Open Collections

UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

Early transition metal complexes supported by amidophosphine and amidocarbene ligands Spencer, Liam Patrick 2006

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
831-ubc_2006-200971.pdf [ 12.23MB ]
Metadata
JSON: 831-1.0061126.json
JSON-LD: 831-1.0061126-ld.json
RDF/XML (Pretty): 831-1.0061126-rdf.xml
RDF/JSON: 831-1.0061126-rdf.json
Turtle: 831-1.0061126-turtle.txt
N-Triples: 831-1.0061126-rdf-ntriples.txt
Original Record: 831-1.0061126-source.json
Full Text
831-1.0061126-fulltext.txt
Citation
831-1.0061126.ris

Full Text

EARLY TRANSITION METAL COMPLEXES SUPPORTED BY AMIDOPHOSPHINE AND AMIDOCARBENE LIGANDS  by  L I A M P A T R I C K SPENCER  B.Sc. (Hons.), The University of Victoria, 2000 M.Sc. The University of Windsor, 2002 A THESIS SUBMITTED IN P A R T I A L F U L F I L L M E N T OF T H E REQUIREMENTS FOR THE D E G R E E OF  DOCTOR OF PHILOSOPHY in T H E F A C U L T Y OF G R A D U A T E STUDIES  (CHEMISTRY)  T H E UNIVERSITY OF BRITISH C O L U M B I A  September 2006  © Liam Patrick Spencer,2006  ABSTRACT 1  0  The reactivity of the tantalum dinitrogen complex ([NPN]Ta)2(u-H)2(u-n :n -N2) (where [NPN] = [(PhNSiMe CH2)2PPh] ") with several zirconium hydride reagents is 2  2  explored. The addition of [Cp2Zr(Cl)H] leads to the unanticipated reduction of the N - N x  bond without Zr-H addition.  The coordinated N2 ligand is cleaved to form a triply  bridging nitride and a phosphinimide functional group that bridges between Ta and Zr centres. A series of experiments to determine the mechanism of this reaction reveals that a " C p 2 Z r " species promotes reduction of the N - N unit. This type of dinitrogen reduction is extended to include the insertion of a " C p 2 T i " fragment into the N - N bond. The synthesis of early transition metal complexes employing a tridentate diamido N-heterocyclic carbene (NHC) ligand set (denoted  [NCN]) is also investigated.  Aminolysis reactions with diamino-NHC precursors and  M(NMe2)4  ( M = T i , Zr, Hf)  provide bis(amido)-NHC-metal complexes that can be further converted to chloro and alkyl derivatives. Zr(CH2R)4  Alkyl elimination reactions with the diamino-NHC ligands and  (R=Ph, SiMe ) yield dialkyl-NHC-zirconium complexes. The central position 3  of the N H C donor in this tridentate architecture renders the carbene stable to dissociation from the metal centre in strongly coordinating solvents. The hafnium dialkyl complexes are thermally stable with the exception of the dialkyl complex, (where  Mes  Mes  [NCN]Hf(CH CH ) , 2  3  2  [ N C N ] = (2,4,6-Me -C6H2NHCH2CH2)2N2C H2) which undergoes (3-hydrogen 3  3  transfer and subsequent C - H bond activation with an ortho-methyl substituent on the mesityl group. Activation of {  Mes  Mes  [NCN]M(CH ) 3  [NCN]MCH }{B(C F5)4}  catalyst.  3  6  3  2  ( M = Zr, Hf) with [Ph C][B(C F ) ] yields 3  6  5  4  which is a moderately active ethylene polymerization  The hafnium dialkyl complexes also insert carbon monoxide, substituted  isocyanides, and substituted cumulenes into a hafnium-sp -carbon bond to yield expected 3  insertion products.  In some circumstances, further C-C bond coupling occurs to yield  enediolate and eneamidolate metallacycles. Attempts to reduce presence of dinitrogen lead to mixtures of products.  Mes  [ N C N ] Z r C l 2 in the  In one case, an ether cleavage  product is isolated, which is a result of C - 0 bond activation of the solvent used in the reaction.  ii  Aminolysis and alkyl elimination reactions with the diamino-NHC ligand and tantalum(V) reagents provide complexes with an amide-amine donor configuration. Attempts to promote coordination of the remaining pendant amine donor have been unsuccessful. Metathesis reactions with the lithiated diamido-NHC ligand (Li2 [NCN]) Ar  and Cl Ta(NR.2)5- derivatives provide a successful method to coordinate both amide x  x  donors, yielding the desired [NCN]TaCl (NR2)3- complexes. Ar  x  x  Attempts to prepare  trialkyl tantalum complexes by this methodology resulted in the formation of a metallaaziridine derivative. D F T calculations on model complexes suggest the lowest energy pathway involves a tantalum alkylidene intermediate, which undergoes amido CH bond activation to form the metallaaziridine moiety. This mechanism was confirmed by examining the distribution of deuterium atoms in an experiment between  Mes  [NCN]Li2  and Cl Ta(CD Ph) . 2  2  3  The preparation of chiral [NCN] group 4 complexes is achieved by aminolysis and alkyl elimination reactions with a chiral diamino-NHC ligand and suitable group 4 reagents.  The titanium and zirconium derivatives are investigated in the asymmetric  intramolecular hydroamination of an aminoalkene in an attempt to promote selectivity in the N-heterocycle synthesized. While the titanium [NCN] complex shows no activity, the zirconium [NCN] complex is an efficient catalyst for the intramolecular formation of a substituted pyrollidine. Examination of the steroselectivity in the N-heterocyclic product formed reveals very low enantioselective excess.  iii  T A B L E OF CONTENTS  ABSTRACT  ii  T A B L E OF CONTENTS  iv  LIST OF T A B L E S  viii  LIST OF FIGURES  xii  G L O S S A R Y OF T E R M S  xviii  ACKNOWLEDGEMENTS  xxiii  DEDICATION  xxiv  S T A T E M E N T OF AUTHORSHIP  Chapter One  xxv  Dinitrogen Chemistry and Ligand Design  1.1.  Origins of Coordination and Organometallic Chemistry  1  1.2.  Reactivity of Dinitrogen  3  1.3.  Coordinated Dinitrogen Complexes  5  1.4.  Dinitrogen Cleavage  7  1.5.  Amidophosphine Ligands for N 2 Activation  10  1.6.  Introduction to Carbenes  14  1.7.  Isolation of Stable Carbenes  1.8.  1.7.1. Acyclic Carbenes  16  1.7.2. N-Heterocyclic Carbenes  19  Transition Metal Complexes With Carbene Ligands 1.8.1. Transition Metal Acyclic Carbene Complexes..  21  1.8.2. Transition Metal N H C Complexes  23  1.9.  Late Transition Metal N H C Complexes in Homogeneous Catalysis  1.10.  Scope of This Thesis  25  1.11.  References  27  Chapter Two  \ 24  Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.1.  Introduction  34  2.2.  Attempted Hydrozirconation of 2.5  38  iv  2.3.  Reduction and Functionalization of 2.5 with Cp2Ti(II)  43  2.4.  Conclusions  44  2.5.  Experimental  45  2.6.  2.5.1. General Considerations  45  2.5.2. Materials and Reagents  45  2.5.3. Synthesis and Characterization of 2.10 and 2.13  46  References  ,  Chapter Three  49  Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Carbene  Complexes 3.1.  Introduction  3.2.  Synthesis of [ N C N ] H  3.3.  Attempted Syntheses of an [ N C N ] Ligand with an Aryl Backbone  59  3.4.  Synthesis of Group 4 [NCN] Aamido, Chloride, and Alkyl Complexes  62  3.5.  Conclusions  75  3.6.  Experimental  77  3.7.  51 Ar  2  and Lithium Derivatives Ar  54  3.6.1. General Considerations  77  3.6.2. Materials and Reagents  77  3.6.3. Synthesis and Characterization of Complexes 3.1 - 3.40  77  References  Chapter Four  94  Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Carbene  Complexes 4.1.  Introduction  97  4.2.  H f and Zr Cation Formation and Polymerization Studies  98  4.3.  Formation of [NCN] Hafnium n -Iminoacyls and an Eneamidolate 2  Metallacycle  100  4.4.  Formation of a Hafnium Vinyl-enolate and Enediolate Metallacycle  108  4.5.  Formation of Amidate and Amidinate Metallacycles  115  4.6.  Attempted Synthesis of Group 4 [NCN] Dinitrogen Complexes  120  4.7.  Synthesis of Hydrazido(l-) Hafnium [NCN] Complexes  125  v  4.8.  Conclusions  130  4.9.  Experimental  132  4.9.1. General Considerations  132  4.9.2. Materials and Reagents  132  4.9.3. Synthesis and Characterization of Complexes 4.4 - 4.18, 132  4.24 -4.26  4.10. References  Chapter Five  143  Synthesis and DFT Studies of Tantalum [NCN] Transition Metal Complexes  5.1.  Introduction  148  5.2.  Synthesis of Amine-Amide [NCNH] Tantalum Derivatives  150  5.3.  Successful Synthesis of Ta[NCN] Amide Complexes  154  5.4.  Isolation of Cyclometallated [NCCNJTa Dialkyl Derivatives  157  5.5.  Mechanistic Insight Into the Formation of 5.7-5.9  160  5.6.  Determination of Mechanism by DFT Calculations  161  5.7.  Verification of the Mechanism Proposed by DFT Calculations  165  5.8.  Conclusions  168  5.9.  Experimental  170  5.9.1. General Considerations 5.9.2. Materials and Reagents 5.9.3. Synthesis and Characterization of Complexes 5.1 - 5.10 5.10.  Reference s  Chapter Six  170 170 170 177  Thesis Extensions: Chiral Group 4 [NCN] Complexes  6.1.  Introduction  180  6.2.  