0376(10) 8.9(5) C(23) 0.2047(8) 0.443(1) 0.0057(4) 7.5(3) Cl(4) 0.1298(5) 0.3205(5) 0.0212(2) 13.6(2) H(l) 0.2137 0.6541 0.3113 6.4230 Cl(5a) 0.260(2) 0.442(2) -0.043(1) 12.6(6) H(2) 0.2060 0.5359 0.4049 8.2484 Cl(5) 0.2856(5) 0.3493(6) -0.0337(2) 14.6(2) H(3) 0.3458 0.3953 0.4573 7.5466 Cl(6a) 0.098(2) 0.569(2) -0.017(1) 12.8(7) H(4) 0.4915 0.3695 0.4154 5.4526 Cl(6) 0.1479(4) 0.5544(4) -0.0523(2) 10.2(1) H(5) 0.5730 0.1717 0.1347 5.3062 P(l) 0.5415(1) 0.4696(1) 0.29727(7) 2.58(3) H(6) 0.5592 -0.0138 0.1952 5.9504 N(l) 0.3663(4) 0.6589(5) 0.2503(3) 3.4(1) H(7) 0.5504 0.0024 0.3042 5.5698 N(2) 0.5690(4) 0.4175(5) 0.1698(2) 3.1(1) H(8) 0.5493 0.2040 0.3514 4.5193 C(l) 0.4373(5) 0.4911(6) 0.3367(3) 3.1(1) H(9) 0.6147 0.6675 0.3941 4.6958 C(2) 0.3564(5) 0.5789(6) 0.3069(3) 3.5(1) H(10) 0.7735 0.7073 0.4789 5.4268 C(3) 0.2716(7) 0.5944(7) 0.3322(5) 5.4(2) H(ll) 0.9187 0.5641 0.4974 6.5206 C(4) 0.2674(8) 0.5254(9) 0.3875(5) 6.9(3) H(12) 0.9083 0.3847 0.4272 6.1282 C<5) 0.3487(8) 0.4426(9) 0.4180(4) 6.3(3) H(13) 0.7488 0.3464 0.3417 4.9052 C(6) 0.4329(6) 0.4270(7) 0.3931(3) 4.5(2) H(14) 0.2135 0.7251 0.2278 6.1805 C(7) 0.5538(5) 0.3077(5) 0.2703(3) 2.8(1) H(15) 0.2671 0.7442 0.1695 6.1805 C(8) 0.5610(5) 0.2985(5) 0.2059(3) 2.8(1) H(16) 0.2268 0.6057 0.1838 6.1805 C(9) 0.5655(6) 0.1795(7) 0.1792(4) 4.4(2) H(17) 0.4809 0.7718 0.3127 6.2375 C(10) 0.5593(6) 0.0705(7) 0.2152(4) 5.0(2) H(18) 0.4201 0.8422 0.2453 6.2375 C(ll) 0.5534(6) 0.0797(6) 0.2787(4) 4.6(2) H(19) 0.3617 0.8247 0.3014 6.2375 C(12) 0.5519(5) 0.1974(6) 0.3058(3) 3.8(2) H(20) 0.4498 0.3753 0.0849 5.7151 C(13) 0.6660(5) 0.5001(6) 0.3614(3) 2.8(1) H(21) 0.5349 0.4763 0.0735 5.7151 C(14) 0.6751(6) 0.6080(7) 0.4014(3) 3.9(2) H(22) 0.5657 0.3281 0.0830 5.7151 C(15) 0.7680(6) 0.6315(8) 0.4510(3) 4.5(2) H(23) 0.7219 0.3802 0.1708 4.9781 C(16) 0.8533(6) 0.5486(9) 0.4613(4) 5.4(2) H(24) 0.6908 0.5281 0.1600 4.9781 C(17) 0.8470(6) 0.4426(8) 0.4206(4) 5.1(2) H(25) 0.7138 0.4658 0.2316 4.9781 C(18) 0.7533(6) 0.4202(7) 0.3707(3) 4.1(2) H(26) 0.2486 0.4825 0.0465 9.0503 Table TI.2 Bond lengths (A) with estimated standard deviations a t o m a t o m d i s t a n c e a t o m a t o m d i s t a n c e Ru(l) Cl(l) 2.316(2) Ru(l) Cl(2) 2.359(2) Ru(l) Cl(3) 2.482(2) Ru(l) P(l) 2.199(2) Ru(l) N(l) 2.207(5) Ru(l) N(2) 2.209(5) CI(4) C(23) 1.70(1) Cl(4a) C(23) 1.77(2) Cl(5) C(23) 1.81(1) Cl(5a) C(23) 1.42(3) Cl(6) C(23) 1.70(1) Cl(6a) C(23) 1.87(3) P(l) C(l) 1.804(6) P(l) C(7) 1.811(6) P(l) C(13) 1.816(6) N(l) C(2) 1.500(8) N(l) C(19) 1.479(9) N(l) C(20) 1.510(8) N(2) C(8) 1.482(7) N(2) C(21) 1.508(8) N(2) C(22) 1.474(8) C(l) C(2) 1.403(9) C(l) C(6) 1.388(9) C(2) C(3) 1.372(9) C(3) C(4) 1.39(1) C(4) C(5) 1.38(1) C(5) C(6) 1.36(1) C(7) C(8) 1.400(8) C(7) C(12) 1.383(8) C(8) C(9) 1.378(8) C<9) C(10) 1.39(1) C(10) C(l l ) 1.37(1) C(l l) C(12) 1.363(9) C(13) C(14) 1.398(8) C(13) C(18) 1.378(9) C(14) C(15) 1.375(9) C(15) C(16) 1.38(1) C(16) C(17) 1.39(1) C(17) C(18) 1.383(9) 264 Appendix II Table n.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle Cl(l) Ru(l) CI(2) 177.65(6) Cl(l) Ru(l) Cl(3) 87.81(7) Cl(l) Ru(l) P(l) 92.12(6) Cl(l) Ru(l) N(l) 98.6(1) Cl(l) Ru(l) N(2) 96.5(1) Cl(2) Ru(l) Cl(3) 90.03(6) Cl(2) Ru(l) P(l) 90.05(5) Cl(2) Ru(l) N(l) 82.5(1) Cl(2) Ru(l) N(2) 83.0(1) Cl(3) Ru(l) P(l) 179.88(6) Cl(3) Ru(l) N(l) 95.2(2) Cl(3) Ru(l) N(2) 98.4(1) P(l) Ru(l) N(l) 84.7(1) P(l) Ru(l) N(2) 81.7(1) N(l) Ru(l) N(2) 160.0(2) Ru(l) P(l) C(l) 103.1(2) Ru(l) P(l) C(7) 101.2(2) Ru(l) P(l) C(13) 128.7(2) C(l) P(l) C(7) 114.3(3) C(l) P(l) C(13) 105.0(3) C(7) P(l) C(13) 105.0(3) Ru(l) N(l) C(2) 110.3(4) Ru(l) N(l) C(19) 112.9(4) Ru(l) N(l) C(20) 110.3(4) C(2) N(l) C(19) 110.8(5) C(2) N(l) C(20) 105.6(5) C(19) N(l) C(20) 106.6(5) Ru(l) N(2) C(8) 108.0(3) Ru(l) N(2) C(21) 110.5(4) Ru(l) N(2) C(22) 112.1(4) C(8) N(2) C(21) 110.9(5) C(8) N(2) C(22) 108.1(5) C(21) N(2) C(22) 107.2(5) P(l) C(l) C(2) . 116.2(5) P(l) C(l) C(6) 124.5(5) C(2) C(l) C(6) 119.4(6) N(l) C(2) C(l) 119.9(6) N(l) C(2) C(3) 120.9(6) C(l) C(2) C(3) 119.1(7) C(2) C(3) C(4) 120.1(8) C(3) C(4) C(5) 120.7(8) C(4) C(5) C(6) 119.3(8) C(l) C(6) C(5) 121.3(8) P(l) C(7) C(8) 114.2(4) P(l) C(7) C(12) 126.3(5) C(8) C(7) C(12) 119.4(6) N(2) C(8) C(7) 118.8(5) N(2) C(8) C(9) 122.0(6) C(7) C(8) C(9) 119.1(6) C(8) C(9) C(10) 120.0(7) C(9) C(10) C(ll) 120.7(7) C(10) C(ll) C(12) 119.2(7) C(7) C(12) C(ll) 121.4(6) P(l) C(13) C(14) 119.8(5) P(l) C(13) C(18) 121.4(5) C(14) C(13) C(18) 118.8(6) C(13) C(14) C(15) 120.7(7) C(14) C(15) C(16) 119.9(7) C(15) C(16) C(17) 120.3(7) C(16) C(17) C(18) 119.2(7) C(13) C(18) C(17) 121.0(7) Cl(4) C(23) CI(5) 97.2(7) Cl(4) C(23) CI(6) 120.3(6) Cl(5) C(23) Cl(6) 103.1(6) Cl(4a) C(23) Cl(5a) 153(1) Cl(4a) C(23) Cl(6a) 71.8(10) Cl(5a) C(23) Cl(6a) 107(1) 265 Appendix III APPENDIX III X-Ray Crystallographic Analysis of (n-0)(u-Cl)2[RuCl(P-N)]2 (17) Figure ITI.1 Stereoview of the molecular structure of 17. 266 Appendix III Figure ITJ.2 Pluto plot of the molecular structure of 17. 267 Appendix III E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula C 4 3H4«CL,N 2 OjP 2 Ru 2 Formula Weight 1028.75 Crystal Colour, Habit green, plate Crystal Dimensions 0.01 X 0.30X0.55 mm Crystal System monoclinic Lattice Type Primitive Lattice Parameters a = 18.1176(14) A b = 9.5777(11) A c = 25.2917(7) A P = 100.1564(7)° V = 4320.0(5) A 3 Space Group P2!/a(#14) Z value 4 D c J c 1.582 g/cm3 Fooo 2080.00 KMoKa) 10.59 cm"1 B. Diffract ometer Radiation Detector Aperture Temperature Data Images <t> oscillation Range (x = -90) <a oscillation Range (x = -90) Detector Position Detector Swing Angle 20m« No. of Reflections Measured Corrections Measurements Rigaku/ADSC CCD MoKa (X = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 768 exposures of 60.0 seconds 0.0 -189.9° -23.0 -17.8° 39.258(6) mm -10.0° 60.1° Total: 39452 Unique: 11225 (Ri„ = 0.094) Lorentz-polarization Absorption/decay/scaling (coor. Factors: 0.6295 - 1.0000) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R; Rw Goodness of Fit Indicator No. Observations (I>3a(I)) Residuals (on F 2 , all data): R; Rw Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares S«.(|FO2|-|FC2|)2 I CD = rj (Fo ) 0.0000 All non-hydrogen atoms 11225 496 22.63 0.153; 0.098 1.35 3859 0.055; 0.040 0.0006 3.00 eVA3 (between C(10) and Cl(3)) -3.46 eVA3 268 Appendix III Table III.1 Atomic coordinates and B, atom X y z atom X y z B e q Ru(l) 0.72083(3) 0.41704(6) 0.25277(2) 1.801(12) C(17) 0.4598(5) 0.2111(11) 0.1549(4) 6.1(3) Ru(2) 0.64051(3) 0.57839(6) 0.32240(2) 1.685(12) C(18) 0.4184(5) 0.3212(14) 0.1326(4) 6.9(4) Cl(l) 0.76031(8) 0.4739(2) 0.35309(6) 2.16(4) C(19) 0.4540(5) 0.4358(11) 0.1188(3) 5.8(3) Cl(2) 0.69933(9) 0.6629(2) 0.24119(7) 2.43(4) C(20) 0.5327(4) 0.4481(9) 0.1272(3) 4.0(2) Cl(3) 0.84755(8) 0.4379(2) 0.23658(7) 2.94(4) C(21) 0.4945(3) 0.5886(7) 0.3750(2) 1.43(13) Cl(4) 0.67119(9) 0.7912(2) 0.37062(7) 2.42(4) C(22) 0.4790(3) 0.6651(6) 0.3293(2) 1.64(15) P(l) 0.67526(9) 0.3530(2) 0.16885(7) 2.01(4) C(23) 0.4092(3) 0.7319(7) 0.3158(3) 2.00(15) P(2) 0.58551(9) 0.5041(2) 0.38946(7) 1.78(4) C(24) 0.3581(3) 0.7210(7) 0.3505(3) 2.3(2) 0(1) 0.6258(2) 0.4166(4) 0.27649(13) 1.68(9) C(25) 0.3734(4) 0.6434(7) 0.3972(3) 2.4(2) 0(2) 0.5569(4) 0.2216(10) -0.0333(4) 13.3(4) C(26) 0.4425(3) 0.5790(7) 0.4095(2) 1.99(14) N(l) 0.7412(3) 0.1931(5) 0.2664(2) 2.27(14) C(27) 0.4975(3) 0.5850(8) 0.2421(2) 2.8(2) N(2) 0.5308(3) 0.6688(5) 0.2906(2) 1.66(12) C(28) 0.5398(4) 0.8156(7) 0.2716(3) 2.7(2) C(l) 0.7092(3) 0.1753(7) 0.1662(3) 2.2(2) C(29) 0.6327(3) 0.5612(7) 0.4553(2) 1.51(14) C(2) 0.7416(3) 0.1156(7) 0.2153(3) 2.3(2) C(30) 0.7023(4) 0.5020(7) 0.4764(3) 2.3(2) C(3) 0.7691(4) -0.0200(7) 0.2167(3) 2.9(2) C(31) 0.7426(3) 0.5487(7) 0.5242(3) 2.6(2) C(4) 0.7698(4) -0.0899(8) 0.1697(3) 3.3(2) C(32) 0.7171(4) 0.6571(8) 0.5517(3) 2.9(2) C(5) 0.7389(4) -0.0344(8) 0.1206(3) 3.5(2) C(33) 0.6492(4) 0.7187(8) 0.5307(3) 3.5(2) C(6) 0.7084(4) 0.0988(8) 0.1191(3) 2.8(2) C(34) 0.6058(4) 0.6717(7) 0.4829(3) 2.6(2) C(7) 0.6803(4) 0.1345(7) 0.2932(3) 2.6(2) G(35) 0.5624(3) 0.3219(7) 0.3969(2) 1.84(15) C(8) 0.8156(4) 0.1698(7) 0.3038(3) 3.0(2) C(36) 0.5216(4) 0.2524(7) 0.3529(3) 2.6(2) C(9) 0.7005(4) 0.4435(7) 0.1107(3) 2.3(2) C(37) 0.4954(4) 0.1202(8) 0.3561(3) 3.0(2) C(10) 0.7573(4) 0.5398(8) 0.1167(3) 3.1(2) C(38) 0.5088(4) 0.0514(7) 0.4046(3) 3.5(2) C(l l ) 0.7793(4) 0.6043(8) 0.0730(3) 4.2(2) C(39) 0.5497(4) 0.1145(7) 0.4498(3) 3.1(2) C(12) 0.7443(5) 0.5710(10) 0.0230(3) 4.9(3) C(40) 0.5759(4) 0.2486(8) 0.4468(3) 2.8(2) C(13) 0.6867(5) 0.4748(9) 0.0156(3) 5.0(3) C(41) 0.4689(7) 0.1501(13) -0.1049(5) 11.3(5) C(14) 0.6638(4) 0.4096(8) 0.0592(3) 3.3(2) C(42) 0.4920(7) 0.1920(12) -0.0484(6) 8.2(4) C(15) 0.5746(4) 0.3356(8) 0.1506(3) 2.4(2) C(43) 0.4366(7) 0.1869(15) -0.0121(6) 12.6(5) C(16) 0.5387(4) 0.2209(9) 0.1646(3) 4.2(2) Table TJI.2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance Ru(l) Ru(2) 2.9173(7) Ru(l) Cl(l) 2.570(2) Ru(l) Cl(2) 2.396(2) Ru(l) Cl(3) 2.411(2) Ru(l) P(l) 2.224(2) Ru(l) O(l) 1.921(4) Ru(l) N(l) 2.193(5) Ru(2) Cl(l) 2.3921(15) Ru(2) Cl(2) 2.604(2) Ru(2) Cl(4) 2.390(2) Ru(2) P(2) 2.230(2) Ru(2) O(l) 1.926(4) Ru(2) N(2) 2.187(5) P(l) C(l) 1.815(7) P(l) C(9) 1.832(6) P(l) C(15) 1.807(6) P(2) C(21) 1.816(6) P(2) C(29) 1.816(6) P(2) C(35) 1.812(7) 0(2) C(42) 1.205(11) N(l) C(2) 1.492(7) N(l) C(7) 1.504(8) N(l) C(8) 1.520(7) N(2) C(22) 1.471(7) N(2) C(27) 1.500(7) N(2) C(28) 1.504(8) C(l) C(2) 1.398(8) C(l) C(6) 1.397(8) C(2) C(3) 1.390(9) C(3) C(4) 1.367(9) C(4) C(5) 1.376(9) C(5) C(6) 1.389(9) C(9) C(10) 1.371(8) C(9) C(14) 1.392(8) C(10) C(ll) 1.387(9) C(ll) C(12) 1.348(9) C(12) C(13) 1.379(10) C(13) C(14) 1.393(9) C(15) C(16) 1.355(10) C(15) C(20) 1.390(9) C(16) C(17) 1.410(10) C(17) C(18) 1.358(13) C(18) C(19) 1.349(13) C(19) C(20) 1.410(10) C(21) C(22) 1.355(8) C(21) C(26) 1.395(7) C(22) C(23) 1.405(8) C(23) C(24) 1.386(8) C(24) C(25) 1.383(8) C(25) C(26) 1.381(8) C(29) C(30) 1.400(8) C(29) C(34) 1.403(8) C(30) C(31) 1.372(8) C(31) C(32) 1.375(9) C(32) C(33) 1.384(9) C(33) C(34) 1.394(9) C(35) C(36) 1.393(8) C(35) C(40) 1.427(8) C(36) C(37) 1.360(9) C(37) C(38) 1.375(9) C(38) C(39) 1.387(9) C(39) C(40) 1.375(9) C(41) C(42) 1.470(14) C(42) C(43) 1.48(2) 269 Appendix III Table HI.