Synthesis of Group 4 [NCN] Complexes  184  6.3.  Asymmetric Intramolecular Hydroamination Studies  191  6.4.  Conclusions and Future Work  193  6.5.  Experimental  197  6.5.1. General Considerations  vi  197  6.5.2. Materials and Reagents 6.5.3.  Synthesis and Characterization of Complexes 6.8 - 6.13, 6.14-6.15  6.7.  197  197  References  203  Chapter Seven  Thesis Summary and Future Work  Appendix A  X-ray Crystal Structure Data  206  A.l.  General Considerations  208  A.2.  References  210  A. 3.  Tables of Crystallographic Data  211  Appendix B  Evaluating the Formation of a Tantalum Metallaaziridine Complex by DFT Calculations  B. l.  Evaluation of a o-Bond Metathesis Mechanism  B.2.  Investigation of an Alkylidene Intermediate Followed by C - H Bond Activation  B.3.  219  221  Thermodynamic Considerations for the Formation of Metallated Ta [NCCN] Derivatives  224  B.4.  General Considerations  232  B.5.  References  233  vii  LIST OF TABLES Chapter Two  Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  Table  Title  Pase  Table 2.1.  Selected bond distances ( A ) and angles (deg) for ([NP(N)N]Ta(pH) (p-N)(Ta[NPN])(ZrCp ) (2.10) 2  Chapter Three  41  2  Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Carbene  Complexes Table Table 3.1.  Title  Pase  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  [ N C N ] H - C l (3.5) and 2  Table 3.2.  2  [NCN]Zr(NEt ) , (3.17) 2  64  2  [ N C N H ] T i ( N M e ) , (3.22) 2  3  [NCN]ZrCl (py), (3.30)  68  2  Selected Bond Distances ( A ) and Bond Angles (°) for tol  [NCN]Zr(CH SiMe ) , (3.31) 2  Table 3.6.  66  Selected Bond Distances ( A ) and Bond Angles (°) for tol  Table 3.5.  57  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  Table 3.4.  [ N C N ] H , (3.8)  Selected Bond Distances ( A ) and Bond Angles (°) for tol  Table 3.3.  Mes  3  2  71  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  [ N C N ] H f B u , (3.38)  73  2  Chapter Four  Synthesis of Group 4 Bis(amidq)-N-Heterocyclic  Carbene  Complexes Table  Title  Table 4.1.  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  Table 4.2.  Pase  [NCN]Hf(ri -XyNCCH3)(CH3), (4.7) 2  Selected Bond Distances ( A ) and Bond Angles (°) for  vm  103  [ N C N ] H f ( r ) - X y N C C H ) , (4.8)  Mes  3  Table 4.3.  2  Selected Bond Distances ( A ) and Bond Angles (°) for [NCN]Hf(OC(CH )=C(CH )NXy) (4.11)  Mes  3  Table 4.4.  105  2  3  ;  Selected Bond Distances ( A ) and Bond Angles (°) for ( [NCN]Hf)20-OC( Bu)=C( Bu)O)2, Mes  Table 4.5.  [NCN]Hf(Me)(n - BuNC(Me)0), (4.17) 3  t  [NCN]Hf(Me)(n - PrNC(Me)N Pr), (4.18)  112  117  3  i  i  119  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  [ N C N ] Z r ( C l ) ( O C H C H C H C H 3 ) , (4.24) 2  Table 4.8.  (4.16)  i  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  Table 4.7.  i  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  Table 4.6.  108  2  2  124  Selected Bond Distances ( A ) and Bond Angles (°) for Mes  [NCN]Hf(Me)(n -NHNMe ), (4.25). 2  2  Chapter Five  129  Synthesis and DFT Studies of Tantalum [NCN] Transition Metal Complexes  Table  Title  Table 5.1.  Selected bond distances ( A ) and angles (°) for tol  Pase  [NCNH]Ta(NMe ) , 5.1 2  Table 5.2.  152  4  Selected bond distances ( A ) and angles (°) for Mes  [NCNH]Ta(CHPh)(CH Ph) (5.2) 2  Table 5.3.  Selected bond distances ( A ) and angles (°) for tol  [NCN]Ta(NMe ) (5.3) 2  Table 5.4.  154  2  '.  3  Selected bond distances ( A ) and angles (°) for ^ [ N C C N J T a ^ H z ^ u ^ (5.7)  Table 5.5.  156  159  Selected bond distances ( A ) and angles (°) for Mes  [NCCN]Ta(Cl)(CH Bu) (5.10) t  2  ix  167  Chapter Six  Thesis Summary and Extensions: Chiral Group 4 [NCN] Complexes  Table  Title  Pase  Table 6.1.  Selected Bond  Distances (A) and Bond Angles (°) for (-)-  (li?,2'5,47?)-2-(l,7,7-trimethylbicyclo[2.2.1]hept-2-ylamino)ethyl ammonium chloride, (6.8)  186  X-ray Crystal Structure Data  Appendix A Table  Title  Pase  Table A.l.  Crystallographic and structure refinement for [NP(N)N]Ta(p-H) (p2  N)(Ta[NPN])(ZrCp )  (2.10),  2  Mes  Mes  (NCHN)H -Cl  (3.5),  2  and  ( N C N ) H (3.8)  211  2  Table A.2.  Crystallographic and structure refinement for '[NCN]Zr(NEt ) t0  2  2  (3.17), [ N C N H ] T i ( N M e ) (3.22), and [NCN]ZrCl (py) (3.30).. 212 Mes  tol  2  Table A.3.  Crystallographic tol  2  and  [NCN]Zr(CH SiMe ) 2  Mes  3  3  structure  (3.30),  2  [NCN]HfBu  2  for  (3.38), and  [ N C N ] H f ( r i - X y N C C H X C H ) (4.7)  213  2  3  Table A.4.  Mes  refinement  3  Crystallographic and structure refinement for  Mes  [NCN]Hf(ri 2  X y N C C H ) (4.8), [NCN]Hf(OC(CH )=C(CH )NXy) (4.11), and Mes  3  2  3  3  ^ [ N C ^ H f l ^ - O C C B ^ ^ C B ^ O ^ (4.16)  Table A.5.  Crystallographic and structure refinement for t  BuNC(Me)0) (4.17),  Mes  214 Mes  [NCN]Hf(Me)(r) 3  [NCN]Hf(Me)(n - PrNC(Me)N Pr) (4.18), 3  i  i  and [NCN]Zr(Cl)(OBu) (4.22)  215  Mes  Table A.6.  Crystallographic and structure refinement for Mes  [NCN]Hf(Me)(n -NNMe )  (4.23),  2  2  and  Table A.7.  Mes  tol  [NCNH]Ta(NMe ) 2  4  (5.1),  [NCNH]Ta(CHPh)(CH Ph) (5.2) 2  216  2  Crystallographic and structure refinement for [NCN]Ta(NMe ) tol  2  3  (5.3), [ N C C N ] T a ( C H B u ) (5.7), and Mes  t  2  2  ^ [ N C C N J T a ^ l X C H / B u ) (5.10)  217  Table A.8.  Crystallographic and structure refinement for (-)-(17?,2'5',4i?)-2(l,7,7-trimethylbicyclo[2.2.1]hept-2-ylamino)ethyl  ammonium  chloride (6.8)  Appendix B  218  Evaluating the Formation of a Tantalum Metallaaziridine Complex by DFT Calculations  Table  Title  .  Table B.l.  Gas-phase relative energies (kcal/mol) of the intermediates and transition states in a a-bond metathesis mechanism  Table B.2.  ,  ^  Pa  221  Gas-phase relative energies (kcal/mol) of the intermediates and transition states in a mechanism involving a-H abstraction followed by alkylidene mediated C-H bond activation  Table B.3.  N B O Occupancies of bonding and anti-bonding orbitals in the trimethyl complex A and the metallaaziridine complex D  Table B.4.  223  227  Important second order perturbation theory analysis N B O donoracceptor interactions AEy (kcal/mol) that contribute to shorter Tacarbene and Ta-Me bonds in the metallaaziridine product D relative to the trimethyl complex A  228  xi  e  L I S T O F F I G U R E S  Chapter One Figure Figure  Dinitrogen Chemistry and Ligand Design Title  1.1.  Page  Interpretation of the coordination sphere of  C0CI2  • 6 N H by (a) 3  Blomstrand/Jorgensen and (b) Werner  2  Figure  1.2.  Catalytic formation of N-containing compounds from N  Figure  1.3.  The first reported transition metal dinitrogen complex (X" = Br",  4  2  T, BF 4 ", PF 6 ")  5  Figure  1.4.  Examples of zirconocene-based dinitrogen complexes  6  Figure  1.5.  Successful catalyst for the synthesis of NH3 from N  10  Figure  1.6.  Design of a diamido-N-heterocyclic carbene [NCN] ligand  14  Figure  1.7.  Possible electronic configurations of carbenes  15  Figure  1.8.  Attempted synthesis of an N H C by chloroform elimination  20  Figure  1.9.  Reported methodology for the synthesis of NHCs  20  Figure  1.10.  a) 71-Stabilization and b) inductive effects of NHCs  21  Figure  1.11.  (a) A n example and (b) schematic representation of donor-  2  acceptor bonding in Fischer-carbene complexes Figure  1.12.  22  (a) A n example and (b) schematic representation of covalent bonding in Schrock-alkylidene complexes  22  Figure  1.13.  Metal-NHC complexes reported by Wanzlick and Ofele  23  Figure  1.14.  Modification to a Ru catalyst with an N H C ligand  25  Figure  1.15.  Examples of a) phosphine and b) pyridine N H C metal complexes for Heck catalysis  Chapter Two  25  Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  Figure Figure  Title 2.1.  ORTEP  Page view  of  ([NP(N)N]Ta(^-H) (p.-N)(Ta[NPN])(ZrCp ) 2  (2.10) depicted with 5 0 % ellipsoids; all hydrogen atoms, silyl methyl and phenyl ring carbon atoms except ipso carbons have  xii  2  been omitted for clarity  Chapter Three  40  Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Carbene  Complexes Figure  Title  Pase  Figure 3.1.  ORTEP view of  Mes  [ N C H N ] H - C l (3.5) depicted with 50% thermal 2  ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.2.  ORTEP view of  Mes  [ N C N ] H , (3.8) depicted with 50% thermal 2  ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.3.  58  Imidazolium (3.12) and imidazolinium (3.13) candidates with an aryl backbone  Figure 3.4.  56  59  ORTEP view of [NCN]Zr(NEt )  (3.17) depicted with 50%  tol  2  2  thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.5.  64  ORTEP view of [ N C N H ] T i ( N M e ) (3.22) depicted with 50% Mes  2  3  thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.6.  65  ORTEP view of [NCN]ZrCl (py) (3.30) depicted with 50% tol  2  thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.7.  68  ORTEP view of [NCN]Zr(CH SiMe ) (3.31) depicted with 50% tol  2  3  2  thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 3.8.  71  ORTEP view of  Mes  [NCN]HfBu  2  (3.39) depicted with 50%  thermal ellipsoids; all hydrogen atoms have been omitted for clarity  Chapter Four  73  Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Carbene  Complexes Fisure  Title  Pase  Figure 4.1.  Examples of Group 4 olefin polymerization catalysts  xiii  98  Figure 4.2.  ORTEP view of  Mes  [NCN]Hf(Ti -XyNCCH )(CH ) (4.7) (THF 2  3  3  omitted), depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity Figure 4.3.  ORTEP  view of  Mes  103  [NCN]Hf(n -XyNCCH )  (4.8) (CH C1  2  3  2  2  2  omitted), depicted with 50% ellipsoids; all hydrogen atoms and mesityl groups have been omitted for clarity Figure 4.4.  104  ORTEP view of [NCN]Hf(OC(CH )=C(CH )NXy), (4.11) (1/2 Mes  3  3  E t 0 omitted), depicted with 50% ellipsoids; all hydrogen atoms 2  and mesityl groups have been omitted for clarity Figure 4.5.  108  ORTEP view of [NCN]Hf) ( u-OC( Bu)=C( Bu)0) , (4.16) Mes  i  2  i  /  2  (4 C 6 H omitted), depicted with 50% ellipsoids; all hydrogen 6  atoms and mesityl groups have been omitted for clarity Figure 4.6.  ORTEP  view  of  Mes  112  [NCN]Hf(Me)(n - BuNC(Me)0) 3  t  (4.17)  depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity Figure 4.7.  ORTEP  117  view of  Mes  [NCN]Hf(Me)(n - PrNC(Me)N Pr) (4.18) 3  i  i  depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity Figure 4.8.  ORTEP  view  119  of  Mes  [NCN]Zr(Cl)(OCH CH CH CH ) 2  2  2  3  (4.24)  depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity  124  Figure 4.9.  Coordination modes of hydrazido ligands  126  Figure 4.10.  Examples of hydrazido(l-) and hydrazido(2-) titanium complexes.. 127  Figure 4.11.  ORTEP view of [NCN]Hf(Me)(n -NHNMe ) (4.25) depicted Mes  2  2  with 50% ellipsoids; with the exception of HI00, all hydrogen atoms have been omitted for clarity.'  Chapter Five  128  Synthesis and DFT Studies of Tantalum [NCN] Transition Metal Complexes  Figure  Title  Page  Figure 5.1.  ORTEP view of [NCNH]Ta(NMe ) (5.1) ( C H C H tol  2  xiv  4  3  6  5  omitted)  depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 5.2.  ORTEP view of  Mes  152  [NCNH]Ta(CHPh)(CH Ph) 2  2  (5.2), depicted  with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity with the exception of HI 01 Figure 5.3.  ORTEP view of [NCN]Ta(NMe ) tol  2  3  154  (5.3), depicted with 50%  thermal ellipsoids; all hydrogen atoms have been omitted for clarity Figure 5.4.  156  ORTEP view of [NCCN]Ta(CH Bu) (5.7), depicted with 50% Mes  t  2  2  thermal ellipsoids; all hydrogen atoms have been omitted for clarity  159  Figure 5.5.  Potential pathways for ligand P-H abstraction  161  Figure 5.6.  Computational model of the trimethyl tantalum starting complex... 162  Figure 5.7.  Relative energies of the intermediates and transition states in a potential a-bond metathesis mechanism  163  Figure 5.8.  JIMP Pictures of the one-step a-bond metathesis pathway  163  Figure 5.9.  Relative energies of the intermediates and transition states in a potential  two-step  a-H abstraction/alkylidene  mediated C - H  activation mechanism Figure 5.10.  164  JIMP Pictures of alkylidene mediated C-H activation of the ligand backbone  Figure 5.11.  165  ORTEP view of [NCCN]Ta(Cl)(CH Bu) (5.10), depicted with Mes  t  2  50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity  Chapter Six  167  Thesis Summary and Extensions: Chiral Group 4 [NCN] Complexes  Figure  Title  Page  Figure 6.1.  ' H N M R spectrum  of (l^,2' S,4i?)-2-(l,7,7-trimethylbicyclo1  [2.2.1]hept-2-ylamino)ethyl ammonium chloride (6.8) in CDCI3. (* denotes V equivalent of C H C ( 0 ) C H ) . 2  3  xv  3  185  Figure 6.2.  ORTEP  view  of (-)-(li?,2'5,4i2)-2-(l,7,7-trimethylbicyclo-  [2.2.1]hept-2-ylamino)ethylammonium chloride (6.8) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity  Figure 6.3.  186  'H N M R spectrum of (17?,2'S,4i?)-2-(l,7,7-trimethylbicyclo[2.2.1]hept-2-ylamino)ethyl chloride (6.9) in CDC1 . (* denotes 3  E t 0 impurity)  .  2  Figure 6.4.  ' H N M R spectrum of  scam  187  [ N C H N ] H - C l (6.10) in d - C D O D (* 2  4  3  denotes THF impurity)  188  Figure 6.5.  ' H N M R spectrum of  Figure 6.6.  Aminolysis of a Zr-N bond in  Figure 6.7.  ' H N M R spectrum of  scam  [ N C N ] T i ( N M e ) (6.12) in C D 2  scam  scam  2  6  [NCN]Zr(CH Ph) 2  190  6  193  2  [ N C H ] H - C l (6.15) in d -DMSO (* 6  denotes contamination with H 0 and § denotes a trace amount of 2  Et 0)  195  2  Figure 6.8.  ' H N M R spectrum of [NC]H"(6.16) in C D scam  6  Appendix B  6  ,  '.. ' 196  Evaluating the Formation of a Tantalum Metallaaziridine Complex by DFT Calculations  Figure  Title  Pase  Figure B.l.  Relative energies of the intermediates and transition states in a potential a-bond metathesis mechanism  220  Figure B.2.  JIMP Pictures of the one-step a-bond metathesis pathway  221  Figure B.3.  Relative energies of the intermediates and transition states in a potential two-step  a-H abstraction/alkylidene  mediated C - H  activation mechanism Figure B.4.  222  JIMP Pictures of a-H abstraction by a methyl group to generate a [NCN]Ta(=CHR')R alkylidene intermediate  Figure B.5.  224  JIMP view of A. Selected bond distances ( A ) and angles (deg): T a l - C l 2.381, Tal-C2 2.252, Tal-C3 2.248, Tal-C4 2.238, T a l N l 2.053, Tal-N2 2.020, C l - T a l - C 2 139.6, C l - T a l - C 3 142.0, C2-Tal-C3 76.4  226  xvi  Figure B.6.  JIMP view of D. Selected bond distances ( A ) and angles (deg): T a l - C l 2.248, Tal-C2 2.219, Tal-C3 2.173, Tal-C4 2.257, T a l N l 2.065, Tal-N2 1.982, C l - T a l - C 2 130.5, C l - T a l - C 3 122.7, C2-Tal-C3 106.1, C4-Tal-N2 38.2  Figure B.7.  Gaussview representations  of selected  226 N B O bonding and  antibonding orbitals in the trimethyl complex A Figure B.8.  Figure B.9.  Gaussview representations  of selected  229  N B O bonding and  antibonding orbitals in the trimethyl complex D  230  JIMP Pictures of A' and D'  231  xvii  GLOSSARY OF TERMS  ,  The following abbreviations, most of which are commonly found in the literature, are used in this thesis.  A  Angstrom  a, b, c  unit cell dimensions, lengths (A)  a, P, Y  unit cell dimensions, angles (°)  Anal.  analysis  atm  atmosphere  Ar  aryl  B  equivalent isotropic parameter  e q  BBI  broad band inverse  Bn  benzyl, - C H C H  br  broad  n-Bu  «-butyl group, - C H C H C H C H  2  6  5  2  2  2  3  carbon-13 C\,  C2,  c  2v  Schoenflies symmetry designations  cal  calories  Calcd  calculated  CCD  charge coupled device  cm  centimetres  Cp  cyclopentadienyl, C5H5  Cp*  pentamethylcyclopentadienyljCsMes  cryst  crystal  Cy  cyclohexyl,  d  doublet  dd  doublet of doublets  dq  doublet of quartets  dt  doublet of triplets  deg (or °)  degrees  diox  1,4-dioxane  -C6H11  xviii  °c  degrees Celsius  DFT  density functional theory  DME  1,2-dimethoxyethane  dt  numbers of ^-electrons  d  n-deuterated  n  AE  0  zero point corrected electronic energy  AE  e  electronic energy  EI-MS  electron ionization/mass spectrometry  Et  ethyl group, - C H C H  ETM  early transition metal  AG  free energy  2  0  3  g  grams  gof  goodness of fit  GC-MS  gas chromatography/mass spectrometry  AH  enthalpy  0  'H  proton  {'H}  proton decoupled  h  hour  HIPT  hexaisopropylterphenyl, -(3,5-(2,4,6-'Pr  H M D SO  hexamethyldisiloxane  HOMO  highest occupied molecular orbital  Hz  Hertz, seconds"  IR  infrared  N  T JAB  1  n-bond scalar coupling constant betwee  K  Kelvin  kcal  kilocalories  kJ  kiloJoules  Li  lithium-6  L  neutral two-electron donor  LTM  late transition metal  LUMO  lowest unoccupied molecular orbital  6  xix  M  central metal atom (or molar, when referring to concentration)  M  +  parent ion  m  meta  m  multiplet (NMR spectroscopy)  mm  millimetres  mM  millimolar  Me  methyl group  Mes  mesityl group, -2,4,6-Me C6H  mg  milligram(s)  MHz  megaHertz  MgADP  adenosine diphosphate, magnesium salt  MgATP  adenosine triphosphate, magnesium salt  mL  millilitre  mmol  millimole  MO  molecular orbital  mol  mole  MS  mass spectrometry  no.  number  1 5  N  3  2  