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle Cl(l) Ru(l) Cl(2) 85.62(6) Cl(l) Ru(l) Cl(3) 92.44(5) Cl(l) Ru(l) P(l) 173.00(6) Cl(l) Ru(l) O(l) 78.51(11) Cl(l) Ru(l) N(l) 92.43(14) Cl(2) Ru(l) Cl(3) 92.11(6) Cl(2) Ru(l) P(l) 97.44(6) Cl(2) Ru(l) O(l) 84.54(13) Cl(2) Ru(l) N(l) 178.03(15) Cl(3) Ru(l) P(l) 93.74(6) Cl(3) Ru(l) O(l) 170.54(12) Cl(3) Ru(l) N(l) 88.20(14) P(l) Ru(l) O(l) 95.46(11) P(l) Ru(l) N(l) 84.48(14) O(l) Ru(l) N(l) 94.9(2) Cl(l) Ru(2) Cl(2) 84.94(5) Cl(l) Ru(2) Cl(4) 94.31(6) Cl(l) Ru(2) P(2) 96.96(6) Cl(l) Ru(2) O(l) 83.11(11) Cl(l) Ru(2) N(2) 177.18(14) Cl(2) Ru(2) Cl(4) 92.68(6) Cl(2) Ru(2) P(2) 177.50(6) Cl(2) Ru(2) O(l) 78.86(12) Cl(2) Ru(2) N(2) 93.34(14) Cl(4) Ru(2) P(2) 88.80(6) Cl(4) Ru(2) O(l) 171.33(12) Cl(4) Ru(2) N(2) 87.99(14) F(2) Ru(2) O(l) 99.72(12) P(2) Ru(2) N(2) 84.70(14) O(l) Ru(2) N(2) 94.4(2) Ru(l) Cl(l) Ru(2) 71.92(4) Ru(l) Cl(2) Ru(2) 71.25(5) Ru(l) P(l) C(l) 102.9(2) Ru(l) P(l) C(9) 122.2(2) Ru(l) P(l) C(15) 117.2(2) C(l) P(l) C(9) 106.3(3) C(l) P(l) C(15) 103.7(3) C(9) P(l) C(15) 102.8(3) Ru(2) P(2) C(21) 102.5(2) Ru(2) P(2) C(29) 113.6(2) Ru(2) P(2) C(35) 121.9(2) C(21) P(2) C(29) 108.3(3) C(21) P(2) C(35) 103.4(3) C(29) P(2) C(35) 105.9(3) Ru(l) 0(1) Ru(2) 98.6(2) Ru(l) N(l) C(2) 112.2(4) Ru(l) N(l) C(7) 108.6(4) Ru(l) N(l) C(8) 110.4(4) C(2) N(l) C(7) 108.8(5) C(2) N(l) C(8) 109.1(5) C(7) N(l) C(8) 107.7(5) Ru(2) N(2) C(22) 113.0(4) Ru(2) N(2) C(27) 107.3(4) Ru(2) N(2) C(28) 110.2(4) C(22) N(2) C(27) 108.6(5) C(22) N(2) C(28) 110.6(5) C(27) N(2) C(28) 106.8(5) P(l) C(l) C(2) 116.3(5) P(l) C(l) C(6) 124.7(5) C(2) C(l) C(6) 118.9(6) N(l) C(2) C(l) 120.0(6) N(l) C(2) C(3) 119.9(6) C(l) C(2) C(3) 119.9(6) C(2) C(3) C(4) 119.5(7) C(3) C(4) C(5) 122.1(7) C(4) C(5) C(6) 118.4(6) C(l) C(6) C(5) 120.9(6) P(l) C(9) C(10) 121.2(5) P(l) C(9) C(14) 119.7(6) C(10) C(9) C(14) 119.0(7) C(9) C(10) C(ll) 121.9(7) C(10) C(ll) C(12) 119.2(8) C(l l ) C(12) C(13) 120.4(8) C(12) C(13) C(14) 121.0(7) C(9) C(14) C(13) 118.5(7) P(l) C(15) C(16) 121.2(6) P(l) C(15) C(20) 119.2(6) C(16) C(15) C(20) 119.2(7) C(15) C(16) C(17) 121.8(8) C(16) C(17) C(18) 119.3(9) C(17) C(18) C(19) 119.1(9) C(18) C(19) C(20) 123.0(9) C(15) C(20) C(19) 117.5(8) P(2) C(21) C(22) 117.1(5) P(2) C(21) C(26) 122.3(5) C(22) C(21) C(26) 120.6(5) N(2) C(22) C(21) 121.4(5) N(2) C(22) C(23) 118.7(5) C(21) C(22) C(23) 119.6(6) C(22) C(23) C(24) 119.1(6) C(23) C(24) C(25) 121.7(6) C(24) C(25) C(26) 118.0(6) C(21) C(26) C(25) 121.0(6) P(2) C(29) C(30) 118.3(5) P(2) C(29) C(34) 122.4(5) C(30) C(29) C(34) 119.0(6) C(29) C(30) C(31) 120.5(6) C(30) C(31) C(32) 121.3(6) C(31) C(32) C(33) 118.8(6) C(32) C(33) C(34) 121.6(7) C(29) C(34) C(33) 118.9(6) P(2) C(35) C(36) 118.5(5) P(2) C(35) C(40) 124.0(5) C(36) C(35) C(40) 117.1(6) C(35) C(36) C(37) 122.6(7) C(36) C(37) C(38) 119.4(7) C(37) C(38) C(39) 120.7(7) C(38) C(39) C(40) 120.1(6) C(35) C(40) C(39) 120.0(6) 0(2) C(42) C(41) 117.9(14) 0(2) C(42) C(43) 122.9(13) C(41) C(42) C(43) 119.1(12) 270 Appendix IV APPENDIX IV X-Ray Crystallographic Analysis of Cis-RuCl2(P-N)(PPh3)(SH2)-(acetone) (18a) Figure IV.l Stereoview of the molecular structure of 18a. 271 Appendix IV Figure 1Y.2 Pluto plot of the molecular structure of 18a. 272 Appendix W E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula C41H43CI2NOP2RUS Formula Weight 831.78 Crystal Colour, Habit yellow-brown, prism Crystal Dimensions 0.28X0.30X0.38 mm Crystal System monoclinic Lattice Type Primitive Lattice Parameters a =14.843(2) A b = 16.0292(9) A c = 16.0099(8) A (3 = 95.286(2)° V = 3792.8(5) A 3 Space Group P2[/n(#14) Z value 4 1.457 g/cm3 Fooo 1712.00 H(MoKa) 7.27 cm"1 B. Diflractometer Radiation Detector Aperture Temperature Data Images <|> oscillation Range (x = -90) a> oscillation Range (x = -90) Detector Position Detector Swing Angle No. of Reflections Measured Corrections Measurements Rigaku/ADSC CCD MoKa (X = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 462 exposures of 25.0 seconds 0.0 -190.0° -23.0 -18.0° 39.12(2) mm -10.0° 60.5° Total: 33910 Unique: 9547 (RM = 0.041) Lorentz-polarization Absorption/decay/scaling (coor. factors: 0.6722 -1.0000) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R; Rw Goodness of Fit Indicator No. Observations (I>3o(I)) Residuals (on F, I>3a(I)): R; Rw Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares 2>(|Fo 2 | - | F c 2 | ) 2 1 co = rj (Fo ) 0.0000 All non-hydrogen atoms 9547 450 21.22 0.057; 0.053 1.33 6176 0.028; 0.025 0.001 1.23 e/A3(1.3 AfromRu) -1.44 e7A3 273 Appendix IV Table IV. 1 Atomic coordinates and B e q atom X y z B e ( I atom X y z B eq Ru(l) 0.554502(13) 0.283305(11) 0.145131(11) 1.080(4) C(19) 0.5709(2) 0.2491(2) 0.48977(15) 2.56(6) Cl(l) 0.58901(4) 0.15775(4) 0.22620(3) 1.798(13) C(20) 0.5824(2) 0.26798(15) 0.40674(14) 2.07(6) Cl(2) 0.56129(4) 0.21320(4) 0.00832(3) 1.816(12) C(21) 0.3357(2) 0.30713(13) 0.05269(13) 1.36(5) S(l) 0.53144(5) 0.40235(4) 0.06015(4) 1.739(14) C(22) 0.3279(2) 0.27515(15) -0.02924(13) 1.81(5) P(l) 0.57168(4) 0.36457(4) 0.26173(4) 1.294(13) C(23) 0.2852(2) 0.3213(2) -0.09406(14) 2.38(6) P(2) 0.40269(4) 0.24894(4) 0.13544(3) 1.129(12) C(24) 0.2500(2) 0.3995(2) -0.0801(2) 2.60(6) O(l) 0.5462(2) 0.11557(13) 0.64837(15) 4.94(6) C(25) 0.2579(2) 0.43209(15) 0.0000(2) 2.26(6) N(l) 0.71069(13) 0.30310(11) 0.14625(11) 1.38(4) C(26) 0.3012(2) 0.38647(14) 0.06561(14) 1.83(6) C(l) 0.6948(2) 0.37990(14) 0.27835(13) 1.50(5) C(27) 0.3390(2) 0.26065(13) 0.22842(13) 1.23(5) C(2) 0.7506(2) 0.34595(14) 0.22231(13) 1.59(5) C(28) 0.3817(2) 0.22950(14) 0.30367(14) 1.62(5) C(3) 0£442(2) 0.3553(2) 0.23560(15) 2.67(6) C(29) 0.3383(2) 0.23284(15) 0.37661(14) 2.05(6) C(4) 0.8820(2) 0.3993(2) 0.3038(2) 3.49(8) C(30) 0.2528(2) 0.26722(15) 0.37567(15) 2.29(6) C(5) 0.8270(2) 0.4349(2) 0.3602(2) 3.09(7) C(31) 0.2092(2) 0.29703(14) 0.3018(2) 2.11(6) C(6) 0.7345(2) 0.4247(2) 0.34751(14) 2.29(6) C(32) 0.2515(2) 0.29249(14) 0.22761(13) 1.67(5) C(7) 0.7560(2) 0.2203(2) 0.13675(15) 2.31(6) C(33) 0.3679(2) 0.14043(14) 0.10693(13) 1.44(5) C(8) 0.7326(2) 0.35434(15) 0.07325(14) 2.01(6) C(34) 0.2751(2) 0.12268(15) 0.09950(14) 1.98(6) C(9) 0.5254(2) 0.46976(14) 0.24666(13) 1.56(5) C(35) 0.2445(2) 0.0430(2) 0.07878(15) 2.49(6) C(10) 0.5786(2) 0.5379(2) 0.2301(2) 2.58(7) C(36) 0.3061(2) -0.01970(15) 0.06471(15) 2.40(6) C(l l ) 0.5376(2) 0.6154(2) 0.2111(2) 3.69(8) C(37) 0.3972(2) -0.00304(14) 0.07251(14) 2.19(6) C(12) 0.4455(2) 0.6248(2) 0.2091(2) 3.82(8) C(38) 0.4294(2) 0.07721(14) 0.09302(13) 1.69(5) C(13) 0.3923(2) 0.5579(2) 0.2268(2) 3.14(7) C(39) 0.5517(2) 0.0398(2) 0.6511(2) 3.20(7) C(14) 0.4314(2) 0.48073(15) 0.24470(15) 2.18(6) C(40) 0.4781(3) -0.0132(2) 0.6113(2) 5.86(11) C(15) 0.5477(2) 0.34172(14) 0.37028(13) 1.57(5) C(41) 0.6293(2) -0.0034(2) 0.6950(2) 3.72(8) C(16) 0.5014(2) 0.39607(15) 0.41948(15) 2.38(6) H(l) 0.466(2) 0.440(2) 0.078(2) 5.3(7) C(17) 0.4894(2) 0.3761(2) 0:5032(2) 3.22(7) H(2) 0.503(2) 0.372(2) -0.013(2) 5.3(7) C(18) 0.5238(2) 0.3028(2) 0.53796(15) 2.96(7) Table IV.2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance Ru(l) Cl(l) 2.4238(6) Ru(l) Cl(2) 2.4721(5) Ru(l) S(l) 2.3503(6) Ru(l) P(l) 2.2712(6) Ru(l) P(2) 2.3110(7) Ru(l) N(l) 2.338(2) P(l) C(l) 1.838(3) P(l) C(9) 1.828(2) P(l) C(15) 1.842(2) P(2) C(21) 1.836(2) P(2) C(27) 1.845(2) P(2) C(33) 1.859(2) O(l) C(39) 1.218(3) N(l) C(2) 1.474(3) N(l) C(7) 1.503(3) N(l) C(8) 1.489(3) C(l) C(2) 1.388(3) C(l) C(6) 1.403(3) C(2) C(3) 1.394(3) C(3) C(4) 1.375(3) C(4) C(5) 1.395(4) C(5) C(6) 1.380(4) C(9) C(10) 1.388(3) C(9) C(14) 1.404(3) C(10) C(ll) 1.404(3) C(ll) C(12) 1.372(4) C(12) C(13) 1.377(4) C(13) C(14) 1.386(3) C(15) C(16) 1.398(3) C(15) C(20) 1.395(3) C(16) C(17) 1.406(3) C(17) C(18) 1.378(4) C(18) C(19) 1.387(3) C(19) C(20) 1.389(3) C(21) C(22) 1.403(3) C(21) C(26) 1.393(3) C(22) C(23) 1.380(3) C(23) C(24) 1.385(4) C(24) C(25) 1.380(3) C(25) C(26) 1.388(3) C(27) C(28) 1.401(3) C(27) C(32) 1.395(3) C(28) C(29) 1.386(3) C(29) C(30) 1.382(3) C(30) C(31) 1.381(3) C(31) C(32) 1.396(3) C(33) C(34) 1.402(3) C(33) C(38) 1.395(3) C(34) C(35) 1.385(3) C(35) C(36) 1.391(4) C(36) C(37) 1.374(4) C(37) C(38) 1.401(3) C(39) C(40) 1.481(4) C(39) C(41) 1.467(4) S(l) H(l) 1.20(3) S(l) H(2) 1.30(3) 274 Appendix IV Table IV.3 Bond angles (°) with estimated standard deviations Atom atom atom angle atom atom atom angle Cl(l) Ru.(l) Cl(2) 94.19(2) Cl(l) Ru(l) S(l) 175.18(2) Cl(l) Ru(l) P(l) 91.95(2) Cl(l) Ru(l) P(2) 89.70(2) Cl(l) Ru(l) N(l) 87.03(5) Cl(2) Ru(l) S(l) 82.63(2) Cl(2) Ru(l) P(l) 168.03(2) Cl(2) Ru(l) P(2) 87.21(2) Cl(2) Ru(l) N(l) 86.97(4) S(l) Ru(l) P(l) 90.54(2) S(l) Ru(l) P(2) 93.76(2) S(l) Ru(l) N(l) 89.18(5) P(l) Ru(l) P(2) 103.11(2) P(l) Ru(l) N(l) 83.09(5) P(2) Ru(l) N(l) 173.09(5) Ru(l) P(l) C(l) 103.33(7) Ru(l) P(l) C(9) 114.09(8) Ru(l) P(l) C(15) 130.13(8) C(l) P(l) C(9) 104.60(11) C(l) P(l) C(15) 99.52(10) C(9) P(l) C(15) 101.83(10) Ru(l) P(2) C(21) 112.78(7) Ru(l) P(2) C(27) 119.37(8) Ru(l) P(2) C(33) 119.09(8) C(21) P(2) C(27) 104.30(10) C(21) P(2) C(33) 100.29(10) C(27) P(2) C(33) 98.17(10) Ru(l) N(l) C(2) 113.11(13) Ru(l) N(l) C(7) 109.41(13) Ru(l) N(l) C(8) 110.90(14) C(2) N(l) C(7) 110.2(2) C(2) N(l) C(8) 106.9(2) C(7) N(l) C(8) 106.0(2) P(l) C(l) C(2) 119.9(2) P(l) C(l) C(6) 121.5(2) C(2) C(l) C(6) 118.6(2) N(l) C(2) C(l) 119.9(2) N(l) C(2) C(3) 119.7(2) C(l) C(2) C(3) 120.4(2) C(2) C(3) C(4) 120.3(2) C(3) C(4) C(5) 120.3(3) C(4) C(5) C(6) 119.3(2) C(l) C(6) C(5) 121.2(2) P(l) C(9) C(10) 122.6(2) P(l) C(9) C(14) 118.6(2) C(10) C(9) C(14) 118.6(2) C(9) C(10) C(ll) 119.7(3) C(10) C(ll) C(12) 120.9(3) C(l l ) C(12) C(13) 119.9(3) C(12) C(13) C(14) 120.0(3) C(9) C(14) C(13) 120.9(2) P(l) C(15) C(16) 123.8(2) P(l) C(15) C(20) 117.9(2) C(16) C(15) C(20) 118.3(2) C(15) C(16) C(17) 120.5(2) C(16) C(17) C(18) 120.3(2) C(17) C(18) C(19) 119.4(2) C(18) C(19) C(20) 120.6(2) C(15) C(20) C(19) 120.8(2) P(2) C(21) C(22) 118.8(2) P(2) C(21) C(26) 122.6(2) C(22) C(21) C(26) 118.2(2) C(21) C(22) C(23) 120.0(2) C(22) C(23) C(24) 121.2(2) C(23) C(24) C(25) 119.5(2) C(24) C(25) C(26) 119.8(2) C(21) C(26) C(25) 121.3(2) P(2) C(27) C(28) 115.6(2) P(2) C(27) C(32) 125.1(2) C(25) C(27) C(32) 119.1(2) C(27) C(28) C(29) 120.1(2) C(28) C(29) C(30) 120.3(2) C(29) C(30) C(31) 120.4(2) C(30) C(31) C(32) 119.9(2) C(27) C(32) C(31) 120.2(2) P(2) C(33) C(34) 117.3(2) P(2) C(33) C(35) 123.2(2) C(34) C(33) C(38) 119.4(2) C(33) C(34) C(35) 120.3(2) C(34) C(35) C(36) 120.0(3) C(35) C(36) C(37) 120.1(2) C(36) C(37) C(38) 120.8(2) C(33) C(35) C(37) 119.4(2) O(l) C(39) C(40) 120.8(3) O(l) C(39) C(41) 122.3(3) C(40) C(39) C(41) 116.8(3) Ru(l) S(l) H(l) 110.7(12) Ru(l) S(l) H(2) 103.3(11) H(l) S(l) H(2) 101.7(17) 275 APPENDIX V Appendix V X-Ray Crystallographic Analysis of as-RuBr2(P-N)(PPh3)(SH2)(benzene) (18b) E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type Lattice Parameters Space Group Z value D c l k Fooo KMoKa) C^jBrjNOPjRuS 940.72 orange, prism 0.15X0.20X0.25 mm monoclinic Primitive a = 9.6668(13) A b = 18.976(2) A c= 11.6270(4) A P = 110.3292(7)° V = 2000.0(3) A 3 P 2 i (#4) 2 1.562 g/cm3 948.00 25.61 cm"1 B. Intensity Measurements Diflractometer Radiation Detector Aperture Temperature Data Images <t> oscillation Range (x = -90) to oscillation Range (x = -90) Detector Position Detector Swing Angle 20max No. of Reflections Measured Corrections Rigaku/ADSC CCD MoKa (A, = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 460 exposures of 90.0 seconds -22.0 -18.0° 0.0 -190.0° 39.214(8) mm -10° 60.2° Total: 18513 Unique: 5 2 3 4 ^ = 0.031) Lorentz-polarization Absorption/scaling (tarns, factors: 0.7689 -1.0119) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals: R; Rw Goodness of Fit Indicator No. Observations (I>3c?(I)) Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares 2 > ( | F o 2 | - | F c 2 | f 1 IT (Fo ) 1 2 2 2 -1 = [c (Fo ) + p Fo ] 0.0200 All non-hydrogen atoms 8318 467 17.81 0.059; 0.074 1.32 8318 0.01 1.10 e/A 3 (near Ru) -1.45 e"/A3 276 Appendix V Table V . l Atomic coordinates and B, atom X y z B e q atom X y z B e , Ru(l) 0.69024(3) 0.49960 0.48061(3) 0.974(6) C(21) 0.3513(4) 0.5885(2) 0.3319(4) 1.13(8) Br(l) 0.84461(5) 0.46441(3) 0.34204(4) 1.971(9) C(22) 0.3884(5) 0.6572(2) 0.3755(4) 1.58(9) Br(2) 0.79833(5) 0.62373(2) 0.52259(4) 1.685(9) C(23) 0.2828(5) 0.7021(2) 0.3901(5) 2.12(10) S(l) 0.62276(12) 0.38149(5) 0.44294(11) 1.66(2) C(24) 0.1386(5) 0.6797(2) 0.3637(5) 2.41(11) P(l) 0.57993(11) 0.51236(5) 0.62198(9) 1.07(2) C(25) 0.1003(5) 0.6113(2) 0.3214(5) 2.26(10) P(2) 0.50310(11) 0.53847(5) 0.30884(10) 1.04(2) C(26) 0.2067(5) 0.5663(2) 0.3042(4) 1.72(9) N(l) 0.8909(4) 0.4653(2) 0.6569(3) 1.41(7) C(27) 0.4155(4) 0.4690(2) 0.1949(4) 1.46(8) C(l) 0.7313(4) 0.5070(2) 0.7691(4) 1.50(8) C(28) 0.3113(5) 0.4211(2) 0.2077(5) 2.03(10) C(2) 0.8685(5) 0.4873(2) 0.7721(4) 1.74(9) C(29) 0.2507(5) 0.3689(2) 0.1211(5) 2.62(11) C(3) 0.9851(5) 0.4842(2) 0.8832(5) 2.68(11) C(30) 0.2949(6) 0.3630(3) 0.0202(5) 3.19(12) C(4) 0.9620(6) 0.5003(3) 0.9910(4) 3.20(11) C(31) 0.4023(7) 0.4079(3) 0.0083(5) 3.22(13) C(5) 0.8245(6) 0.5192(3) 0.9896(4) 2.72(11) C(32) 0.4617(6) 0.4608(3) 0.0949(5) 2.41(10) C(6) 0.7089(5) 0.5234(2) 0.8793(4) 2.01(10) C(33) 0.5422(5) 0.6023(2) 0.2036(4) 1.37(8) C(7) 0.9140(5) 0.3871(2) 0.6642(5) 2.22(10) C(34) 0.4218(5) 0.6270(2) 0.1060(4) 1.93(9) C(8) 1.0309(5) 0.4969(3) 0.6534(5) 2.43(10) C(35) 0.4414(6) 0.6713(2) 0.0189(5) 2.56(11) C(9) 0.4826(5) 0.5901(2) 0.6489(4) 1.35(8) C(36) 0.5825(6) 0.6921(2) 0.0293(5) 2.55(11) C(10) 0.5638(5) 0.6523(2) 0.6835(4) 1.63(9) C(37) 0.7017(6) 0.6698(2) 0.1269(5) 2.16(10) C(l l) 0.4970(5) 0.7129(2) 0.7091(4) 1.89(10) C(38) 0.6842(5) 0.6239(2) 0.2145(4) 1.58(9) C(12) 0.3512(5) 0.7116(2) 0.7016(5) 2.11(10) C(39) 0.8763(9) 0.2664(5) 0.9539(7) 5.5(2) C(13) 0.2718(5) 0.6500(2) 0.6693(5) 2.35(11) C(40) 0.9556(9) 0.2086(4) 1.0012(9) 5.2(2) C(14) 0.3371(5) 0.5893(2) 0.6427(5) 1.92(10) C(41) 1.0087(7) 0.1966(3) 1.1218(8) 4.4(2) C(15) 0.4616(5) 0.4370(2) 0.6272(4) 1.40(9) C(42) 0.9868(8) 0.2433(4) 1.2002(6) 4.5(2) C(16) 0.5166(5) 0.3825(2) 0.7115(4) 1.72(9) C(43) 0.9073(7) 0.3033(3) 1.1567(8) 4.5(2) C(17) 0.4344(6) 0.3211(2) 0.7047(5) 2.58(12) C(44) 0.8511 0.3161(3) 1.0317(9) 5.6(2) C(18) 0.2979(6) 0.3135(2) 0.6141(5) 2.66(12) H(l) 0.599(8) 0.378(3) 0.331(7) 5.6(12) C(19) 0.2418(5) 0.3675(2) 0.5300(5) 2.06(10) H(2) 0.686(7) 0.366(3) 0.440(5) 4.1(11) C(20) 0.3241(4) 0.4283(2) 0.5370(4) 1.52(9) Table V .2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance Ru(l) Br(l) 2.6343(5) Ru(l) Br(2) 2.5540(4) Ru(l) S(l) 2.3330(10) Ru(l) P(l) 2.2617(10) Ru(l) P(2) 2.3011(11) Ru(l) N(l) 2.372(3) P(l) C(l) 1.827(4) P(l) C(9) 1.834(4) P(l) C(15) 1.845(4) P(2) C(21) 1.845(4) P(2) C(27) 1.852(4) P(2) C(33) 1.851(4) N(l) C(2) 1.488(6) N(l) C(7) 1.499(6) N(l) C(8) 1.494(5) C(l) C(2) 1.367(6) C(l) C(6) 1.407(6) C(2) C(3) 1.390(7) C(3) C(4) 1.382(8) C(4) C(5) 1.371(8) C(5) C(6) 1.379(7) C(9) C(10) 1.397(6) C(9) C(14) 1.383(6) C(10) C(l l ) 1.400(6) C(l l) C(12) 1.383(7) C(12) C(13) 1.377(7) C(13) C(14) 1.399(6) C(15) C(16) 1.398(6) C(15) C(20) 1.387(6) C(16) C(17) 1.395(6) C(17) C(18) 1.380(8) C(18) C(19) 1.390(7) C(19) C(20) 1.387(6) C(21) C(22) 1.399(6) C(21) C(26) 1.386(6) C(22) C(23) 1.385(6) C(23) C(24) 1.386(7) C(24) C(25) 1.391(7) C(25) C(26) 1.405(6) C(27) C(28) 1.403(6) C(27) C(32) 1.391(6) C(28) C(29) 1.389(6) C(29) C(30) 1.385(8) C(30) C(31) 1.387(9) C(31) C(32) 1.396(7) C(33) C(34) 1.395(6) C(33) C(38) 1.396(6) C(34) C(35) 1.379(6) C(35) C(36) 1.384(7) C(36) C(37) 1.374(7) C(37) C(38) 1.394(6) C(39) C(40) 1.341(11) C(39) C(44) 1.385(12) C(40) C(41) 1.335(12) C(41) C(42) 1.339(10) C(42) C(43) 1.369(10) C(43) C(44) 1.384(11) S(l) H(l) 1.25(7) S(l) H(2) 1.34(6) 277 Appendix V Table V.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle Br(l) Ru(l) Br(2) 94.00(2) Br(l) Ru(l) S(l) 79.77(3) BrO) Ru(l) P(l) 169.09(3) Br(l) Ru(l) P(2) 89.54(3) Br(l) Ru(l) N(l) 89.55(8) Br(2) Ru(l) S(l) 172.31(3) Br(2) Ru(l) P(l) 91.57(3) Br(2) Ru(l) P(2) 90.94(3) Br(2) Ru(l) N(l) 86.01(8) S(l) Ru(l) P(l) 93.87(4) S(l) Ru(l) P(2) 93.48(4) S(l) Ru(l) N(l) 89.43(9) P(l) Ru(l) P(2) 99.76(4) P(l) Ru(l) N(l) 81.47(8) P(2) Ru(l) N(l) 176.75(9) Ru(l) P(l) C(l) 104.35(13) Ru(l) P(l) C(9) 127.55(13) Ru(l) P(l) C(15) 113.28(13) C(l) P(l) C(9) 100.2(2) C(l) P(l) C(15) 103.3(2) C(9) P(l) C(15) 104.9(2) Ru(l) P(2) C(21) 117.65(13) Ru(l) P(2) C(27) 114.75(13) Ru(l) P(2) C(33) 120.25(14) C(21) P(2) C(27) 106.4(2) C(21) P(2) C(33) 96.6(2) C(27) P(2) C(33) 98.1(2) Ru(l) N(l) C(2) 111.7(2) Ru(l) N(l) C(7) 112.4(3) Ru(l) N(l) C(8) 110.1(3) C(2) N(l) C(7) 107.0(3) C(2) N(l) C(8) 109.2(3) C(7) N(l) C(8) 106.3(3) P(l) C(l) C(2) 119.6(3) P(l) C(l) C(6) 120.9(3) C(2) C(l) C(6) 119.5(4) N(l) C(2) C(l) 119.8(4) N(l) C(2) C(3) 120.0(4) C(l) C(2) C(3) 120.1(4) C(2) C(3) C(4) 119.9(4) C(3) C(4) C(5) 120.6(4) C(4) C(5) C(6) 119.7(5) C(l) C(6) C(5) 120.2(4) P(l) C(9) C(10) 117.3(3) P(l) C(9) C(14) 123.7(3) C(10) C(9) C(14) 118.9(4) C(9) C(10) C(ll) 120.1(4) C(10) C(ll) C(12) 120.4(4) C(l l ) C(12) C(13) 119.5(4) C(12) C(13) C(14) 120.5(4) C(9) C(14) C(13) 120.5(4) P(l) C(15) C(16) 120.5(3) P(l) C(15) C(20) 120.7(3) C(16) C(15) C(20) 118.2(4) C(15) C(16) C(17) 120.5(4) C(16) C(17) C(18) 120.4(4) C(17) C(18) C(19) 119.7(4) C(18) C(19) C(20) 119.7(4) C(15) C(20) C(19) 121.6(4) P(2) C(21) C(22) 114.5(3) P(2) C(21) C(26) 126.7(3) C(22) C(21) C(26) 118.6(4) C(21) C(22) C(23) 120.7(4) C(22) C(23) C(24) 120.8(4) C(23) C(24) C(25) 119.2(4) C(24) C(25) C(26) 120.0(4) C(21) C(26) C(25) 120.7(4) P(2) C(27) C(28) 123.5(3) P(2) C(27) C(32) 118.5(3) C(28) C(27) C(32) 117.9(4) C(27) C(28) C(29) 121.5(5) C(28) C(29) C(30) 119.7(5) C(29) C(30) C(31) 119.8(4) C(30) C(31) C(32) 120.3(5) C(27) C(32) C(31) 120.8(5) P(2) C(33) C(34) 117.0(3) P(2) C(33) C(38) 123.6(3) C(34) C(33) C(38) 119.4(4) C(33) C(34) C(35) 121.0(4) C(34) C(3S) C(36) 119.5(5) C(35) C(36) C(37) 120.2(4) C(36) C(37) C(38) 121.1(4) C(33) C(38) C(37) 118.9(4) C(40) C(39) C(44) 119.6(7) C(39) C(40) C(41) 121.8(7) C(40) C(41) C(42) 120.5(6) C(41) C(42) C(43) 120.0(6) C(42) C(43) C(44) 119.9(6) C(39) C(44) C(43) 118.2(6) Ru(l) S(l) H(l) 100.9(26) Ru(l) S(l) H(2) 115.2(22) H(l) S(l) H(2) 98.0(39) 278 Appendix VI APPENDIX VI X-Ray Crystallographic Analysis of as-RuCl2(P-N)(PPh3)(MeSH)-(acetone) (20) 279 Appendix VI H3 H36 Figure VJ..2 Pluto plot of the molecular structure of 20. 