nitrogen-15  NHC  N-heterocyclic carbene  NMR  nuclear magnetic resonance  Np  Neopentyl group, - C H C ( C H )  [NPN]  diamidophosphine ligand, -(PhNSiMe CH ) PPh  o  ortho  ORTEP  Oakridge Thermal Ellipsoid Program  p  para  p  pentet  Pi  inorganic phosphate, P 0 "  31  P  2  3  2  3  4  phosphorus-31  { P}  phosphorus-31 decoupled  Ph  phenyl group, -C6H5  31  3  xx  2  2  PhH  benzene  PhMe  toluene  [PNP]  amidodiphosphine ligand, -(R PCH SiMe2)2N  [P N ]  diamidodiphosphine ligand, -PhP(CH SiMe NSiMe CH )2PPh  ppm  parts per million  'Pr  isopropyl group, -CH(CH3)2  py  pyridine  q  quartet  R, R'  hydrocarbon substituents  R, R  residual errors, (X-ray crystallography)  R  2  2  w  2  2  2  2  2  R  coefficient of determination for a linear regression  re fins  reflections (X-ray crystallography)  rt  room temperature  s  singlet  sept  septet  syst  system  t  triplet  T  temperature in Kelvin or °C  THF  tetrahydrofuran  TMS  trimethylsilyl group, -Si(CH )  U(eq)  equivalent isotropic displacement parameter  V  unit cell volume  VT  variable temperature  X  halide substituent  XHYDEX  hydride location program  Z  asymmetric units per unit cell  3  2  3  x-d  Complex x has n number of H atoms replaced by H atoms  x- 7v2  Complex x has a N 2 labeled dinitrogen moiety  n  n-hapto  !  n  15  n  2  15  [i  bridging or absorption coefficient (X-ray crystallography)  p  density  xxi  p i ca  c  calculated density  A.  wavelength  8  chemical shift in ppm  a , 71, 8  notations for bonding symmetries  xxii  ACKNOWLEDGEMENTS  I wish to acknowledge first and foremost, Dr. Michael D. Fryzuk. M y studies at U B C under his supervision have been memorable and truly a learning experience. During this time, I have learned an immense amount of chemistry and have been challenged on a daily basis to thoroughly investigate not only chemistry that pertains to me, but research that exists outside my expertise.  Despite his busy schedule, he has  always found the time to listen to my ideas (and problems), and offered words of encouragement and guidance when needed. I would also like to thank those post-docs, graduate and undergraduate students who I have worked with in the Fryzuk in the past and present. I especially wish to thank: Erin MacLachlan for all her help and enthusiasm in the lab and always going for a coffee run whenever one was needed. Howard Jong for his assistance with crystallographic questions and his expertise in restaurants. Fiona Hess for all her assistance with editing and critical comments on this thesis. Kevin Noonan for his help with polarimetry and other thought provoking discussions, and also golf. Bryan Shaw for his golfing prowess and the introduction to a "turbo". The department of chemistry at U B C has also been an immense help in making my research here easy and enjoyable. I would especially like to thank Howie Jong and Dr. Brian Patrick for their expertise in X-ray crystallography. I would also like to thank Dr. Nick Burlinson and the N M R personnel for their assistance with any questions and concerns I had with running the N M R spectrometers.  I am also grateful to Brian  Ditchburn for his timely help in glassblowing the many broken J. Young tubes I brought to him. I also must acknowledge the personnel in the mechanical and electronics shops with the timely help they provided during the many crisis periods encountered with the glovebox.  xxiii  dedication This work is dedicated to the two important women in my life. To my mother, Carolyn Norris, you have always been there for me and I greatly appreciate all that you have given me (especially my sense of humour ("Illigitimus Non Carborundum")). If it wasn't for you, I hesitate to think where I would be. To my soon to be wife, Dr. Pauline Vykruta, your approach to life is truly inspirational. You have challenged me in many ways, and I look forward to spending the rest of my life with you, milacku.  xxiv  STATEMENT OF AUTHORSHIP  Chapters two, three, four, five and six were conducted in collaboration with Professor Michael D. Fryzuk, the research supervisor for this thesis, who assisted with identification and design of the research presented. Chapter two features some initial research performed by a previous graduate student, Dr. Bruce MacKay, under the supervision of Professor Michael D. Fryzuk. Chapter three and appendix B presents DFT calculations that were performed by Dr. Chad L. Beddie at the Texas A & M University under the supervision of Professor Michael Hall. A l l experimental research, data analysis, and manuscript preparation were performed by the thesis author.  xxv  Chapter One: Dinitrogen Chemistry and Ligand Design  Chapter One  Dinitrogen Chemistry and Ligand Design 1.1.  Origins of Coordination and Organometallic Chemistry Our modern view of coordination chemistry began at the end of the 19 century at th  a time when the understanding of valence bonding and geometry in transition metal complexes was in a state of confusion.  Prior to this period, the configuration and  composition of many inorganic compounds were written in accordance with a theory described by the Swedish chemist, Jons Jacob Berzelius. Berzelius ardently attempted to 1  sort all chemical compounds using a paired system which he called "the two-component theory".  The Swedish chemists, Christian Wilhelm Blomstrand and Sophus Mads  Jorgensen, ' applied this theory to describe the bonding and geometry of hexaammine 2 3  cobalt(II) complexes. Blomstrand and J 0 r g e n s e n postulated that in a material with the composition  C0CI2  • 6 N H 3 , the divalent C o  2+  metal centre could only form two bonds to  the ammonia molecules. As a result, the binding of the ammonia residues to the metal centre must occur in a linking fashion that would form chains (Figure 1.1).  1  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  2®  CI  / \  2CP  Co  N^—N-—NH3 H H 3  CI  3  (b)  (a)  Figure 1.1.  Interpretation of the coordination sphere of C 0 C I 2 • 6 N H 3 by (a) Blomstrand/Jorgensen and (b) Werner.  Upon examination of Blomstrand and Jorgensen's research, Alfred Werner noted several anomalies that did not corroborate physical and chemical experimentation. This evidence led Werner to postulate that "single atoms or ions act as central positions, where a certain number of other compounds, atoms, ions, or other molecules are ordered in simple geometrical patterns" (Figure l . l ) . ' 6  7  Werner found that this hypothesis could  successfully explain experimental discrepancies that were observed in the structures of the complexes proposed by Blomstrand and J0rgensen. Werner also introduced the term coordination number, which describes the number of atoms that are grouped around a central nucleus. For his seminal work in this area, Alfred Werner was awarded the Nobel Prize in Chemistry in 1913 "in recognition of his work on the linkage of atoms in molecules". Werner's contributions led to conception of the term ligand, which refers to 3  o  atoms or groups attached to a central atom in the formation of a coordination compound. The progress in coordination chemistry stimulated interest in the coordination of other ligands and one mature area of chemistry which has emerged is the study of organometallic complexes.  Organometallic chemistry is defined as the study of 7Q  compounds  containing a metal-carbon  bond. '  Despite the prior isolation of  organometallic compounds like Zn(CH2CH3)2 and Ni(CO)4,  9  the origins of modern  organometallic chemistry are believed to have begun with the discovery of ferrocene, reported separately by both Wilkinson and Fischer. " 10  12  The importance of this finding in  the field of chemistry was embodied in the awarding of the Nobel Prize in Chemistry in 1973 to both scientists.  The field of organometallic chemistry has grown since this  discovery to include transition metal complexes with ligands such as C O , CN", and benzene.  9  Bonding in these complexes is usually described by molecular orbital theory 2  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  and the reactivity dictated by the effective atomic number (EAN) or "18-eIectron rule". '  Organometallic complexes are of interest from both an academic perspective in  terms of their synthesis and bonding implications, and from an industrial perspective regarding their potential to mediate catalytic reactions. Indeed, two recent Nobel Prizes in Chemistry were awarded in 2001 to Knowles, Noyori, and Sharpless and in 2005 to 14  Chauvin, Grubbs, and Schrock  13  for research involving the use of organometallic  catalysts in organic synthesis. The emergence of organometallic chemistry and the continued relevance of coordination chemistry has also been driven in part by its application and relevance in other areas of science.  