280 Appendix VI E X P E R I M E N T A L DETAILS A . Crystal Data Empirical Formula C2H45CI2NOP2RUS Formula Weight 845.81 Crystal Colour, Habit yellow-brown, prism Crystal Dimensions 0.13 X 0.25 X 0.35 mm Crystal System monoclinic Lattice Type Primitive Lattice Parameters a = 14.2074(12) A b = 16.275(2) A c = 16.7122(3) A p = 92.6672(5)° V = 3860.1(4) A 3 Space Group P2i/n (#4) Z value 4 Dcjc 1.455 g/cm3 Fooo 1744.00 H(MoKa) 7.16 cm 1 B. Diffractometer Radiation Detector Aperture Temperature Data Images <)> oscillation Range (x = -90) co oscillation Range (x = -90) Detector Position Detector Swing Angle 29 l m x No. of Reflections Measured Corrections Measurements Rigaku/ADSC CCD MoKa (X = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 462 exposures of 90.0 seconds 0.0 -190.0° -23.0 -18.0° 39.202(6) mm -10° 60.1° Total: 36449 Unique: 9917 (Ri« = 0.062) Lorentz-polarization Absorption/scaling (trans, factors: 0.7658 -1.0060) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R;Rw Goodness of Fit Indicator No. Observations (I>3a(I)) Residuals (on F, I>3o(I)): R; Rw Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares I<o( |Fo 2 | - |Fc 2 | ) 2 1 CO = 2 2 CT (FfJ ) 0.0000 All non-hydrogen atoms 9917 455 21.80 0.071; 0.116 1.09 7067 0.039; 0.0525 0.001 1.60 e'/A3 (near Ru) -3.08 e'/A3 (near Ru) 281 Appendix VI Table V . l Atomic coordinates and B, Atom X y z Ru(l) 0.563404(14) 0.272801(13) 0.156709(12) 0.911(5) Cl(l) 0.58012(5) 0.14832(4) 0.23574(4) 1.84(2) Cl(2) 0.58406(5) 0.19478(5) 0.03359(4) 1.83(2) S(l) 0.55643(6) 0.39499(5) 0.08285(4) 1.72(2) P(l) 0.57184(5) 0.35445(5) 0.26770(4) 1.099(14) P(2) 0.40451(5) 0.24444(4) 0.13879(4) 0.983(14) O(l) 0.4602(2) -0.1088(2) 0.3703(2) 4.24(7) N(l) 0.7269(2) 0.2886(2) 0.16336(13) 1.46(5) C(l) 0.6987(2) 0.3746(2) 0.2826(2) 1.56(6) C(2) 0.7607(2) 0.3402(2) 0.2315(2) 1.69(6) C(3) 0.8571(2) 0.3553(3) 0.2429(2) 2.91(8) C(4) 0.8905(2) 0.4047(3) 0.3055(2) 3.63(9) C(5) 0.8288(2) 0.4382(3) 0.3577(2) 3.61(9) C(6) 0.7334(2) 0.4225(2) 0.3471(2) 2.40(7) CO) 0.7609(2) 0.3252(2) 0.0872(2) 2.32(7) C<8) 0.7711(2) 0.2057(2) 0.1698(2) 2.43(7) C(9) 0.5441(2) 0.3309(2) 0.3727(2) 1.39(6) C(10) 0.5808(2) 0.2589(2) 0.4067(2) 1.80(7) C(l l) 0.5686(2) 0.2407(2) 0.4866(2) 2.48(8) C(12) 0.5192(3) 0.2940(3) 0.5336(2) 2.84(8) C(13) 0.4836(3) 0.3656(2) 0.5014(2) 3.01(8) C(14) 0.4965(2) 0.3847(2) 0.4212(2) 2.25(7) C(15) 0.5186(2) 0.4568(2) 0.2558(2) 1.47(6) C(16) 0.4213(2) 0.4630(2) 0.2568(2) 2.01(7) C(17) 0.3765(2) 0.5384(2) 0.2456(2) 2.74(8) C(18) 0.4295(3) 0.6077(2) 0.2328(2) 3.13(9) Atom X y z Beq C(19) 0.5254(3) 0.6026(2) 0.2305(2) 2.96(8) C(20) 0.5710(2) 0.5274(2) 0.2424(2) 2.14(7) C(21) 0.3484(2) 0.3022(2) 0.0551(2) 1.26(6) C(22) 0.3189(2) 0.3829(2) 0.0627(2) 1.72(6) C(23) 0.2831(2) 0.4273(2) -0.0030(2) 2.41(7) C(24) 0.2779(2) 0.3902(2) -0.0781(2) 2.82(8) C(25) 0.3077(2) 0.3110(2) -0.0865(2) 2.56(8) C(26) 0.3428(2) 0.2663(2) -0.0214(2) 1.84(7) C(27) 0.3280(2) 0.2622(2) 0.2229(2) 1.40(6) C(28) 0.3627(2) 0.2345(2) 0.2978(2) 1.86(7) C(29) 0.3093(3) 0.2439(2) 0.3645(2) 2.60(8) C(30) 0.2218(3) 0.2808(2) 0.3582(2) 2.84(8) C(31) 0.1867(2) 0.3075(2) 0.2841(2) 2.61(8) C(32) 0.2385(2) 0.2970(2) 0.2161(2) 1.80(6) C(33) 0.3648(2) 0.1390(2) 0.1112(2) 1.40(6) C(34) 0.4244(2) 0.0732(2) 0.1004(2) 1.76(6) C(35) 0.3880(3) -0.0029(2) 0.0754(2) 2.49(7) C(36) 0.2912(3) -0.0134(2) 0.0616(2) 2.60(8) C(37) 0.2313(2) 0.0518(2) 0.0721(2) 2.62(8) C(38) 0.2672(2) 0.1278(2) 0.0970(2) 2.09(7) C(39) 0.5506(2) 0.3847(2) -0.0248(2) 2.16(7) C(40) 0.4625(3) -0.0350(3) 0.3664(2) 3.12(9) C(41) 0.3850(3) 0.0114(3) 0.3244(3) 5.18(12) C(42) 0.5446(4) 0.0127(3) 0.3996(3) 5.67(13) H(l) 0.488(3) 0.414(2) 0.092(2) 4.2(8) Table VI.2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance Ru(l) Cl(l) 2.4241(7) Ru(l) Cl(2) 2.4472(7) Ru(l) S(l) 2.3403(7) Ru(l) P(l) 2.2803(7) Ru(l) P(2) 2.3100(7) Ru(l) N(l) 2.335(2) S(l) C(39) 1.805(3) P(l) C(l) 1.838(3) P(l) C(9) 1.856(3) P(l) C(15) 1.837(3) P(2) C(21) 1.835(3) P(2) C(27) 1.840(3) P(2) C(33) 1.858(3) O(l) C<40) 1.203(5) N(l) C(2) 1.476(4) N(l) C(7) 1.505(4) N(l) C(8) 1.489(4) C(l) C(2) 1.374(4) C<1) C(6) 1.401(4) C(2) C(3) 1.396(4) C<3) C(4) 1.387(5) C(4) C(5) 1.378(5) C(5) C(6) 1.382(4) C(9) C(10) 1.394(4) C(9) C(14) 1.390(4) C(10) C(ll) 1.385(4) C(l l) C(12) 1.383(5) C(12) C(13) 1.371(5) C(13) C(14) 1.396(4) C(15) C(16) 1.386(4) C(15) C(20) 1.393(4) C(16) C(17) 1.391(4) C(17) C(18) 1.378(5) C(18) C(19) 1.368(5) C(19) C(20) 1.394(5) C(21) C(22) 1.387(4) C(21) C(26) 1.405(4) C(22) C(23) 1.390(4) C(23) C(24) 1.392(5) C(24) C(25) 1.366(5) C(25) C<26) 1.382(4) C(27) C(28) 1.399(4) C(27) C<32) 1.391(4) C(28) C(29) 1.385(4) C(29) C(30) 1.381(5) C(30) C(31) 1.383(5) C(31) C(32) 1.393(4) C(33) C(34) 1.383(4) C(33) C(38) 1.408(4) C(34) C(35) 1.398(4) C(35) C(36) 1.393(5) C(36) C(37) 1.376(5) C(37) C(38) 1.394(4) C(40) C(41) 1.484(5) C(40) C(42) 1.487(5) S(l) H(l) 1.03(4) 282 Appendix VI Table VI.3 Bond angles (°) with estimated standard deviations Atom atom atom angle atom atom atom angle Cl(l) Ru(l) Cl(2) 90.69(3) Cl(l) Ru(l) S(l) 176.61(3) Cl(l) Ru(l) P(l) 92.50(3) Cl(l) Ru(l) P(2) 88.51(3) Cl(l) Ru(l) N(l) 89.66(6) Cl(2) Ru(l) S(l) 90.07(3) Cl(2) Ru(l) P(l) 169.27(3) Cl(2) Ru(l) P(2) 86.67(3) Cl(2) Ru(l) N(l) 86.51(6) S(l) Ru(l) P(l) 86.17(3) S(l) Ru(l) P(2) 94.83(3) S(l) Ru(l) N(l) 87.09(6) P(l) Ru(l) P(2) 103.65(3) P(l) Ru(l) N(l) 83.26(6) P(2) Ru(l) N(l) 172.92(6) Ru(l) S(l) C(39) 116.49(11) Ru(l) P(l) C(l) 103.19(10) Ru(l) P(l) C(9) 130.05(10) Ru(l) P(l) C(15) 115.75(8) C(l) P(l) C(9) 99.13(12) C(l) P(l) C(15) 104.45(14) C(9) P(l) C(15) 100.67(13) Ru(l) P(2) C(21) 112.57(9) Ru(l) P(2) C(27) 118.57(10) Ru(l) P(2) C(33) 120.03(9) C(21) P(2) C(27) 104.52(13) C(21) P(2) C(33) 99.64(12) C(27) P(2) C(33) 98.69(12) Ru(l) N(l) C(2) 112.7(2) Ru(l) N(l) C(7) 111.2(2) Ru(l) N(l) C(8) 108.6(2) C(2) N(l) C(7) 108.7(2) C(2) N(l) C(8) 109.8(2) C(7) N(l) C(8) 105.6(2) P(l) C(l) C(2) 119.7(2) P(l) C(l) C(6) 120.8(2) C(2) C(l) C(6) 119.5(3) N(l) C(2) C(l) 121.1(2) N(l) C(2) C(3) 119.2(3) C(l) C(2) C(3) 119.7(3) C(2) C(3) C(4) 120.4(3) C(3) C(4) C(5) 120.1(3) C(4) C(5) C(6) 119.6(3) C(l) • C(6) C(5) 120.7(3) P(l) C(9) C(10) 117.8(2) P(l) C(9) C(14) 123.5(2) C(10) C(9) C(14) 118.3(3) C(9) C(10) C(l l ) 120.7(3) C(10) C(ll) C(12) 120.2(3) C(ll) C(12) C(13) 119.9(3) C(12) C(13) C(14) 120.2(3) C(9) C(14) C(13) 120.6(3) P(l) C(15) C(16) 118.0(2) P(l) C(15) C(20) 123.0(2) C(16) C(15) C(20) 118.9(3) C(15) C(16) C(17) 120.8(3) C(16) C(17) C(18) 119.6(3) C(17) C(18) C(19) 120.4(3) C(18) C(19) C(20) 120.4(3) C(15) C(20) C(19) 119.9(3) P(2) C(21) C(22) 122.5(2) P(2) C(21) C(26) 119.0(2) C(22) C(21) C(26) 118.2(3) C(21) C(22) C(23) 121.4(3) C(22) C(23) C(24) 119.3(3) C(23) C(24) C(25) 119.9(3) C(24) C(25) C(26) 121.2(3) C(21) C(26) C(25) 120.1(3) P(2) C(27) C(28) 115.9(2) P(2) C(27) C(32) 124.8(2) C(28) C(27) C(32) 119.2(3) C(27) C(28) C(29) 120.0(3) C(28) C(29) C(30) 120.8(3) C(29) C(30) C(31) 119.4(3) C(30) C(31) C(32) 120.6(3) C(27) C(32) C(31) 119.9(3) P(2) C(33) C(34) 124.6(2) P(2) C(33) C(38) 116.6(2) C(34) C(33) C(38) 118.8(3) C(33) C(34) C(35) 120.3(3) C(34) C(35) C(36) 120.5(3) C(35) C(36) C(37) 119.7(3) C(36) C(37) C(38) 120.1(3) C(33) C(38) C(37) 120.6(3) O(l) C(40) C(41) 120.8(4) O(l) C(40) C(42) 121.5(4) C(41) C(40) C(42) 117.6(4) Ru(l) S(l) H(l) 101.5(21) C(39) S(l) H(l) 100.1(18) 283 APPENDIX VII Appendix VII X-Ray Crystallographic Analysis of Cis-RuCl2(P-N)(PPh3)(EtSH)(1.5C6D6) (21) E X P E R I M E N T A L DETAILS A . Crystal Data Empirical Formula C49H5oCl2NOP2RuS Formula Weight 918.92 Crystal Colour, Habit yellow, prism Crystal Dimensions 0.30 X 0.30 X 0.20 mm Crystal System monoclinic Lattice Type Primitive Lattice Parameters a = 16.6933(8) A b= 12.4262(12) A c = 21.8288(6) A p = 106.3313(8)° V = 4345.3(4) A 3 Space Group P2i/n (#14) Z value 4 Dcjc 1-405 g/cm3 Fooo 1900.00 u(MoKa) 6.41 cm"1 B. Diffract ometer Radiation Detector Aperture Temperature Data Images <f> oscillation Range (x = -90) co oscillation Range (x = -90) Detector Position Detector Swing Angle 2©mut No. of Reflections Measured Corrections Measurements Rigaku/ADSC CCD MoKa (A. = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 462 exposures of 70.0 seconds 0.0 -190.0° -23.0 -18.0° 39.23(2) mm -10.0° 60.1° Total: 39270 Unique: 11495 (Ri« = 0.031) Lorentz-polarization Absorption/scaling (trans, factors: 0.7251-1.0060) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R;Rw Goodness of Fit Indicator No. Observations (I>3a(I)) Residuals (on F, I>3o(I)): R;Rw Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares Z c o ( | F o 2 | - | F c 2 | ) 2 1 <B = 2 / c 2 N a (Fo ) 0.0000 All non-hydrogen atoms 11495 509 22.58 0.056; 0.058 1.96 7749 0.033; 0.027 0.003 1.01 e"/A3 -0.93 e/A 3 2 8 4 Appendix VII Table VH.1 Atomic coordinates and B eq atom X y z B e q atom X y z B e q Ru(l) 0.418466(10) 0.570955(14) 0.208292(9) 1.617(4) C(23) 0.46229(13) 0.3100(2) 0.26619(11) 1.72(5) Cl(l) 0.37043(3) 0.58327(5) 0.09307(3) 2.601(13) C(24) 0.53731(13) 0.3180(2) 0.31406(11) 1.85(5) Cl(2) 0.27352(3) 0.53219(5) 0.20834(3) 2.664(13) C(25) 0.54974(14) 0.2641(2) 0.37205(12) 2.56(6) S(l) 0.45307(3) 0.56662(5) 0.31981(3) 2.001(12) C(26) 0.4856(2) 0.2017(2) 0.38268(13) 2.92(6) P(l) 0.54808(3) 0.63933(4) 0.21880(3) 1.628(12) C(27) 0.41101(15) 0.1924(2) 0.33560(13) 2.92(6) P(2) 0.44387(3) 0.39156(4) 0.19320(3) 1.637(12) C(28) 0.39846(13) 0.2459(2) 0.27738(12) 2.25(5) N(l) 0.38559(10) 0.75368(14) 0.21865(10) 2.23(4) C(29) 0.53372(12) 0.3589(2) 0.16258(11) 1.71(5) C(l) 0.37686(15) 0.5025(2) 0.35372(13) 2.96(6) C(30) 0.53938(13) 0.4141(2) 0.10888(11) 2.17(5) C(2) 0.4146(2) 0.4868(2) 0.42421(15) 4.25(8) C(31) 060449(15) 0.3941(2) 0.08185(12) 2.76(6) C(3) 0.53772(13) 0.7826(2) 0.23543(11) 1.96(5) C(32) 0.66430(14) 0.3189(2) 0.10925(13) 2.87(6) C(4) 0.45912(13) 0.8249(2) 0.23178(12) 2.26(5) C(33) 0.65814(14) 0.2609(2) 0.16161(12) 2.46(6) C(5) 0.45044(14) 0.9361(2) 0.23961(14) 3.31(6) C(34) 0.59347(13) 0.2800(2) 0.18855(11) 2.10(5) C(6) 0.5190(2) 1.0021(2) 0.2518(2) 4.30(8) C(35) 0.36373(13) 0.3085(2) 0.13691(11) 2.07(5) C(T) 0.5975(2) 0.9604(2) 0.25654(15) 3.86(7) C(36) 0.28266(14) 0.3435(2). 0.10819(12) 2.65(6) C(8) 0.60632(14) 0.8517(2) 0.24811(13) 2.81(6) C(37) 0.22415(14) 0.2740(2) 0.06924(13) 3.22(6) C(9) 0.34489(15) 0.7699(2) 0.27102(14) 3.09(6) C(38) 0.2455(2) 0.1712(2) 0.05829(13) 3.43(7) C(10) 0.32383(15) 0.7897(2) 0.15837(14) 3.48(6) C(39) 0.3260(2) 0.1356(2) 0.08558(14) 3.70(7) C(l l ) 0.63106(12) 0.5926(2) 0.28861(11) 1.86(5) C(40) 0.38463(15) 0.2035(2) 0.12465(13) 3.05(6) C(12) 0.64354(14) 0.6398(2). 0.34871(12) 2.57(6) C(41) 0.4097(3) 0.2249(3) 0.5167(2) 6.98(13) C(13) 0.69956(15) 0.5943(2) 0.40198(12) 3.41(7) C(42) 0.4784(2) 0.1826(3) 0.5610(2) 5.11(9) C(14) 0.74447(15) 0.5036(2) 0.39619(14) 3.63(7) C(43) 0.4715(3) 0.0864(3) 0.5852(3) 11.27(15) C(15) 0.73424(14) 0.4578(2) 0.33736(15) 3.10(6) C(44) 0.3948(3) 0.0346(4) 0.5678(3) 13.0(2) C(16) 0.67789(13) 0.5009(2) 0.28361(12) 2.29(5) C(45) 0.3318(2) 0.0694(3) 0.5223(3) 8.62(13) C(17) 0.60383(13) 0.6527(2) 0.15717(11) 1.89(5) C(46) 0.3373(2) 0.1666(4) 0.4959(2) 7.25(13) C(18) 0.55905(14) 0.6784(2) 0.09574(13) 2.83(6) C(47) 0.5458(2) 0.0922(3) 0.0024(2) 5.69(10) C(19) 0.5985(2) 0.6926(2) 0.04784(13) 3.66(7) C(48) 0.5394(2) 0.0452(3) 0.0584(2) 5.58(10) C(20) 0.6839(2) 0.6798(2) 0.06154(15) 3.93(8) C(49) 0.4943(2) -0.0467(3) 0.0559(2) 5.66(10) C(21) 0.73024(15) 0.6572(2) 0.12359(15) 3.42(7) H(l) 0.5074(12) 0.493(2) 0.3353(10) 2.7(5) C(22) 0.69093(14) 0.6441(2) 0.17145(12) 2.42(6) Table VH..2 Bond lengths (A) with estimated standard deviations atom atom distance atom atom distance Ru(l) Cl(l) 2.4204(6) Ru(l) Cl(2) 2.4674(5) Ru(l) S(l) 2.3391(6) Ru(l) P(l) 2.2753(5) Ru(l) P(2) 2.3100(6) Ru(l) N(l) 2.362(2) S(l) C(l) 1.825(2) P(l) C(3) 1.835(2) P(l) C(ll) 1.841(2) P(l) C(17) 1.846(2) P(2) C(23) 1.840(2) P(2) C(29) 1.851(2) P(2) C(35) 1.855(2) N(l) C(4) 1.474(3) N(l) C(9) 1.498(3) N(l) C(10) 1.494(3) C(l) C(2) 1.502(4) C(3) C(4) 1.395(3) C(3) C(8) 1.396(3) C(4) C(5) 1.405(3) C(5) C(6) 1.372(3) C(6) C(7) 1.386(3) C(7) C(8) 1.376(3) C(ll) C(12) 1.398(3) C(l l ) C(16) 1.404(3) C(12) C(13) 1.391(3) C(13) C(14) 1.379(4) C(14) C(15) 1.371(4) C(15) C(16) 1.388(3) C(17) C(18) 1.377(3) C(17) C(22) 1.403(3) C(18) C(19) 1.394(3) C(19) C(20) 1.383(4) C(20) C(21) 1.386(4) C(21) C(22) 1.391(3) C(23) C(24) 1.391(3) C(23) C(28) 1.405(3) C(24) C(25) 1.395(3) C(25) C(26) 1.394(3) C(26) C(27) 1.378(4) C(27) C(28) 1.397(3) C(29) C(30) 1.384(3) C(29) C(34) 1.399(3) C(30) C(31) 1.397(3) C(31) C(32) 1.375(3) C(32) C(33) 1;379(3) C(33) C(34) 1.388(3) C(35) C(36) 1.391(3) C(35) C(40) 1.396(3) C(36) C(37) 1.398(3) C(37) C(38) 1.365(4) C(38) C(39) 1.382(4) C(39) C(40) 1.388(3) C(41) C(42) 1.380(5) C(41) C(46) 1.372(5) C(42) C(43) 1.324(5) C(43) C(44) 1.388(5) C(44) C(45) 1.300(5) C(45) C(46) 1.353(5) C(47) C(48) 1.385(5) C(47) C(49)* 1.382(5) C(48) C(49) 1.361(4) S(l) H(l) 1.27(2) *symmetry operation: 1-x, -y, z 285 Appendix VII Table "VTI.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle Cl(l) Ru(l) Cl(2) 88.54(2) Cl(l) Ru(l) S(l) 174.63(2) Cl(l) Ru(l) P(l) 96.25(2) Cl(l) Ru(l) P(2) 86.17(2) Cl(l) Ru(l) N(l) 91.19(5) Cl(2) Ru(l) S(l) 87.15(2) Cl(2) Ru(l) P(l) 167.88(2) Cl(2) Ru(l) P(2) 91.78(2) Cl(2) Ru(l) N(l) 86.18(4) S(l) Ru(l) P(l) 87.37(2) S(l) Ru(l) P(2) 97.16(2) S(l) Ru(l) N(l) 85.33(5) P(l) Ru(l) P(2) 99.63(2) P(l) Ru(l) N(l) 82.61(4) P(2) Ru(l) N(l) 176.71(5) Ru(l) S(l) C(l) 115.84(9) Ru(l) P(l) C(3) 104.02(7) Ru(l) P(l) C(ll) 116.00(6) Ru(l) P(l) C(17) 128.33(8) C(3) P(l) C(ll) 103.46(10) C(3) P(l) C(17) 98.72(9) C(ll) P(l) C(17) 102.45(10) Ru(l) P(2) C(23) 113.63(7) Ru(l) P(2) C(29) 117.58(7) Ru(l) P(2) C(35) 120.28(8) C(23) P(2) C(29) 103.70(10) C(23) P(2) C(35) 100.42(10) C(29) P(2) C(35) 98.37(10) Ru(l) N(l) C(4) 113.09(12) Ru(l) N(l) C(9) 111.69(13) Ru(l) N(l) C(10) 108.99(14) C(4) N(l) C(9) 107.6(2) C(4) N(l) C(10) 108.8(2) C(9) N(l) C(10) 106.5(2) S(l) C(l) C(2) 109.4(2) P(l) C(3) C(4) 119.6(2) P(l) C(3) C(8) 121.2(2) C(4) C(3) C(8) 119.1(2) N(l) C(4) C(3) 120.2(2) N(l) C(4) C(5) 120.3(2) C(3) C(4) C(5) 119.4(2) C(4) C(5) C(6) 120.2(2) C(5) C(6) C(7) 120.7(2) C(6) C(7) C(8) 119.4(2) C(3) C(8) C(7) 121.2(2) P(l) C(l l ) C(12) 121.6(2) P(l) C(l l ) C(16) 119.8(2) C(12) C(l l ) C(16) 118.3(2) C(ll) C(12) C(13) 120.1(2) C(12) C(13) C(14) 120.7(3) C(13) C(14) C(15) 119.8(2) C(14) C(15) C(16) 120.5(2) C(l l ) C(16) C(15) 120.5(2) P(l) C(17) C(18) 118.9(2) P(l) C(17) C(22) 122.3(2) C(18) C(17) C(22) 118.6(2) C(17) C(18) C(19) 121.2(2) C(18) C(19) C(20) 119.9(3) C(19) C(20) C(21) 119.5(2) C(20) C(21) C(22) 120.4(2) C(17) C(22) C(21) 120.2(2) P(2) C(23) C(24) 120.5(2) P(2) C(23) C(28) 120.8(2) C(24) C(23) C(28) 118.5(2) C(23) C(24) C(25) 121.3(2) C(24) C(25) C(26) 119.6(2) C(25) C(26) C(27) 119.8(2) C(26) C(27) C(28) 120.8(2) C(23) C(28) C(27) 120.1(2) P(2) C(29) C(30) 116.9(2) P(2) C(29) C(34) 124.4(2) C(30) C(29) C(34) 118.6(2) C(29) C(30) C(31) 121.1(2) C(30) C(31) C(32) 119.6(2) C(31) C(32) C(33) 120.1(2) C(32) C(33) C(34) 120.7(2) C(29) C(34) C(33) 119.9(2) P(2) C(35) C(36) 123.6(2) P(2) C(35) C(40) 118.3(2) C(36) C(35) C(40) 118.0(2) C(35) C(36) C(37) 120.4(2) C(36) C(37) C(38) 120.8(2) C(37) C(38) C(39) 119.6(2) C(38) C(39) C(40) 120.1(3) C(35) C(40) C(39) 121.0(2) C(42) C(41) C(46) 120.7(3) C(41) C(42) C(43) 118.4(3) C(42) C(43) C(44) 119.1(4) C(43) C(44) C(45) 122.7(5) C(44) C(45) C(46) 119.0(4) C(41) C(46) C(45) 119.4(4) C(48) C(47) C(49)* 120.2(3) C(47) C(48) C(49) 119.9(3) C(47)* C(49) C(48) 119.9(3) Ru(l) S(l) H(l) 104.1(9) C(l) S(l) H(l) 96.0(9) 286 Appendix VIII APPENDIX VIII (Parti) X-Ray Crystallographic Analysis of rra/is-RuCI2(P-N)(PPh3)(OH2>(2C6H6) (33a, I) Figure VHI.1 Stereoview of the molecular structure of 33a, I. 287 Appendix VIII E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type Lattice Parameters C5oH49Cl2NOP2Ru 913.87 pink, prism 0.08X0.12X0.30 mm monoclinic Primitive a = 10.5773(6) A b = 16.979(2) A c = 24.2616(6) A p = 90.7065(5)° Space Group Z value Fooo u(MoKa) V = 4356.9(4) A 3 P2i/n(#14) 4 1.393 g/cm3 1888.00 5.94 cm"1 B. Intensity Measurements Diifractometer Radiation Detector Aperture Temperature Data Images <)> oscillation Range (% = -90) co oscillation Range (% = -90) Detector Position Detector Swing Angle 20™! No. of Reflections Measured Corrections Rigaku/ADSC CCD MoKa (X = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 769 exposures of 50.0 seconds 0.0 -190.2° -23.0 -17.8° 39.216(5) mm -10.0° 60.1° Total: 38827 Unique: 10693 (Ri« = 0.054) Lorentz-polarization ' Absorption/decay/scaling (coor. factors: 0.6090 - 1.0000) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R;Rw Goodness of Fit Indicator No. Observations (I>3a(I)) Residuals (on F, I>3or(I)): R;Rw Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares 2>(|FO2|-|FC2|)2 l a (Fo ) 0.0000 All non-hydrogen atoms 10693 514 20.80 0.117; 0.082 1.81 4878 0.056; 0.035 0.01 1.98 e"/A3 (near C(45-50) benzene) -2.61 e"/A3(nearRu) 288 Appendix VIII Table VTH.1 Atomic coordinates and Beq a t o m X y z a t o m X y z B e q Ru(l) 0.43571(3) 0.53463(2) 0.370059(15) 1.856(8) C(23) 0.5213(4) 0.2267(3) 0.3686(2) 3.64(14) Cl(l) 0.27219(8) 0.61626(7) 0.33187(5) 2.39(3) C(24) 0.4757(4) 0.1773(3) 0.3293(2) 3.65(14) Cl(2) 0.58439(8) 0.46816(7) 0.43054(4) 2.14(2) C(25) 0.3817(4) 0.2000(3) 0.2931(2) 3.32(13) P(l) 0.57846(8) 0.52747(8) 0.30347(5) 1.85(3) C(26) 0.3338(4) 0.2759(3) 0.2965(2) 2.67(12) P(2) 0.31168(9) 0.42776(7) 0.34521(5) 1.95(3) C(27) 0.1829(3) 0.4090(3) 0.3952(2) 2.17(11) O(l) 0.3252(2) 0.5512(2) 0.44726(11) 2.33(7) C(28) 0.1727(4) 0.3401(3) 0.4259(2) 2.69(12) N(l) 0.5543(3) 0.6440(2) 0.39354(15) 1.97(9) C(29) 0.0703(4) 0.3288(3) 0.4605(2) 3.51(13) C(l) 0.7103(3) 0.5847(3) 0.3314(2) 2.13(10) C(30) -0.0228(4) 0.3866(3) 0.4646(2) 3.40(13) C(2) 0.6869(3) 0.6319(3) 0.3769(2) 2.07(10) C(31) -0.0135(3) 0.4554(3) 0.4344(2) 2.96(12) C(3) 0.7860(4) 0.6726(3) 0.4033(2) 3.12(12) C(32) 0.0896(3) 0.4668(3) 0.4002(2) 2.38(10) C(4) 0.9070(4) 0.6657(3) 0.3829(2) 3.56(14) C(33) 0.2142(3) 0.4375(3) 0.2820(2) 2.11(10) C(5) 0.9303(4) 0.6220(3) 0.3361(2) 3.25(13) C(34) 0.0964(4) 0.4039(3) 0.2753(2) 2.83(12) C(6) 0.8325(4) 0.5809(3) 0.3106(2) 2.76(12) C(35) 0.0289(4) 0.4117(3) 0.2271(2) 3.64(14) CCT) 0.5438(4) 0.6607(3) 0.4532(2) 2.83(12) C(36) 0.0782(4) 0.4536(3) 0.1834(2) 3.82(14) C(8) 0.5106(4) 0.7169(3) 0.3636(2) 2.64(12) C(37) 0.1963(4) 0.4866(3) 0.1889(2) 3.56(13) C(9) 0.5665(4) 0.5707(3) 0.2343(2) 2.28(11) C(38) 0.2638(4) 0.4780(3) 0.2376(2) 2.84(12) C(10) 0.4758(4) 0.6282(3) 0.2211(2) 2.32(11) C(39) 0.2650(12) 0.1276(5) 0.4665(4) 10.2(4) C(l l ) 0.4721(4) 0.6632(3) 0.1705(2) 2.92(12) C(40) 0.3849(8) 0.1096(5) 0.4851(4) 7.7(3) C(12) 0.5567(5) 0.6443(3) 0.1300(2) 3.56(13) C(41) 0.4118(6) 0.0953(4) 0.5395(3) 7.1(2) C(13) 0.6481(4) 0.5885(3) 0.1413(2) 3.95(14) C(42) 0.3157(7) 0.0953(4) 0.5770(3) 6.6(2) C(14) 0.6532(4) 0.5509(3) 0.1926(2) 3.11(12) C(43) 0.1960(7) 0.1096(4) 0.5586(4) 7.7(3) C(15) 0.6498(4) 0.4310(3) 0.2898(2) 2.35(11) C(44) 0.1723(9) 0.1238(5) 0.5046(5) 9.3(3) C(16) 0.6021(4) 0.3837(3) 0.2467(2) 3.07(12) C(45) 0.7622(9) 0.1993(10) 0.5105(5) 12.7(5) C(17) 0.6514(5) 0.3085(3) 0.2380(2) 4.08(15) C(46) 0.7873(7) 0.2350(5) 0.5587(5) 7.1(3) C(18) 0.7472(5) 0.2797(3) 0.2718(3) 4.18(15) C(47) 0.8332(8) 0.1906(7) 0.5978(4) 7.5(3) C(19) 0.7924(4) 0.3251(3) 0.3141(2) 3.46(14) C(48) 0.8574(12) 0.1131(9) 0.5931(8) 16.3(6) C(20) 0.7445(4) 0.4003(3) 0.3235(2) 2.67(12) C(49) 0.834(2) 0.0844(10) 0.5421(10) 19.3(9) C(21) 0.3777(3) 0.3281(3) 0.3371(2) 2.23(11) C(50) 0.772(2) 0.120(2) 0.5011(8) 23.3(10) C(22) 0.4724(4) 0.3026(3) 0.3730(2) 2.87(12) Table V H L 2 Bond lengths (A) with estimated standard deviations a t o m a t o m d i s t a n c e a t o m a t o m d i s t a n c e Ru(l) Cl(l) 2.3941(11) Ru(l) Cl(2) 2.4173(10) Ru(l) P(l) 2.2281(11) Ru(l) P(2) 2.3147(12) Ru(l) O(l) 2.238(3) Ru(l) N(l) 2.308(3) P(l) C(l) 1.823(4) P(l) C(9) 1.835(5) P(l) C(15) 1.835(4) P(2) C(21) 1.842(4) P(2) C(27) 1.861(4) P(2) C(33) 1.844(4) N(l) C(2) 1.479(4) N(l) C(7) 1.481(5) N(l) C(8) 1.505(5) C(l) C(2) 1.388(6) C<1) C(6) 1.395(5) C(2) C(3) 1.403(5) C(3) C(4) 1.382(6) C(4) C(5) 1.380(7) C(5) C(6) 1.389(6) C(9) C(10) 1.404(5) C(9) C(14) 1.414(5) C(10) C(l l ) 1.363(6) C(H) C<12) 1.375(6) C(12) C(13) 1.378(6) C(13) C(14) 1.400(6) C(15) C(16) 1.408(6) C(15) C(20) 1.388(6) C(16) C(17) 1.397(6) C<17) C(18) 1.385(7) C(18) C(19) 1.365(7) C(19) C(20) 1.394(6) C(21) C(22) 1.389(6) C(21) C(26) 1.400(6) C(22) C(23) 1.394(6) C(23) C<24) 1.355(7) C(24) C(25) 1.374(6) C(25) C(26) 1.388(6) C(27) C(28) 1.393(6) C(27) C(32) 1.399(5) C(28) C(29) 1.392(6) C(29) C(30) 1.395(6) C(30) C(31) 1.383(6) C(31) C(32) 1.391(5) C(33) C(34) 1.379(5) C(33) C(38) 1.387(6) C(34) C(35) 1.369(6) C(35) C(36) 1.384(6) C(36) C(37) 1.375(6) C(37) C(38) 1.381(6) C(39) C(40) 1.375(10) C(39) C(44) 1.357(12) C(40) C(41) 1.368(9) C(41) C(42) 1.373(8) C(42) C(43) 1.359(8) C(43) C(44) 1.352(11) C(45) C(46) 1.343(12) C(45) C(50) 1.37(3) C(46) C(47) 1.301(10) C(47) C(48) 1.346(13) C(48) C(49) 1.35(2) C(49) C(50) 1.33(4) 289 Appendix VIII Table VTH.3 B o n d angles (°) w i t h estimated standard deviations atom atom atom angle atom atom atom angle Cl(l) Ru(l) C!