In particular, research in the biological field has relied on  fundamental research in both organometallic and inorganic chemistry. Evidence of this comes from the ubiquitous role metal complexes play in living organisms. For example, iron plays a fundamental role in the daily function of human life forms.  16  Other metals,  such as copper, are also known to serve an integral part in enzymatic processes and vitamin synthesis.  17  One important progression in the borderline field of inorganic  chemistry and biology is the area of dinitrogen fixation, which is the topic of discussion in the next section.  1.2.  Reactivity of Dinitrogen  The utilization of molecular nitrogen, or dinitrogen, to form organic nitrogen19 27  containing products is one of the substantial challenges in organometallic chemistry. Nitrogen appears in all biological systems and is vital for the synthesis of amino acids, 28  nucleotides, enzymes, and other biologically important compounds.  One could  envision the synthesis of these organic nitrogen-containing compounds from the catalytic reaction of dinitrogen with simple organic reagents (Figure 1.2). A formidable hurdle for the successful implementation of this catalytic cycle is the inertness of molecular nitrogen. Dinitrogen possesses a strong triple bond that must be completely cleaved and functionalized to form organic compounds. Furthermore, the robust dinitrogen molecule features a large dissociation energy (941 kJ mol" ), the absence of a dipole, and possesses 1  a large H O M O - L U M O gap, which makes oxidation and reduction difficult. 3  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  Amines, N-heterocycles  N-2 + reagents  Figure 1.2.  Catalytic formation of N-containing compounds from N . 2  Notwithstanding its poor reactivity, dinitrogen can be converted to ammonia by several well-known pathways. Several biological systems are known to activate and functionalize dinitrogen to form ammonia. '  29 30  For example, the enzyme nitrogenase is  able to bind to N and other substrates, reducing these bound molecules using electrons 2  provided by metal clusters. This facilitates the protonation of the reduced nitrogen atoms and produces H as a byproduct of the reaction. As a result of this protonation, the bound 2  nitrogen atoms become "fixed" and are released as ammonia (Equation 1.1).  It is  important to note that the reduction of N in this process is energy intensive, requiring 16 2  equivalents of MgATP.  While the mechanistic details of this transformation remain 31  unclear, the catalytic process has been scrutinized in detail. *- 2 N H . + H + 16 MgADP + 16 P, (1.1)  N = N + 8 H + 8 e" + 16 MgATP +  3  2  The most significant example in which dinitrogen is converted to ammonia is the Haber-Bosch process. '  Both N and H are reacted at high temperature (400-450°C)  32 33  2  2  and pressure (270 atm) in the presence of a Fe or Ru catalyst to yield ammonia (Equation 1.2).  In this process, H is both a reducing agent and substrate for the production of 2  ammonia. The impact of this discovery to the field of chemistry was monumental as both Haber and Bosch each received the Nobel Prize in Chemistry in 1918 and 1931, respectively, ' for their discovery and refinement of the technique. 34 35  N = N (g) + 3 H'2(g)  Fe or Ru catalyst  2NH  3 ( g )  (1.2)  100 to 300 atm 400 to 550°C  4  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  One feature consistent with the known examples of dinitrogen fixation is the incidence of transition metals at the active site during catalysis. This fact has shifted research efforts towards the development of other transition-metal-assisted dinitrogen reduction systems with an aim to achieve a homogeneous version of the Haber-Bosch process.  To this end, the coordination of dinitrogen to transition metals has been  investigated and will be discussed further.  1.3.  Coordinated Dinitrogen Complexes  The necessity of a transition metal catalyst in the Haber-Bosch process suggests that the activation of N can be induced by a transition metal. 2  This assumption has  stimulated interest in the potential coordination of N to transition metals. In 1965, Allen 2  and Senoff serendipitously discovered the first metal dinitrogen complex by the reaction of R.UCI3 with hydrazine hydrate.  36,37  This result was revolutionary, as it became  apparent that N could act as a ligand in a coordination complex. In these complexes, 2  dinitrogen is typically "activated" when coordinated to the transition metal.  This  activation can decrease the bond order of the N=N bond to varying degrees. In general, late transition metal (LTM) complexes feature an N ligand that is weakly activated. A n 2  examination of the N - N bond lengths by X-ray crystallography in 1.1 and many other L T M dinitrogen complexes reveals distances that are close to free N (1.0975 A ) . ' 19  38  39  2  2+  N  III N  NH  H-sN HUN'  Ru-  3  'NH,  2X"  NH,  1.1 Figure 1.3.  The first reported transition metal dinitrogen complex (X" = Br", I", BF4", PF ")6  5  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  Early transition metals (ETMs) have also been extensively studied for the coordination and activation of dinitrogen.  In general, stronger activation of the  dinitrogen ligand is observed compared to L T M complexes.  One series of E T M  complexes that have been examined for their potential to activate molecular dinitrogen are substituted zirconium metallocenes. The reduction of (r^-CsMes^ZrCb with Na/Hg amalgam under nitrogen produces [(r^-CsMes^Zr (n -N2)]2(|>V | -N2) with three bound l  N ligands (Figure 1.4).  40  2  :T 1  A slight modification in the cyclopentadienyl ancillary ligand  reveals a different bonding mode for N2 and higher degree of activation  4 1  The reduction  of ( n - C M e H ) Z r C l with Na/Hg amalgam under N yields ((n -C Me H) Zr) (u-r| :ri 5  5  5  4  2  2  2  2  5  4  2  2  2  N ) (1.3), a side-on bound dinitrogen complex with a N - N bond length of 1.377(3) A , 2  which is significantly lengthened from free N2 (1.0976 A ) . ' 3 8  1.2  Figure 1.4.  3 9  1.3  Examples of zirconocene-based dinitrogen complexes.  Although dinitrogen complexes of almost all the transition metals have been reported, including the actinides and lanthanides, the transformation of the dinitrogen ligand in these complexes has proven to be difficult. One goal of dinitrogen activation via transition metal complexes is the complete cleavage of the N=N bond. This objective is quite challenging since dinitrogen possesses characteristics that make N2 an unreactive ligand. Attempts to cleave the "activated" N=N bond with chemical reagents reveal the inert N ligand is susceptible to displacement by more reactive ligands such as H 2 , " 4 2  4 7  2  CO, " 44  49  and olefins. ' ' ' ' 42  44  48  50  51  6  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  1.4.  Dinitrogen Cleavage  The synthesis of ammonia from N by biological methods and the Haber-Bosch 2  process requires the cleavage of the N=N bond.  Several assays have focused on  promoting the cleavage of molecular nitrogen with ETMs. Perhaps the most recognized example of dinitrogen cleavage involves molybdenum amide complexes reported by Cummins. '  52 53  A three-coordinate Mo[NR(Ar)]3 stabilized by bulky N-ter?-butyl anilide  ligands (1.4) is able to bind to N to yield a dinuclear end-on bound dinitrogen complex 2  at -35°C (Scheme 1.1). Warming solutions of this product to room temperature results in the cleavage of the N=N bond to form the terminal nitride complex N=Mo[NR(Ar)]3 (1.5). Density functional theory calculations on this transformation suggest that bond cleavage proceeds through a zig-zag dinuclear molybdenum dinitrogen transition state.  54  This process is remarkable as the reduction of the N ligand occurs under mild conditions 2  and requires no added reagents. In this example, the reducing power required for N - N bond scission originates from the two molybdenum metal centres from which six reducing equivalents reductively cleave the N=N triple bond.  While ammonia synthesis  from this nitride species has not been reported, a niobium analog of 1.5 has recently been used in a nitrogen atom transfer reaction with acid chlorides to generate new organic nitrile products.  