(2) 165.18(4) Cl(l) Ru(l) P(l) 104.11(4) Cl(l) Ru(l) P(2) 87.05(4) Cl(l) Ru(l) O(l) 82.47(7) Cl(l) Ru(l) N(l) 91.01(9) Cl(2) Ru(l) P(l) 88.45(4) Cl(2) Ru(l) P(2) 98.88(4) Cl(2) Ru(l) O(l) 83.87(7) Cl(2) Ru(l) N(l) 83.01(9) P(l) Ru(l) P(2) 98.94(4) P(l) Ru(l) O(l) 168.33(7) P(l) Ru(l) N(l) 81.48(9) P(2) Ru(l) O(l) 90.94(8) P(2) Ru(l) N(l) 178.06(9) O(l) Ru(l) N(l) 88.85(11) Ru(l) P(l) C(l) 102.95(14) Ru(l) P(l) C(9) 127.00(13) Ru(l) P(l) C(15) 117.63(14) C(l) P(l) C(9) 99.8(2) C(l) P(l) C(15) 103.2(2) C(9) P(l) C(15) 102.4(2) Ru(l) P(2) C(21) 122.25(13) Ru(l) P(2) C(27) 112.44(14) Ru(l) P(2) C(33) 117.09(14) C(21) P(2) C(27) 101.2(2) C(21) P(2) C(33) 101.7(2) C(27) P(2) C(33) 98.6(2) Ru(l) N(l) C(2) 109.6(3) Ru(l) N(l) C(7) 110.4(2) Ru(l) N(l) C(8) 112.3(2) C(2) N(l) C(7) 112.1(3) C(2) N(l) C(8) 105.6(3) C(7) N(l) C(8) 106.8(3) P(l) C(l) C(2) 117.3(3) P(l) C(l) C(6) 123.3(4) C(2) C(l) C(6) 119.3(4) N(l) C(2) C(l) 118.5(4) N(l) C(2) C(3) 120.8(4) C(l) C(2) C(3) 120.5(4) C(2) C(3) C(4) 119.0(5) C(3) C(4) C(5) 121.0(4) C(4) C(5) C(6) 119.9(4) C(l) C(6) C(5) 120.2(5) P(l) C(9) C(10) 121.8(3) P(l) C(9) C(14) 121.4(3) C(10) C(9) C(14) 116.7(4) C(9) C(10) C(ll) 121.4(4) C(10) C(ll) C(12) 121.9(4) C(ll) C(12) C(13) 118.7(5) C(12) C(13) C(14) 120.7(4) C(9) C(14) C(13) 120.6(4) P(l) C(15) C(16) 120.0(4) P(l) C(15) C(20) 121.6(4) C(16) C(15) C(20) 118.2(4) C(15) C(16) C(17) 120.2(5) C(16) C(17) C(18) 120.3(5) C(17) C(18) C(19) 119.6(5) C(18) C(19) C(20) 121.1(5) C(15) C(20) C(19) 120.6(5) P(2) C(21) C(22) 119.4(4) P(2) C(21) C(26) 122.3(3) C(22) C(21) C(26) 118.3(4) C(21) C(22) C(23) 120.4(4) C(22) C(23) C(24) 119.8(5) C(23) C(24) C(25) 121.7(5) C(24) C(25) C(26) 119.0(5) C(21) C(26) C(25) 120.8(4) P(2) C(27) C(28) 123.7(3) P(2) C(27) C(32) 117.4(3) C(28) C(27) C(32) 118.9(4) C(27) C(28) C(29) 120.3(4) C(28) C(29) C(30) 120.1(5) C(29) C(30) C(31) 120.1(4) C(30) C(31) C(32) 119.7(4) C(27) C(32) C(31) 120.9(4) P(2) C(33) C(34) 123.8(3) P(2) C(33) C(38) 118.5(3) C(34) C(33) C(38) 117.6(4) C(33) C(34) C(35) 121.4(4) C(34) C(35) C(36) 120.5(4) C(35) C(36) C(37) 119.0(4) C(36) C(37) C(38) 120.0(4) C(33) C(38) C(37) 121.4(4) C(40) C(39) C(44) 115.9(9) C(39) C(40) C(41) 122.4(8) C(40) C(41) C(42) 119.5(7) C(41) C(42) C(43) 118.5(7) C(42) C(43) C(44) 120.8(8) C(39) C(44) C(43) 122.7(9) C(46) C(45) C(50) 125.1(16) C(45) C(46) C(47) 116.1(11) C(46) C(47) C(48) 125.2(12) C(47) C(48) C(49) 113.4(17) C(48) C(49) C(50) 127.2(21) C(45) C(50) C(49) 111.2(14) 2 9 0 Appendix VIII (Partn) X-Ray Crystallographic Analysis of rra«s-RuCl2(P-N)(PPh3)(OH2)-(1.5C6H6) (33a, II) Figure VTH.2 Stereoview of the molecular structure of 33a, EL 291 Appendix VIII E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula C 4 7H4 6 Cl 2 NOP2Ru Formula Weight 874.81 Crystal Colour, Habit yellow-brown, prism Crystal Dimensions 0.10X0.15X0.25 mm Crystal System triclinic Lattice Type Primitive Lattice Parameters a = 11.9020(8) A b= 12.7647(13) A c= 15.590(2) A a = 106.371(5)° p = 94.400(3)° Y= 113.7903(10)° V = 2029.9(4) A 3 Space Group -PI (#2) Z value 2 D £ a k 1.431 g/cm3 Fooo 902.00 u(MoKa) 6.34 a n 1 B. Diflractometer Radiation Detector Aperture Temperature Data Images <j> oscillation Range (x = -90) co oscillation Range (x = -90) Detector Position Detector Swing Angle 20m»c No. of Reflections Measured Corrections Measurements Rigaku/ADSC CCD MoKcc (X = 0.71069 A) graphite monochromated 94 mm x 94 mm -93°C 462 exposures of 60.0 seconds 0.0 -190.0° -23.0 -18.0° 39.229(9) mm -10.0° 60.0° Total: 18577 Unique: 9139 (R w = 0.039) Lorentz-polarization Absorption/decay/scaling (coor. factors: 0.6605 - 1.0000) Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations No. Variables Reflection/Parameter Ratio Residuals (on F 2 , all data): R;Rw Goodness of Fit Indicator No. Observations (I>3o(I)) Residuals (on F, I>3o(I)): R; Rw Max Shifi/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map C. Structure Solution and Refinement Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares Z<o(|Fo2| - |Fc 2 | ) 2 1 CT (Fo ) 0.0000 All non-hydrogen atoms 9139 495 18.46 0.060; 0.055 1.20 5971 0.032; 0.025 0.004 1.18 eVA3 (near Ru) -1.02 eVA3 (near Ru) 292 Appendix VIII Table VTJJ.4 Atomic coordinates and B e q atom X y z Beq Ru(l) 0.20221(2) 0.21923(2) 0.174034(15) 1.018(5) Cl( l) 0.02663(5) 0.17778(6) 0.06146(4) 1.477(14) Cl(2) 0.36596(6) 0.20758(6) 0.26845(4) 1.633(15) P(l) 0.27389(6) 0.41616(6) 0.19006(5) 1.067(15) P(2) 0.09942(6) 0.21503(6) 0.29362(5) 1.087(15) O(l) 0.1283(2) 0.0212(2) 0.13264(15) 1.70(5) N(l) 0.3051(2) 0.2195(2) 0.05420(14) 1.23(5) C<1) 0.2977(2) 0.4152(3) 0.0750(2) 1.35(6) C(2) 0.3057(2) 0.3146(3) 0.0174(2) 1.41(6) C(3) 0.3216(3) 0.3080(3) -0.0709(2) 2.36(7) C(4) 0.3282(3) 0.4010(3) -0.1015(2) 2.89(8) C(5) 0.3190(3) 0.5011(3) -0.0458(2) 2.33(7) C(6) 0.3056(2) 0.5089(3) 0.0429(2) 1.83(6) C(7) 0.4405(2) 0.2494(3) 0.0856(2) 2.21(7) C(8) 0.2462(2) 0.0974(3) -0.0181(2) 2.16(7) C(9) 0.4258(2) 0.5418(3) 0.2584(2) 1.35(6) C(10) 0.5203(2) 0.5183(3) 0.2964(2) 1.60(6) C(H) 0.6393(2) 0.6133(3) 0.3402(2) 2.01(7) C(12) 0.6663(2) 0.7318(3) 0.3474(2) 2.24(7) C(13) 0.5734(3) 0.7560(3) 0.3107(2) 2.57(7) C(14) 0.4547(2) 0.6625(3) 0.2676(2) 1.99(7) C(15) 0.1675(2) 0.4879(2) 0.2114(2) 1.30(6) C(16) 0.0749(2) 0.4702(3) 0.1405(2) 1.69(6) C(17) -0.0136(2) 0.5135(3) 0.1594(2) 2.43(7) C(18) -0.0132(3) 0.5720(3) 0.2485(2) 2.61(8) C<19) 0.0791(3) 0.5921(3) 0.3197(2) 2.39(7) C(20) 0.1696(2) 0.5504(3) 0.3006(2) 1.74(6) C(21) 0.1733(2) 0.3498(2) 0.3990(2) 1.27(6) Table VTH.5 Bond lengths (A) with estimated Atom atom distance Ru(l) Cl(l) 2.3976(6) Ru(l) P(l) 2.2344(8) Ru(l) O(l) 2.187(2) P(l) C(l) 1.834(3) P(l) C(15) 1.839(2) P(2) C(27) 1.856(2) N(l) C(2) 1.479(3) N(l) C(8) 1.482(3) C(l) C(6) 1.395(4) C(3) C(4) 1.376(5) C(5) C(6) 1.385(4) C(9) C(14) 1.398(4) C(l l ) C(12) 1.383(4) C(13) C(14) 1.383(4) C(15) C(20) 1.387(3) C(17) C(18) 1.378(4) C(19) C(20) 1.398(3) C(21) C(26) 1.406(3) C(23) C(24) 1.386(3) C(25) C(26) 1.374(4) C(27) C(32) 1.399(4) C(29) C(30) 1.372(4) C(31) C(32) 1.395(3) C(33) C(38) 1.390(4) C(35) C(36) 1.391(4) C(37) C(38) 1.372(4) C(39) C(44) 1.385(4) C(41) C(42) 1.380(4) C(43) C(44) 1.373(4) C(45) C(47)» 1.376(5) O(l) H(l) 0.74(2) •symmetry operation: 1-x, -y, 1 -Z atom X y z Beq C(22) 0.3039(2) 0.4193(3) 0.4204(2) 1.45(6) C(23) 0.3621(2) 0.5273(3) 0.4929(2) 1.82(6) C(24) 0.2925(3) 0.5696(3) 0.5479(2) 2.10(7) C(25) 0.1623(3) 0.4999(3) 0.5293(2) 2.05(7) C(26) 0.1040(2) 0.3920(3) 0.4567(2) 1.65(6) C(27) -0.0658(2) 0.1927(3) 0.2804(2) 1.38(6) C(28) -0.1043(2) 0.2539(3) 0.2333(2) 1.52(6) C(29) -0.2256(2) 0.2462(3) 0.2287(2) 2.27(7) C(30) -0.3087(2) 0.1777(3) 0.2703(2) 2.26(7) C(31) -0.2701(2) 0.1188(3) 0.3193(2) 2.67(7) C(32) -0.1498(2) 0.1254(3) 0.3247(2) 2.06(7) C(33) 0.0834(2) 0.0876(3) 0.3324(2) 1.39(6) C(34) 0.1527(2) 0.1048(3) 0.4156(2) 1.95(7) C(35) 0.1348(3) 0.0054(3) 0.4427(2) 2.70(8) C(36) 0.0487(3) -0.1117(3) 0.3869(2) 2.73(8) C(37) -0.0192(3) -0.1288(3) 0.3035(2) 2.41(7) C(38) -0.0013(2) -0.0303(3) 0.2773(2) 1.76(6) C(39) 0.2545(3) -0.1825(3) 0.1794(2) 3.18(8) C(40) 0.1786(3) -0.2298(3) 0.0923(2) 2.90(8) C(41) 0.2299(3) -0.2079(3) 0.0200(2) 2.73(8) C(42) 0.3575(3) -0.1374(3) 0.0326(2) 2.76(8) C(43) 0.4334(3) -0.0909(3) 0.1182(2) 2.98(8) C(44) 0.3824(3) -0.1122(3) 0.1912(2) 3.44(9) C(45) 0.5558(4) 0.1214(4) 0.5085(3) 4.57(11) C(46) 0.6107(3) 0.0788(5) 0.5604(3) 4.73(11) C(47) 0.5564(4) -0.0421(5) 0.5530(3) 4.50(12) H(l) 0.096(2) -0.023(3) 0.086(2) 0.7(6) H(2) 0.178(3) -0.004(3) 0.143(2) 4.2(8) idard deviations atom atom distance Ru(l) Cl(2) 2.4298(6) Ru(l) P(2) 2.3085(7) Ru(l) N(l) 2.311(2) P(l) C(9) 1.838(3) P(2) C(21) 1.843(3) P(2) C(33) 1.836(3) N(l) C(7) 1.503(3) C(l) C(2) 1.388(4) C(2) C(3) 1.387(4) C(4) C(5) 1.378(4) C(9) C(10) 1.406(3) C(10) C(ll) 1.393(4) C(12) C(13) 1.387(4) C(15) C(16) 1.400(3) C(16) C(17) 1.388(3) C(18) C(19) 1.390(4) C(21) C(22) 1.398(3) C(22) C(23) 1.375(4) C(24) C(25) 1.396(4) C(27) C(28) 1.386(4) C(28) C(29) 1.402(3) C(30) C(31) 1.380(4) C(33) C(34) 1.393(4) C(34) C(35) 1.389(4) C(36) C(37) 1.388(4) C(39) C(40) 1.390(4) C(40) C(41) 1.367(4) C(42) C(43) 1.372(4) C(45) C(46) 1.353(5) C(46) C(47) 1.378(6) O(l) H(2) 0.81(3) 293 Appendix VIII Table VHI.6 Bond angles (°) with estimated standard deviations Atom atom atom angle atom atom atom angle Cl(l) Ru(l) Cl(2) 165.58(2) Cl(l) Ru(l) P(l) 88.02(2) Cl(l) Ru(l) P(2) 96.30(2) Cl(l) Ru(l) O(l) 85.40(6) Cl(l) Ru(l) N(l) 84.09(5) Cl(2) Ru(l) P(l) 105.32(3) Cl(2) Ru(l) P(2) 86.97(2) Cl(2) Ru(l) O(l) 80.63(6) Cl(2) Ru(l) N(l) 92.37(5) P(l) Ru(l) P(2) 99.70(3) P(l) Ru(l) O(l) 169.95(6) P(l) Ru(l) N(l) 81.46(6) P(2) Ru(l) O(l) 88.57(6) P(2) Ru(l) N(l) 178.77(6) O(l) Ru(l) N(l) 90.30(8) Ru(l) P(l) C(l) 102.15(9) Ru(l) P(l) C(9) 127.19(9) Ru(l) P(l) C(15) 118.76(9) C(l) P(l) C(9) 99.45(11) C(l) P(l) C(15) 103.65(11) C(9) P(l) C(15) 101.64(11) Ru(l) P(2) C(21) 116.73(8) Ru(l) P(2) C(27) 121.90(9) Ru(l) P(2) C(33) 112.03(8) C(21) P(2) C(27) 100.05(11) C(21) P(2) C(33) 104.02(12) C(27) P(2) C(33) 99.38(12) Ru(l) N(l) C(2) 110.19(14) Ru(l) N(l) C(7) 111.16(15) Ru(l) N(l) C(8) 110.46(15) C(2) N(l) C(7) 106.5(2) C(2) N(l) C(8) 111.4(2) C(7) N(l) C(8) 107.0(2) P(l) C(l) C(2) 117.7(2) P(l) C(l) C(6) 123.2(2) C(2) C(l) C(6) 119.1(2) N(l) C(2) C(l) 118.6(2) N(l) C(2) C(3) 121.2(2) C(l) C(2) C(3) 120.1(3) C(2) C(3) C(4) 119.8(3) C(3) C(4) C(5) 121.0(3) C(4) C(5) C(6) 119.2(3) C(l) C(6) C(5) 120.6(3) P(l) C(9) C(10) 120.8(2) P(l) C(9) C(14) 121.0(2) C(10) C(9) C(14) 118.0(2) C(9) C(10) C(ll) 120.2(3) C(10) C(ll) C(12) 120.8(3) C(l l ) C(12) C(13) 119.4(3) C(12) C(13) C(14) 120.4(3) C(9) C(14) C(13) 121.3(3) P(l) C(15) C(16) 121.4(2) P(l) C(15) C(20) 119.6(2) C(16) C(15) C(20) 118.7(2) C(15) C(16) C(17) 120.5(3) C(16) C(17) C(18) 120.3(3) C(17) C(18) C(19) 120.0(2) C(18) C(19) C(20) 119.7(3) C(15) C(20) C(19) 120.7(2) P(2) C(21) C(22) 119.1(2) P(2) C(21) C(26) 123.2(2) C(22) C(21) C(26) 117.5(2) C(21) C(22) C(23) 121.3(2) C(22) C(23) C(24) 120.6(2) C(23) C(24) C(25) 118.9(3) C(24) C(25) C(26) 120.5(2) C(21) C(26) C(25) 121.1(2) P(2) C(27) C(28) 119.5(2) P(2) C(27) C(32) 121.7(2) C(28) C(27) C(32) 118.5(2) C(27) C(28) C(29) 120.5(3) C(28) C(29) C(30) 120.8(3) C(29) C(30) C(31) 119.1(2) C(30) C(31) C(32) 120.9(3) C(27) C(32) C(31) 120.2(3) P(2) C(33) C(34) 122.3(2) P(2) C(33) C(38) 119.1(2) C(34) C(33) C(38) 118.7(3) C(33) C(34) C(35) 120.0(3) C(34) C(35) C(36) 120.5(3) C(35) C(36) C(37) 119.4(3) C(36) C(37) C(38) 119.8(3) 0(33) C(38) C(37) 121.6(3) C(40) C(39) C(44) 118.6(3) C(39) C(4C) C(41) 120.4(3) C(40) C(41) C(42) 120.4(3) C(41) C<42) C(43) 119.6(3) C(42) C(43) C(44) 120.2(3) C(39) C(44) C(43) 120.6(3) C(46) C(45) C(47)» 119.3(4) C<45) C(46) C(47) 121.3(4) C(45)' C(47) C(46) 119.4(4) Ru(l) O(l) H(l) 126.6(23) Ru(l) 0(1) H(2) 116.4(25) H(l) O(l) H(2) 97.5(28) 294 APPENDIX IX Appendix IX X-Ray Crystallographic Analysis of Cis-RuCl2(P-N)(PPh3)(r|2-H2) (36) E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula C38H37CI2NP2RU Formula Weight 741.64 Crystal Colour, Habit yellow, block Crystal Dimensions 0.30 X 0.16 X 0.07 mm Crystal System monoclinic Lattice Type ' Primitive Lattice Parameters a = 8.8084(1) A b = 17.2509(3) A c = 11.5902(2) A p = 105.709(1)° V= 1695.38(5) A3 Space Group P2i (#4) Z value 2 D d c 1.453 g/cm3 Fooo 760 Absorption coefficient 0.743 mm"1 B. Intensity Measurements Diflractometer Siemens SMART Platform CCD Wavelength 0.71073 A Temperature -100°C 9 range for data collection 1.83 to 25.01° Index ranges .\o < h < 10, -19 < k < 20, 0 < i < 13 Reflections collected 8555 Independent reflections 4935 (Ri« = 0.0167) C. Structure Solution and Refinement Structure Solution Refinement Function Minimized Weighting scheme Absorption correction Max. and min. transmission Absolute structure parameter Data/restraints/parameters Residuals (on F 2 , all data): R;Rw Residuals (on F,I>2CT(I) = 4816): R;Rw Goodness of Fit on F 2 Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map Direct methods (SHELXTL-V5.0) Full-matrix least-squares on F 2 2 > ( | F o 2 | - i F c 2 | ) 2 to = [o2(Fo2) + (AP)2 + (BP)]"1, where P = (Fo2 + 2Fc2)/3, A = 0.0350, and B = 0.0860 SADABS (Sheldrick, 1996) 1.000 and 0.837 0.01(2) 4935/1/403 0.0.217; 0.0537 0.0208; 0.0532 1.026 0.379 eVA3 -0.320 e"/A3 295 Appendix IX Table IX. 1 Atomic coordinates (x 1 0 4 ) and Ueq (defined as one third of the trance of the orthogonalized Uy tensor.) atom X — M y z U(eq) atom X y * U(eq) Ru(l) 7078(1) 6753(1) 2103(1) 17(1) C(19) 3392(3) 6918(2) 1287(3) 33(1) Cl(l) 6936(1) 5463(1) 2961(1) 28(1) C(20) 4274(4) 5770(2) S07(3) 38(1) Cl(2) 8165(1) 6164(1) 619(1) 26(1) P(2) 9381(1) 6824(1) 3636(1) 18(1) P(l) 6939(1) 7900(1) 1089(1) 18(1) C(21) 10439(3) 7746(2) 3893(2) 24(1) C(l) 8476(3) 8368(2) 520(2) 23(1) C(22) 10600(4) 8214(2) 4899(3) 32(1) C(2) 9286(4) 7938(2) -141(3) 31(1) C(23) 11453(4) 8909(2) 5011(3) 43(1) C(3) 10366(4) 8291(2) -653(3) 39(1) C(24) 12169(4) 9125(2) 4149(4) 48(1) C(4) 10645(4) 9086(2) -512(3) 33(1) C(25) 12026(4) 8664(2) 3140(3) 42(1) C(5) 9843(4) 9512(2) 142(3) 35(1) C(26) 11156(4) 7986(2) 3008(3) 31(1) C(6) 8771(4) 9162(2) 649(3) 29(1) C(27) 9008(3) 6636(2) 5106(2) 25(1) C(7) 6169(3) 8725(2) 1753(2) 21(1) C(28) 7943(4) 7098(2) 5494(3) 37(1) C(8) 7017(4) 8975(2) 2886(3) 31(1) C(29) 7669(4) 6966(2) 6612(3) 47(1) C<9) 6557(4) 9622(2) 3406(3) 34(1) C(30) 8436(5) 6369(2) 7340(3) 46(1) C(10) 5221(4) 10023(2) 2808(3) 33(1) C(31) 9465(5) 5908(2) 6954(3) 43(1) C(l l ) 4350(4) 9777(2) 1687(3) 32(1) C(32) 9759(4) 6038(2) 5846(3) 32(1) C(12) 4820(3) 9136(2) 1159(3) 26(1) C(33) 11022(3) 6160(2) 3634(2) 22(1) C(13) 5446(3) 7703(2) -316(2) 23(1) C(34) 10762(4) 5450(2) 3052(3) 27(1) C(14) 5254(3) 8170(2) -1332(2) 30(1) C(35) 12009(4) 4950(2) 3090(3) 33(1) C(15) 4129(4) 7979(2) -2398(3) 38(1) C(36) 13541(3) 5157(2) 3692(3) 31(1) C(16) 3244(4) 7315(2) -2442(3) 39(1) C(37) 13819(3) S864(2) 4266(3) 29(1) C(17) 3422(3) 6849(2) -1441(2) 33(1) C(38) 12585(3) 6364(2) 4257(2) 25(1) C(18) 4504(3) 7046(2) -363(2) 24(1) H(l*) 6189(28) 7090(13) 3026(20) 81(7) N(l) 4641(2) 6609(1) 746(2) 23(1) H(l*) = double-occupancy hydrogen atom (r| -H2) refined isotropically Table TX.2 Bond lengths (A) with estimated standard deviations Atom atom distance atom atom distance Ru(l) P(l) 2.2884(7) Ru(l) N(l) 2.306(2) Ru(l) P(2) 2.3098(6) Ru(l) Cl(2) 2.4090(6) Ru(l) Cl(l) 2.4543(7) P(l) C(7) 1.832(3) P(l) C(13) 1.827(3) C(l) C(2) 1.394(4) P(l) C(l) 1.844(3) C(2) C(3) 1.391(4) C(l) C(6) 1.395(4) C(3) C(4) 1.394(5) C(7) C(8) 1.392(4) C(4) C(5) 1.380(5) C(8) C(9) 1.381(4) C(5) C(6) 1.378(4) C(9) C(10) 1.379(4) C(7) C(12) 1.396(4) C(10) C(ll) 1.385(4) C(13) C(18) 1.397(4) C(l l ) C(12) 1.380(4) C(14) C(15) 1.398(4) C(13) C(14) 1.399(4) C(15) C(16) 1.377(5) N(l) C(20) 1.492(4) C(16) C(17) 1.386(5) P(2) C(21) 1.827(3) C(17) C(18) 1.392(4) P(2) C(27) 1.848(3) C(21) C(22) 1.394(4) C(18) N(l) 1.466(3) C(22) C(23) 1.401(5) N(l) C(19) 1.503(3) C(23) C(24) 1.370(6) P(2) C(33) 1.845(3) C(24) C(25) 1.393(6) C(21) C(26) 1.404(4) C(25) C(26) 1.383(5) C( 27) C(32) 1.388(4) C(27) C(28) 1.395(4) C(28) C(29) 1.400(4) C(33) C(34) 1.387(4) C(29) C(30) 1.386(5) C(34) C(35) 1.388(4) C(30) C(31) 1.369(5) C(35) C(36) 1.388(5) C(31) C(32) 1.396(4) C(36) C(37) 1.379(4) C<33) C(38) 1.415(4) C(37) C(38) 1.385(4) Ru(l) H(l*) 1.60(2) 2 9 6 Appendix IX Table IX. 3 Bond angles (°) with estimated standard deviations Atom atom atom angle atom atom atom angle P(l) Ru(l) N(l) 80.34(6) P(l) Ru(l) P(2) 105.27(3) N(l) Ru(l) P(2) 172.78(6) P(l) Ru(l) Cl(2) 88.52(2) N(l) Ru(l) Cl(2) 86.78(6) P(2) Ru(l) Cl(2) 97.79(2) P(l) Ru(l) Cl(l) 172.22(2) N(l) Ru(l) Cl(l) 92.20(6) P(2) Ru(l) Cl(l) 82.34(3) Cl(2) Ru(l) Cl(l) 88.86(2) P(l) Ru(l) H(l*) 93.6(8) N(l) Ru(l) H(l*) 87.8(8) P(2) Ru(l) H(l») 87.3(8) Cl(2) Ru(l) H(l») 173.8(8) Cl(l) Ru(l) H(l») 88.3(8) C(13) P(l) C(7) 105.10(13) C(13) P(l) C(l) 100.61(12) C(7) P(l) C(l) 101.61(13) C(13) P(l) Ru(l) 102.84(9) C(7) P(l) Ru(l) 115.43(8) C(l) P(l) Ru(l) 128.31(9) C(2) C(l) C(6) 118.3(3) C(2) C(l) P(l) 119.8(2) C(6) C(l) P(l) 121.7(2) C(3) C(2) C(l) 120.8(3) C(2) C(3) C(4) 120.0(3) C(5) C(4) C(3) 119.2(3) C(6) C(5) C(4) 120.8(3) C(5) C(6) C(l) 120.9(3) C(8) C(7) C(12) 118.4(3) C(8) C(7) P(l) 118.2(2) C(12) C(7) P(l) 123.4(2) C(9) C(8) C(7) 121.1(3) C(10) C(9) C(8) 119.8(3) C(9) C(10) C(ll) 119.9(3) C(12) C(U) C(10) 120.4(3) C(l l ) C(12) C(7) 120.4(3) C(18) C(13) C(14) 120.0(2) C(18) C(13) P(l) 117.6(2) C(14) C(13) P(l) 122.5(2) C(15) C(14) C(13) 120.2(3) C(16) C(15) C(14) 119.2(3) C(15) C(16) C(17) 121.1(3) C(16) C(17) C(18) 120.3(3) C(17) C(18) C(13) 119.2(3) C(17) C(18) N(l) 122.3(3) C(13) C(18) N(l) 118.4(2) C(18) N(l) C(20) 111.9(2) C(18) N(l) C(19) 106.7(2) C(20) N(l) C(19) 105.9(2) C(18) N(l) Ru(l) 112.5(2) C(20) N(l) Ru(l) 110.2(2) C(23) C(24) C(25) 120.1(3) C(21) P(2) C(33) 100.10(14) C(25) C(26) C(21) 121.0(3) C(33) P(2) C(27) 103.11(12) C(32) C(27) P(2) 121.7(2) C(33) P(2) Ru(l) 119.45(9) C(27) C(28) C(29) 120.4(3) C(22) C(21) C(26) 118.4(3) C(31) C(30) C(29) 119.4(3) C(26) C(21) P(2) 116.7(2) C(34) C<33) P(2) 121.5(2) C(24) C(23) C(22) 120.5(3) C(37) C(38) C(33) 120.1(3) C(26) C(25) C(24) 119.8(3) C(34) C(33) C(38) 118.5(3) C(32) C(27) C(28) 118.3(3) C(38) C<33) P(2) 120.0(2) C(28) C(27) P(2) 120.0(2) C(34) C(35) C(36) 120.6(3) C(30) C(29) C(28) 120.4(3) C(36) C(37) C(38) 120.7(3) C(30) C(31) C(32) 120.7(3) 297 AppendixX APPENDIX X X-Ray Crystallographic Analysis of Cis-RuCl2(P-N)(PPh3)(=C=CHPh) (45) Figure X.1 Pluto plot of the molecular structure of 45. 298 Appendix X E X P E R I M E N T A L DETAILS A. Crystal Data Empirical Formula Formula Weight Crystal Colour, Habit Crystal Dimensions Crystal System Lattice Type No. of Reflections Used for Unit Cell Determination (28 range) Omega Scan Peak Width at Half-height Lattice Parameters Space Group Z value D c * Fooo u(CuKa) C«H4iCl 2NP 2Ru 841.76 red-orange, irregular 0.20 X 0.30 X 0.40 mm monoclinic C-centred 25 (53.0 - 73.0°) 0.38° a = 10.1402(12) A b = 21.718(2) A c= 18.187(2) A p = 100.329(11)° V = 3940.3(7) A 3 Cc(#9) 4 1.419 g/cm3 1728 54.94 cm"1 B. Diffractometer Radiation Take-off Angle Detector Aperture Crystal to Detector Distance Voltage, Current Temperature Scan Type Scan Rate Scan Width 28m« No. of Reflections Measured Corrections Measurements Rigaku AFC6S CuKa (A. = 1.54178 A) graphite monochromated 6.0° 6.0 mm horizontal 6.0 mm vertical 285 mm 45kV, 25mA 21.0° £0-20 16°/min (in co) (up to 9 scans) (1.05+ 0.20 tan 8)° 155.0° Total: 4271 Unique: 4137 (R^ = 0.066) Lorentz-polarization Absorption (trans. Factors: 0.624-1.000) Structure Solution Refinement Function Minimized Least Squares Weights p-factor Anomalous Dispersion No. Observations (I>3.00o(I)) No. Variables Reflection/Parameter Ratio Residuals: R; Rw Goodness of Fit Indicator Max Shift/Error in Final Cycle Maximum peak in Final Diff. Map Minimum peak in Final Diff. Map C. Structure Solution and Refinement Patterson Methods (DIRDIF92 PATTY) Full-matrix least-squares 2>(|Fo| - I Fc | )2 co = 1 0.0000 All non-hydrogen atoms 3677 467 7.87 0.043; 0.048 1.04 0.0001 0.90 e"/A3 -0.84 e"/A3 299 Appendix X Table ELI Atomic coordinates and B eq a t o m X y z a t o m X y z B eq Ru(l) 0.49780 0.50642(2) 0.49750 3.056(10) C(21) 0.2864(12) 0.3342(6) 0.2766(6) 6.4(3) Cl(l) 0.4707(3) 0.61174(10) 0.53810(14) 4.50(5) C(22) 0.3252(10) 0.3476(5) 0.3518(6) 5.1(3) Cl(2) 0.6498(3) 0.48129(12) 0.61744(14) 4.76(6) C(23) 0.6327(9) 0.3469(4) 0.5066(5) 3.7(2) P(l) 0.4989(2) 0.40084(10) 0.47436(12) 3.27(4) C(24) 0.6974(10) 0.3114(5) 0.4600(6) 4.4(2) P(2) 0.6725(2) 0.54955(10) 0.44573(14) 3.43(5) C(25) 0.7934(11) 0.2690(5) 0.4863(8) 5.6(3) N(l) 0.3178(7) 0.4800(3) 0.5528(5) 4.0(2) C(26) 0.8309(10) 0.2604(5) 0.5621(9) 5.8(3) C(l) 0.3860(8) 0.5142(4) 0.4082(5) 3.4(2) C(27) 0.7670(11) 0.2925(5) 0.6107(7) 5.5(3) C(2) 0.3014(10) 0.5163(4) 0.3434(5) 4.3(2) C(28) 0.6716(11) 0.3356(5) 0.5842(6) 4.8(2) C(3) 0.2039(8) 0.5651(5) 0.3218(5) 4.2(2) C(29) 0.6120(9) 0.6090(4) 0.3760(5) 3:9(2) C(4) 0.2167(11) 0.6229(5) 0.3542(7) 5.8(3) C(30) 0.5427(11) 0.5936(5) 0.3037(6) 4.8(2) C(5) 0.122(2) 0.6674(7) 0.3332(8) 8.4(4) C(31) 0.493(2) 0.6391(6) 0.2551(8) 5.7(3) C(6) 0.0132(15) 0.6558(8) 0.2778(8) 7.9(4) C(32) 