55  Unfortunately, the formation of these organic nitrogen containing  compounds is still stoichiometric in nature and this process has yet to be developed into a catalytic system.  7  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  N Ar(R)N„ ,'Mo—N(R)Ar  N III  2  I  -35°C,  Ar(R)N Ar(R)N" Ar = 3 , 5 - M e C H 2  6  R = C(CD ) CH 3  2  3  ^-~N(R)Ar  j  Ar(R)N,,,  Ar(R)N 2  3  1.4  ||j Mo—N(R)Ar  Ar(R)N*^  1.5 Mo(N(R)Ar)  3  Ar(R)N Ar(R)N'  Ar(R)N  Mo'  -N(R)Ar  Ar(R)N"  I  Mo'  -N(R)Ar  II  N  N  II  N . ._..„,  Mo  Ar(R)N ' j Ar(R)N 1  . ,„..„, Mo^ Ar(R)N' j Ar(R)N  ^~-N(R)Ar  N(R)Ar  Scheme 1.1. Vanadium complexes are also known to effect N=N bond cleavage. For example, the reduction of the diamidoamine vanadium complex (Me3Si(CH2CH2NSiMe3)2V)2(pCl)2 with potassium graphite (KCg) in the presence of N results in the coordination and 2  cleavage  of  dinitrogen  to  form  the  dimeric  vanadium  (Me Si(CH CH2NSiMe3)2V)2(p-N)2 (1.6) (Scheme 1.2). 3  2  56  bis(nitride)  complex  The vanadium-nitrogen bond  from the cleaved dinitrogen unit can be further reduced with potassium graphite to generate 1.7.  8  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  The cleavage of molecular dinitrogen can also be achieved by the sterically WiPT  encumbered molybdenum triamidoamine complex =[[(3,5-(2,4,6- Pr C6H2)2C6H3)NCH2CH ]3N] "). i  3  3  57>58  2  WIPT  (N3N)MoCl (where  (N3N)  The dinitrogen complex 1.8 (Figure  1.5) can be synthesized by the stepwise reduction and oxidation of  HIPT  (N3N)MoCl.  While no discrete molybdenum nitride species has been isolated as a result of cleavage of the N 2 ligand in 1.8, experiments with a compatible proton source and reducing agent reveal that 1.8 is capable of catalytically transforming dinitrogen into ammonia (four turnovers are reported before the catalyst loses function).  This result and subsequent  modeling studies of the intermediates formed during this reaction demonstrate that cleavage of N 2 is possible under certain conditions.  9  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  'Pr 1.8  Figure 1.5.  Successful catalyst for the synthesis of N H 3 from N2  The activation and cleavage of molecular nitrogen by transition metal complexes can be largely influenced by the ligands encompassing a metal centre.  It has been  demonstrated that this chemistry can be regulated by slight modifications of the ligand architecture.  One aspect of research in the Fryzuk group has been the design and  synthesis of ancillary ligands effective for stabilizing transition metal dinitrogen complexes. For the most part, ancillary ligands involving mixed phosphine and amide donors have been investigated.  /. 5.  Amidophosphine Ligands for N2 Activation  The combination of both phosphine and amido donors into a chelating ligand framework was anticipated to be suitable for the stabilization of different types of transition metals across the transition series in various oxidation states.  Phosphine  donors are well known to coordinate to L T M centres, while anionic amido donors have been used extensively in many E T M complexes. The first ligand that was investigated employing these donor groups was the [PNP] design, utilizing a centrally positioned  10  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  amido donor and two flanking phosphine groups.  59  The preparation of this ligand is  shown in Scheme 1.5, and involves the addition of three equivalents of L i P ' P ^ to commercially available HN(SiMe2CH2CI)2 to generate the lithiated [PNP] ligand. Both early and L T M complexes have been stabilized using this ligand and, in some cases, activated dinitrogen complexes (ie. 1.9) have been isolated. " 59  64  Despite these successful  outcomes, one drawback of the [PNP] design in E T M chemistry is the potential for the phosphine groups to dissociate from the metal centre. ' '  62 65 66  Given this possibility, further  modifications involving phosphine and amide donors have been investigated.  1.9 Scheme  1.5.  A macrocyclic [P2N2] ligand was investigated that employs two neutral phosphine and two anionic amido donor groups. The preparation of this ligand follows a similar synthetic methodology to the [PNP] ligand. A diphosphinoamine precursor is synthesized by the addition of PhPHLi to HN(SiMe2CH2Cl)2.  This reagent is  deprotonated and reacted with a second equivalent of HN(SiMe2CH2Cl)2 to generate the lithiated [P2N2] ligand (Scheme 1.6).  67  The arrangement of the phosphine atoms offers  11  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  the potential for the synthesis of two isomeric forms of the ligand; the syn isomer can be selectively synthesized by controlling the experimental conditions of the reaction. The [P2N2] macrocycle has been effectively used as a supporting ligand for the isolation of several E T M dinitrogen complexes (ie. 1.10). " 68  70  One drawback that has been found of  certain [P2N2] complexes of tantalum has been their lack of reactivity. The additional donor in the ligand, as compared to [PNP], has resulted in several coordinatively and 71  electronically saturated [P2N2] systems that possess diminished reactivity.  S c h e m e 1.6.  Another variant of the amidophosphine ligand involves the [NPN] design that utilizes one phosphine donor and two anionic amido groups. This design reconciles the problems encountered with the reactivity of [P2N2] complexes and still maintains a dianionic bonding nature. The synthesis of the Li2[NPN] ligand involves the addition of four equivalents of o-BuLi to a mixture of one equivalent of PhPPb. and two equivalents  12  References begin on page 27.  Chapter One: Dinitrogen  Chemistry and Ligand  Design  of P h N S i M e C H C l (Scheme 1.7). Metathesis reactions with metal chloride reagents and 2  2  the Li [NPN] ligand were used successfully to synthesize [NPN]MC1 complexes. For 2  2  example, the reaction between Li [NPN] and ZrCL proceeds to give [NPN]ZrCl . This 2  2  complex can be reduced in the presence of nitrogen to form the dinitrogen complex  Modifications to the [NPN] ligand design have generally focused on the replacement of the reactive N-Si bond. '  73 74  Not only is this bond sensitive to water and  air, it can rupture during the reduction process forming products which result from deleterious modification of the [NPN] ligand. " 74  76  One aspect that remains relatively  unexplored is the substitution of the phosphine group for another neutral donor. N Heterocyclic carbenes (NHCs) have come to be regarded as phosphine equivalents and have been extensively studied as essential ligands in homogeneous catalysis and small  13  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  molecule activation processes.  77  Given this parity with phosphines, the substitution of an  NHC in place of the phosphine donor in the [NPN] architecture can be examined, which could generate a [NCN] ancillary ligand (Figure 1.6). The following sections of this chapter will describe the discovery of NHCs and their emergence as ligands in selected areas of organometallic catalysis. .  [NPN] Figure 1.6.  [NCN]  Design of a diamido-N-heterocyclic carbene [NCN] ligand.  1.6. Introduction to Carbenes Our understanding of carbene chemistry has progressed in the past 20 years as a result of greater insight into the electronic structure and stability of carbenes. '  78 79  Carbenes are neutral species that contain a divalent carbon atom with only six electrons.  80  Two nonbonding electrons can be found in two different frontier orbitals, commonly referred to as the a and p^ orbitals. The existence of these valence electrons in these orbitals presents the possibility of two unique electronic configurations (Figure 1.7). The singlet state involves the pairing of these electrons in the same a orbital. In the parallel triplet state, the two electrons can occupy unique a and p^ orbitals.  14  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  o0  R  R  triplet  singlet  Figure 1.7.  R  Possible electronic configurations of carbenes.  The nature of this electronic configuration directly influences the reactivity of the carbene molecule.  Singlet carbenes possess a filled and a vacant orbital and thus  exhibit an ambiphilic nature. As a result, singlet carbenes are very reactive species and difficult to isolate. Attempts to isolate singlet carbenes often result in rearrangement reactions bonds, '  85 86  such as  1,2-migration,  dimerization, '  and insertion into C - H bonds.  