0.4999(15) 0.6985(6) 0.2747(7) 7.0(4) C(7) -0.0005(14) 0.6011(7) 0.2443(8) 6.6(3) C(33) 0.5651(13) 0.7150(5) 0.3477(7) 6.1(3) C(8) 0.0954(9) 0.5547(6) 0.2644(6) 5.1(2) C(34) 0.6162(10) 0.6700(4) 0.3960(6) 4.6(2) C(9) 0.3707(8) 0.3718(4) 0.5228(5) 3.7(2) C(35) 0.7749(8) 0.4969(4) 0.4023(6) 4.1(2) C(10) 0.2925(8) 0.4128(4) 0.5536(5) 3.7(2) C(36) 0.8417(10) 0.4519(5) 0.4474(6) 4.6(2) C(l l) 0.1919(10) 0.3901(5) 0.5902(6) 5.2(3) C(37) 0.9252(10) 0.4089(5) 0.4212(8) 5.8(3) C(12) 0.1702(11) 0.3289(5) 0.5953(6) 5.4(3) C(38) 0.9334(11) 0.4091(6) 0.3460(8) 6.2(3) C(13) 0.2464(11) 0.2874(5) 0.5636(7) 5.3(3) C(39) 0.8676(12) 0.4534(6) 0.3001(7) 6.1(3) C(14) 0.3481(10) 0.3093(5) 0.5273(6) 4.3(2) C(40) 0.7885(10) 0.4984(5) 0.3270(6) 5.2(2) C(15) 0.3390(12) 0.5037(5) 0.6302(6) 5.7(3) C(41) 0.8057(9) 0.5927(4) 0.5065(6) 4.2(2) C(16) 0.1952(10) 0.5107(5) 0.5118(7) 5.6(3) C(42) 0.8048(10) 0.6060(5) 0.5812(6) 4.8(2) C(17) 0.4427(9) 0.3778(4) 0.3766(5) 3.6(2) C(43) 0.9096(13) 0.6399(5) 0.6215(7) 6.2(3) C(18) 0.5226(9) 0.3942(5) 0.3254(5) 4.4(2) C(44) 1.0134(11) 0.6608(5) 0.5906(8) 6.1(3) C(19) 0.4869(14) 0.3802(5) 0.2495(8) 4.9(2) C(45) 1.0140(11) 0.6479(5) 0.5153(8) 5.7(3) C(20) 0.3648(12) 0.3499(5) 0.2266(6) 5.3(3) C(46) 0.9135(9) 0.6137(5) 0.4757(6) 4.9(2) Table X.2 Bond lengths (A) with estimated standard deviations a t o m a t o m d i s t a n c e a t o m a t o m d i s t a n c e Ru(l) Cl(l) 2.434(2) Ru(l) Cl(2) 2.495(2) Ru(l) P(l) 2.332(2) Ru(l) P(2) 2.346(2) Ru(l) N(l) 2.308(7) Ru(l) C(l) 1.814(8) P(l) C(9) 1.809(9) P(l) C(17) 1.837(9) P(l) C(23) 1.808(9) P(2) C(29) 1.836(9) P(2) C(35) 1.818(9) P(2) C(41) 1.841(9) N(l) C(10) 1.480(11) N(l) C(15) 1.478(12) N(l) C(16) 1.488(13) C(l) C(2) 1.329(12) C(2) C(3) 1.455(13) C(3) C(4) 1.382(15) C(3) C(8) 1.393(12) C(4) C(5) 1.37(2) C(5) C(6) 1.38(2) C(6) C(7) 1.33(2) C(7) C(8) 1.40(2) C(9) C(10) 1.377(12) C(9) C(14) 1.383(13) C(10) C(l l ) 1.404(13) C(l l ) C(12) 1.352(15) C(12) C(13) 1.380(15) C(13) C(14) 1.404(13) C(17) C(18) 1.387(12) C(17) C(22) 1.364(12) C(18) C(19) 1.40(2) C(19) C(20) 1.40(2) C(20) C(21) 1.354(15) C(21) C(22) 1.384(14) C(23) C(24) 1.393(13) C(23) C(28) 1.418(13) C(24) C(25) 1.363(14) C(25) C(26) 1.37(2) C(26) C(27) 1.38(2) C(27) C(28) 1.370(14) C(29) C(30) 1.415(13) C(29) C(34) 1.373(13) C(30) C(31) 1.361(15) C(31) C(32) 1.34(2) C(32) C(33) 1.42(2) C(33) C(34) 1.353(14) C(35) C(36) 1.373(13) C(35) C(40) 1.401(13) C(36) C(37) 1.401(14) C(37) C(38) 1.39(2) C(38) C(39) 1.37(2) C(39) C(40) 1.408(14) C(41) C(42) 1.390(14) C(41) C(46) 1.391(13) C(42) C(43) 1.389(14) C(43) C(44) 1.36(2) C(44) C(45) 1.40(2) C(45) C(46) 1.360(13) 300 Appendix X Table IV.3 Bond angles (°) with estimated standard deviations atom atom atom angle atom atom atom angle Cl(l) - Ru(i) Cl(2) 91.50(9) Cl(l) Ru(l) P(l) 169.56(8) Cl(l) Ru(l) P(2) 83.15(8) Cl(l) Ru(l) N(l) 87.8(2) Cl(l) Ru(l) C(l) 95.6(3) Cl(2) Ru(l) P(l) 85.45(8) Cl(2) Ru(l) P(2) 92.61(9) Cl(2) Ru(l) N(l) 88.7(2) Cl(2) Ru(l) C(l) 172.7(3) P(l) Ru(l) P(2) 106.94(8) P(l) Ru(l) N(l) 82.2(2) P(l) Ru(l) C(l) 87.3(3) P(2) Ru(l) N(l) 170.9(2) P(2) Ru(l) C(l) 89.9(3) N(l) Ru(l) C(l) 89.9(3) Ru(l) P(l) C(9) 103.1(3) Ru(l) P(l) C(17) 115.6(3) Ru(l) P(l) C(23) 127.3(3) C(9) P(l) C(17) 104.5(4) C(9) P(l) C(23) 100.3(4) C<17) P(l) C(23) 102.8(4) Ru(l) P(2) C(29) 112.0(3) Ru(l) P(2) C<35) 117.0(3) Ru(l) P(2) C(41) 119.2(3) C(29) P(2) C(35) 106.8(4) C(29) P(2) C(41) 100.1(4) C(35) P(2) C(41) 99.6(4) Ru(l) N(l) C(10) 113.6(5) Ru(l) N(l) C(15) 109.7(6) Ru(l) N(l) C(16) 109.0(6) C(10) N(l) C(15) 109.3(8) C(10) N(l) C(16) 108.4(7) C(15) N(l) C(16) 106.6(8) Ru(l) C(l) C(2) 176.4(8) C(l) C(2) C(3) 124.3(9) C(2) C(3) C(4) 122.6(9) C(2) C(3) C(8) 119.4(10) C(4) C(3) C(8) 117.9(9) C(3) C(4) C(5) 120.9(11) C(4) C(5) C(6) 120.3(14) C(5) C(6) C(7) 120.2(13) C(6) C(7) C(8) 120.8(13) C(3) C(8) C(7) 119.7(11) P(l) C(9) C(10) 119.3(7) P(l) C(9) C(14) 120.8(7) C(10) C(9) C(14) 119.9(8) N(l) C(10) C(9) 121.3(8) N(l) C(10) C(l l ) 119.5(8) C(9) C(10) C(ll) 119.1(9) C(10) C(ll) C(12) 121.3(10) C(ll) C(12) C(13) 120.3(9) C(12) C(13) C(14) 119.2(9) C(9) C(14) C(13) 120.3(9) P(l) C(17) C(18) 117.6(7) P(l) C(17) C(22) 123.6(7) C(18) C(17) C(22) 118.8(9) C(17) C(18) C(19) 121.9(9) C(18) C(19) C(20) 117.1(11) C(19) C(20) C(21) 120.9(10) C(20) C(21) C(22) 120.9(10) C(17) C(22) C(21) 120.3(9) P(l) C(23) C(24) 124.7(8) P(l) C(23) C(28) 119.6(7) C(24) C(23) C(28) 115.6(9) C(23) C(24) C(25) 123.1(11) C(24) C(25) C(26) 119.7(11) C(25) C(26) C(27) 119.9(10) C(26) C(27) C(28) 120.3(11) C(23) C(28) C(27) 121.4(10) P(2) C(29) C(30) 121.6(7) P(2) C(29) C(34) 120.3(7) C(30) C(29) C(34) 117.4(9) C(29) C(30) C(31) 119.7(10) C(30) C(31) C(32) 122.2(13) C(31) C(32) C(33) 119.1(11) C(32) C(33) C(34) 119.1(10) C(29) C(34) C(33) 122.3(10) P(2) C(35) C(36) 116.5(8) P(2) C(35) C(40) 125.0(8) C(36) C(35) C(40) 118.5(9) C(35) C(36) C(37) 122.3(10) C(36) C(37) C(38) 118.7(10) C<37) C(38) C(39) 119.8(10) C(38) C(39) C(40) 121.5(11) C(35) C(40) C(39) 119.1(11) P(2) C(41) C(42) 124.1(7) P(2) C(41) C(46) 118.0(8) C(42) C(41) C(46) 117.9(9) C(41) C(42) C(43) 119.2(10) C(42) C(43) C(44) 122.4(12) C(43) C(44) C(45) 118.6(10) C(44) C(45) C(46) 119.6(11) C(41) C(46) C(45) 122.3(11) 301 APPENDIX XI Appendix XI Thermodynamic Calculations and Data for the Reversible Formation of Cis-RuX2(P-N)(PR3)(L) (X = CI, Br; R = Ph,/Molyl; L = H2S, MeSH, EtSH) For the equilibrium: RuX2(P-N)(PPh3) + L A L K c/5-RuCl2(P-N)(PPh3)(L) B K [B] [A][L] (1) (2) A complete calculation of equilbrium concentrations for the cw-RuCl2(P-N)(PPh3)(SH2) 18a system is given in Section XI. 1; sets of raw data for corresponding systems involving 18b, 19a, 20, and 21 are given similarly in Sections XI.2-XI.5. XL1 Calculations for the Cis-RuCl2(P-N)(PPh3)(SH2) (18a) Equilibrium System in C 6D 6 Table XI.1.1 Integrations Used for Equilibrium Calculations (see Figure 4.30) Value of Integation Signal(s), ppm Reasonance(s) Number of Protons a 3.67 NMe of 18a 3 3.06, 2.97 NMe of 6a, NMe of 18a 6,3 e 1.02 Ru(S#2)ofl8a 2 (0 0.30 free H2S (in solution) 2 The calculation of equilibrium concentrations at any temperature is as follows: [Ru]totai is calculated from the amount of 18a dissolved in a known volume of solvent; this volume of solvent in the NMR tube is measured with a ruler (cm) and converted to (mL) using the calibration plot shown in Figure XI. 1. 302 Appendix XI 12.0 Volume (mL) Figure XI. 1 Calibration plot for measured height (cm) of solvent vs. volume (mL) in 5 mm NMR tubes (type 507-PP from Wilmad Glass Co., Inc.). [18a] _ a/3 ^ s/2 X " [6a] "(p - a ) / 6~(P - a ) / 6 [6a][H2S]s NOte: [H2S] 8 (Solution) = [H2S]uncoordinated " [H2S]headspace (3) [6a] _(P-a)/6 ( 4 ) [BbS ]s © / 2 [6.] = S ^ (5) 1 + x [18a] = [Ru]toul-[6a] (6) [H2S]s = ^  (7) K= [ 1 8 a ] (8) 303 Appendix XI T(°C) a 3 6 CO X y 13.5 5.62 13.85 3.60 1.12 1.37 2.45 18.5A 3.35 10.18 2.05 0.92 0.98 2.47 19.0B 4.36 12.03 2.80 1.00 1.14 2.56 19.2 5.33 14.62 3.45 1.40 1.15 2.21 19.2° 2.91 8.12 1.70 0.78 1.12 2.23 21.5 4.72 16.09 3.32 1.80 0.83 2.11 35.4 1.91 7.29 1.40 1.20 0.71 1.49 50.3 0.90 4.90 0.62 1.00 0.45 1.33 preparation. T(°C) 1/T(K) [6al(M) n8al (M) rH2S]8(M) KOVT1) InK 13.5 0.003489 0.0098 0.0133 0.0040 343 5.84 18.5A 0.003429 0.0117 0.0114 0.0047 208 5.34 19.0B 0.003423 0.0108 0.0123 0.0042 269 5.59 19.2 0.003421 0.0108 0.0123 0.0049 236 5.46 19.2C 0.003421 0.0109 0.0122 0.0049 228 5.43 21.5 0.003394 0.0126 0.0105 0.0060 139 4.93 35.4 0.003241 0.0135 0.0096 0.0090 79 4.36 50.3 0.003092 0.0159 0.0072 0.0119 38 3.63 preparation. XI.2 Calculations for the as-RuBr2(P-N)(PPh3)(SH2) (18b) Equilibrium System in CeDe (under 1 atm H2S) Table XI.2.1 Integrations Used for Equilibrium Calculations Value of Integation Signal(s), ppm Reasonance(s) Number of Protons a 3.93 NMe of 18b 3 P 3.17, 2.87 NMe of 6b, NMe of 18b 6,3 8 1.14 Ru(S#2)ofl8b 2 CO 0.30 free H2S (in solution) 2 . 304 Appendix XI Table XI.2.2 Integration Values and Equilibrium Concentration Ratios (a, ft, s and co) T(°C) a 3 s co X y 20.6 9.12 16.78 5.84 17.01 2.38 0.15 22.5 9.10 15.49 5.10 19.03 2.85 0.11 35.5 8.53 19.85 5.33 24.03 1.51 0.16 45.0 6.85 19.51 4.25 20.10 1.08 0.21 60.2 4.63 17.00 2.84 21.22 0.75 0.19 Table XI.2.: i Equilibrium Concentrations and K ([Ru]totai = 0.0203 M; under 1 atm H2S) T(°C) 1/T(K) T6bl(M) [18bl (M) [H2S]S (M) KOO InK 20.6 0.003404 0.0060 0.0143 0.0400 60 4.09 22.5 0.003382 0.0053 0.0150 0.0471 60 4.10 35.5 0.003240 0.0081 0.0122 0.0516 29 3.38 45.0 0.003143 0.0097 0.0106 0.0464 23 3.15 60.2 0.003000 0.0116 0.0087 0.0597 13 2.53 XI.3 Calculations for the Os-RuCl2(P-N)(P(p-tolyl)3)(SH2) (19a) Equilibrium System in C 6D 6 Table XI.3.1 Integrations Used for Equilibrium Calculations Value of Integation Signal(s), ppm Reasonance(s) Number of Protons a 3.76 NMe of 19a 3 P 3.10, 2.92 NMe of 7a, NMe of 19a 6,3 E 1.15 Ru(SJr72)ofl9a 2 CO 0.30 free 772S (in solution) 2 Table XI.3.2 Integration Values and Equilibrium Concentration Ratios (a, ft, s and co) T(°C) a 3 8 CO x y 19.0 1.94 9.14 1.31 1.20 0.54 2.00 19.3 1.00 5.10 0.55 0.52 0.49 2.63 22.4 0.79 6.43 0.45 0.7 0.28 2.69 35.4 1.37 10.62 1.00 1.45 0.30 2.13 43.4 0.30 7.13 0.25 0.85 0.09 2.68 50.5 0.24 7.60 0.20 0.91 0.07 2.70 305 Appendix XI Table XI.3.3 Equilibrium Concentrations and K ([Ru]^ = 0.00808 M) T(°C) 1/T(K) RalCM) ri9al (M) [H2S]8(M) K (M"1) InK 19.0 0.003423 0.0053 0.0028 0.0026 205 5.32 19.3 0.003419 0.0054 0.0026 0.0021 236 5.46 22.4 0.003384 0.0063 0.0018 0.0024 119 4.78 35.4 0.003241 0.0062 0.0018 0.0029 101 4.62 43.4 0.003159 0.0074 0.0007 0.0028 32 3.46 50.5 0.003090 0.0076 0.0005 0.0028 23 3.14 XI.4 Calculations for the Cis-RuCl2(P-N)(PPh3)(MeSH) (20) Equilibrium System in C 6D 6 Table XI.4.1 Integrations Used for Equilibrium Calculations Value of Integation Signal(s), ppm Reasonance(s) Number of Protons a 3.63 NMe of 20 3 P 3.04 (br) NMe of 6a, NMe of 20 6,3 8 0.78 Ru(C#3SH) of 20 3 CO 1.59 free C#3SH (in solution) 3 Table XI.4.2 Integration Values and Equilibrium Concentration Ratios (a, P