87  [l+2]-cycloadditions to C=C  Conversely, triplet carbenes display a  diradical nature owing to two singly occupied orbitals. As a result, these species have been reported to perform carbene dimerization, " [l+2]-cycloadditions to C=C bonds, 88  90  91  and insertion reactions that are similar to their singlet carbene counterparts but proceed 89  by a different mechanism. The spin multiplicity of a carbene is dictated by the energetic difference between the a and p^ orbitals. " 92  99  A large o-p  n  energy separation favors a singlet ground  configuration, whereas a small energy difference can induce the triplet spin state. The op energy gap can be increased by the presence of a-electron withdrawing substituents n  adjacent to the divalent carbon atom.  These groups inductively stabilize the a-  nonbonding orbital by increasing its 5 character, while leaving the p orbital unchanged. n  This gap can also be increased with adjacent 7i-donating atoms, which quenches the electron deficient nature of the carbene and results in a polarized four electron threecentered n system. Steric effects also influence the ground state multiplicity of a carbene. " 100  102  Bulky substituents on the carbene can dictate the multiplicity in the absence of electronic effects. For example, dimethylcarbene has a bent singlet ground state with a bond angle of 111 at the central carbon atom. 0  100,101  15  Conversely, carbenes with two bulky  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  substituents, such as di(tert-butyl)carbene, exist in the triplet state and exhibit larger bond angles (ie. 143° for di(tert-butyl)carbene).  1.7.  102  Isolation of Stable Carbenes  1.7.1. Acyclic Carbenes  The first discovery of a stable isolable carbene was reported by Bertrand in 1988 (Scheme 1.8). ' '  79 103 104  Phosphanyl(silyl) carbenes can be prepared by the thermolysis or  photolysis of a diazo precursor (1.12). The carbene 1.13 is remarkably stable for weeks at room temperature and can be purified by distillation under vacuum at 75°C-80°C. At the time, the notion that this species was a carbene was met with skepticism as 1.13 does not exhibit reactivity typical of singlet carbenes. For example, 1.13 does not react with simple alkenes but can add to polar C=C bonds to give cyclopropane products (ie. 1.14) '  Nucleophilic reactions were also reported with 1.13 and isonitriles " and  phosphines  109  104 105  106  108  to give 1.15 and 1.16, respectively. Despite this skepticism, the existence  of a carbene was confirmed by both computational methods  110  and an X-ray  crystallographic study on an analog of 1.13." A P-C-Si bond angle of 152.6° was noted, 1  in addition to short C-P and C-Si bond lengths, which suggests the ylide resonance form 1.13' contributes to the overall structure of the acyclic carbene.  16  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  'ProN 'Pr,N  N  >  2  SiMe  3  1.12 hv I  A 'Pr N  'Pr N  2  2  > 'Pr N 2  © P: 'SiMe  Pr H  X  [ 3  2  R  'PrzN  3  PMe  ?  N'Bu 'PrpN  x  'SiMeg  7  SiMe  1.13"  BuNC  R 2  3  1.13"  1.13  'Pr N  SiMe  P= > 'Pr,N  1.14  'Pr N  /  SiMe  2  3  'Pr,N  PMe,  'Pr N  ^SiMe  2  3  1.16  1.15  Scheme 1.8.  Following these results, the isolation of other stable aminocarbenes were pursued. For example, an amino(aryl)carbene is accessible by deprotonation of the iminium salt 112 113  1.17 (Scheme 1.9). '  Although 1.17 could be isolated, its instability represents a  common characteristic consistent of many acyclic carbenes.  Compound 1.17 slowly  decomposes over a period of 1 week to give 1.18, which is a product of an intramolecular 112 cyclization reaction.  17  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  1.18  Scheme 1.9.  The combination of phosphanyl and amino groups on a divalent carbon centre has also been investigated, for example 1.19 in Scheme 1.10.  114  This class of carbenes  exhibits thermal sensitivity and decomposes at temperatures above -20°C. The stability of phosphanyl(amino) carbenes can be enhanced by the alkylation of 1.19 to afford the phosphonium salt 1.20. This phosphonium salt is indefinitely stable in the solid state at room temperature,  115  but susceptible to displacement by nucleophiles like ter/-butoxide.  This substitution of functional groups on the carbene allows for the formation of other amino heteroatom carbenes.  18  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  R a) X = O; R = *Bu b) X = S; R = M e  Scheme  1.10.  1.7.2. N-Heterocyclic Carbenes  In the early 1960's, Wanzlick proposed that the incorporation of a carbene unit in a cyclic structure between two amino substituents would enhance the stability and lead to the isolation of this reactive species. ' '  83 84 116  It was envisioned that the elimination of  chloroform from 1.21 could yield the corresponding carbene product (Figure 1.8). Although the dimeric species 1.22 was the only product isolated from this reaction, recent findings suggest an equilibrium exists between the carbene and 1.22.  117  While these  results did not lead to the isolation of a stable carbene molecule, this idea did stimulate interest into the incorporation of a carbene unit in an N-heterocyclic manifold.  19  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  Ph  ^CCI  -N  -N  N-  •N  N  N'  3  -N  I  Ph  Ph  J  Ph  1.21 Figure 1.8.  Ph  Ph  Ph  Ph  1.22  Attempted synthesis of an N H C by chloroform elimination.  The first stable N H C was isolated by Arduengo in 1991.  118  Deprotonation of  bis(l-adamantyl)imidazolium chloride with NaH provides the first stable crystalline N H C compound, which melts at 240-241°C without decomposition. Since this discovery, other methods for the  syntheses of NHCs have been reported, which includes  desulfurization of imidazole-2(3H)-thiones  119  the  and methanol elimination by thermolysis of  5-methoxy-.l,3,4-triphenyl-4,5-dihydro-lH-l,2,4-triazoles (Figure 1.9).  120  N  N  CI R  ^  N  ^ -  N  ^ -  R  Base  l-l  Figure 1.9.  OMe  Reported methodology for the synthesis of NHCs.  The stability of NHCs originates mainly from electronic factors, but steric factors also play a role. The presence of two adjacent nitrogen donors asserts a mesomeric effect  20  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  on the divalent carbon carbene atom. The electron deficient nature of the carbene atom is reduced by the derealization of the two nitrogen lone pairs into a vacant p orbital on the carbon atom and results in a four electron three-centered % system.  Furthermore, the  carbene lone pair is stabilized inductively by the electronegative nitrogen atoms (Figure 1.10). As a result, a large o-p energy separation is present, which allows NHCs to exist n  in the singlet ground state configuration.  (a) Figure 1.10.  1.8.  (b)  a) 7i-Stabilization and b) inductive effects of NHCs.  Transition Metal Complexes With Carbene Ligands  1.8.1. Transition Metal Acyclic Carbene Complexes 121  The first transition metal-carbene complex was discovered by Fischer in 1964. These complexes, historically referred to as Fischer-carbene complexes, feature a lowvalent transition metal fragment and a carbene bearing at least one 71-donating substituent (Figure 1.11). As a result, the carbene atom has an electrophilic nature. The metal-carbon bond is best described as a donor-acceptor interaction resulting from the superposition of 122  carbene to metal o-donation and metal to carbene 7i-back donation.  21  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  (OC) W=C 5  /  OMe  \  Ph  It Metal  RoC!  (b)  (a)  Figure 1.11. (a) A n example and (b) schematic representation of donor-acceptor bonding in Fischer-carbene complexes. A second class of transition metal-carbene complexes was identified by Schrock in the 1970's.  123  These Schrock-carbene or alkylidene complexes feature a high  oxidation state metal and a carbene bearing two alkyl substituents (Figure 1.12). The carbene possesses a nucleophilic nature and forms a covalent bond with the metal. The metal-carbene bond can be regarded as an interaction between a carbene fragment in the 122 triplet state with two spin parallel electrons on the metal centre.  (CH ) ( BuCH ) Ta=C^ 3  3  t  2  3  H  Metal  (b)  (a)  Figure 1.12.  (a) A n example and (b) schematic representation of covalent bonding in Schrock-alkylidene complexes.  22  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  Transition metal complexes of the acyclic carbenes described in chapter 1.7.1 are also known. The coordination of aryl(phosphoranyl), and aryl(amino)  127  124  amino(silyl), amino(alkyl), 125  126  carbene ligands to rhodium were found to yield thermally stable metal  complexes, which melt at temperatures above 150°C. In one case, a thermally sensitive aryl(phosphoranyl) carbene complex was observed to isomerize to an n'-phosphaalkene complex at -10°C.  124  While the coordination of these carbenes has been investigated,  their application in transition-metal-mediated catalysis has yet to be reported.  1.8.2. Transition Metal NHC Complexes  In 1968, the first metal-NHC complexes were reported independently by Wanzlick and Ofele (Figure 1.13). '  128 129  Since this discovery, N H C complexes of almost  all the transition metals have been reported. NHCs are strong a donors and very weak nacceptors, despite having an empty p,t orbital. Unlike the Fischer- and Schrock-carbene complexes, N H C ligands have been reported to stabilize transition metals in both low and high oxidation states.  Given their a-donating ability, NHCs have been compared to  other strong a-donors such as phosphines. Probably the aspect that has propelled the use of NHCs to prominent levels has been their ability to replace phosphine ligands to generate catalytic precursors 77 78  counterparts. ' '  more  robust  and versatile  than  their  phosphine  1 ^fl 1 "^7  "  These attractive features have stimulated the use of NHCs as  essential ligands for L T M complexes in homogeneous catalysis and small molecule activation processes. 2+  2 CI0 " 4  Figure 1.13.  Metal-NHC complexes reported by Wanzlick and Ofele.  23  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  E T M complexes utilizing N H C ligands have generally been regarded as chemical curiosities, with reports focused on the routine coordination of an N H C ligand to an ETM  133-136  For example, the addition of T i C l to a 1,3-dialkyl substituted N H C gives the 4  N H C titanium complex 1.23 (Equation 1.3).  137  X-ray diffraction studies performed on  this and other E T M N H C complexes show a pure a-donor character of the NHC-metal bond.  Furthermore, the C - N bond distances in these metal complexes feature bond  lengths that are intermediate between free carbenes and imidazolium salts, which suggests a 7c-delocalization in the N H C five membered ring.  Me  (1.3)  TiCL  TiCL  -N Me  1.23 1.9.  Late Transition Metal NHC Complexes in Homogeneous Catalysis  N H C complexes of LTMs have found applications in many different catalytic processes, some of which have been traditionally carried out using phosphine-based systems.  Due to their remarkable stability, N H C complexes have shown promise as  catalysts in C-Si, C-C, C-N, and C - H bond activation processes.  80,138  "  142  One example  where NHCs have matched phosphine analogs in generating an active and robust catalyst involves the Ru-mediated ring closing metathesis of olefins.  142  The replacement of one  tertiary phosphine in complex 1.24 with an N H C ligand yields 1.25 (Figure 1.14). While both 1.24 and 1.25 exhibit similar catalytic activities for the ring closing metathesis of diethyldiallylmalonate, the N H C complex 1.25 shows remarkable stability in air and to prolonged heating. This observation is in marked contrast to 1.24, which decomposes after a short period of heating.  24  References begin on page 27.  Chapter One: Dinitrogen  Chemistry and Ligand  Design  Cy R 3  PCy  1.24 Figure 1.14.  3  1.25  Modification to a Ru catalyst with an N H C ligand.  N H C donors have also been effectively incorporated into a chelating ligand to yield catalysts that can be electronically and sterically attenuated. For example, pincer ligands containing N H C donors have been reported to be effective auxiliary ligands in several palladium catalyzed cross coupling reactions. " 143  145  Both bidentate and tridentate  N H C ligands with phosphine and pyridine donors have been used with good success in the Heck reaction. Examples of these catalysts are given in Figure 1.15.  (a) Figure 1.15.  1.10.  (b)  Examples of a) phosphine and b) pyridine N H C metal complexes for Heck catalysis.  Scope of This Thesis  This introduction has highlighted the origins of coordination and organometallic chemistry, and the potential for organometallic complexes and biological systems to  25  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  promote dinitrogen activation and cleavage. This daunting task has been shown to be influenced by the ligands surrounding the metal centre.  E T M complexes with  amidophosphine ligands have been used extensively in the Fryzuk group for the activation and cleavage of N . Recent work has focused on the effects that changing the 2  electronic nature of the donating group in the ligand and the modification of the ligand backbone would have on dinitrogen activation.  The focus of this thesis is to both  explore the cleavage of an N ligand and to prepare a dinitrogen complex with a 2  coordinated N H C ligand. In chapter 2 the reactivity of the tantalum dinitrogen complex ([NPN]Ta) (u2  H) (|a-n :n -N2) with several zirconium hydride reagents is explored. Activation of the l  2  2  dinitrogen unit occurs and is followed by unique functionalization of one of the cleaved nitrogen atoms.  The mechanism of this process is investigated and new methods to  cleave a coordinated N ligand are suggested. 2  The synthesis of group 4 metal complexes stabilized by the [NCN] ligand is the focus of chapter 3. Several [NCN] precursors are synthesized and used to prepare group 4-amido, -halide, and -alkyl complexes. The stability of the metal-NHC bond towards dissociation from the metal centre is probed, as is the thermal stability of several hafnium dialkyl compounds. Chapter 4 examines the reactivity and application of [NCN] complexes synthesized in chapter 3. The migratory insertion reactivity of the hafnium dialkyl derivatives with carbon monoxide, substituted isocyanides, and several cumulenes is investigated. A cationic zirconium-methyl complex is also evaluated for its potential to polymerize a-olefins. This chapter also explores the attempted synthesis of a group 4 dinitrogen complex in addition to other N - N containing complexes. Chapter 5 explores the synthesis of Ta(V) [NCN] complexes using both synthetic and theoretical methods. The attempted synthesis of a tantalum [NCN] trialkyl complex results in the formation of products that result from C - H bond activation of the [NCN] ligand.  The mechanism of this reaction is probed by DFT calculations and isotopic  labeling experiments. The final chapter briefly details the synthesis of chiral group 4 [NCN] complexes and evaluates their potential as catalysts in asymmetric intramolecular hydroamination.  26  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  1.11.  References  (1)  Kauffman, G. B. Chem. Ind. (London) 1998, 1027.  (2)  Jorgensen, S.M.J. Prakt. Chem. 1886.  (3)  Kauffman, G. B. Educ. Chem. 1967, 4,11.  (4)  Hantzsch, A.; Werner, A. Ber. Dtsch. Chem. Ges. 1890, 23, U.  (5)  Werner, A. Z Anorg. Chem. 1897,15, 1.  (6)  Huheey, J. E. Inorganic Chemistry. 3rd Ed, 1983.  (7)  Douglas, B.; McDaniel, D.; Alexander, J. Concepts and Models of Inorganic Chemistry. 2nd Ed, 1983.  (8)  Kauffman, G. B.; Brock, W. H.; Jensen, K. A.; Klixbuell Joergensen, C. J. Chem. Ed. 1983, 60, 509.  (9)  Collman, J. P.; Hegedus, L. Principles and Applications of Organotransition Metal Chemistry, 1980.  (10)  Wilkinson, G.; Rosenblum, M . ; Whiting, M . C ; Woodward, R. B. J. Am. Chem. Soc. 1952, 74,2125.  (11)  Kealy, T. J.; Paulson, P. L. Nature 1951,168, 1039.  (12)  Miller, S. A.; Tebboth, J. A.; Tremaine, J. F. J. Chem. Soc. 1952, 632.  (13)  Tolman, C. A. Chem. Soc. Rev. 1972,1, 337.  (14)  Ault, A. J. Chem. Ed. 2002, 79, 572.  (15)  Casey, C. P. J. Chem. Ed. 2006, 83, 192.  (16)  Katz, J. H. J. Clin. Invest. 1961, 40, 2143.  (17)  Uauy, R.; Olivares, M . ; Gonzalez, M . Am. J. Clin. Nutr. 1998, 67, 952S.  (18)  MacKay, B. A.; Fryzuk, M . D. Chem. Rev. 2004,104, 385.  (19)  Fryzuk, M . D.; Johnson, S. A. Coord. Chem. Rev. 2000, 200-202, 379.  (20)  Hidai, M . ; Mizobe, Y. Pure Appl. Chem. 2001, 73, 261.  (21)  Hidai, M . ; Mizobe, Y. Met. Ions Biol. Syst. 2002, 39, 121.  (22)  Hidai, M . Coord. Chem. Rev. 1999,185-186, 99.  (23)  Pickett, C. J. J. Biol. Inorg. Chem. 1996,1, 601.  (24)  Chart, J.; Dilworth, J. R.; Richards, R. L. Chem. Rev. 1978, 78, 589.  (25)  Bazhenova, T. A.; Shilov, A . E. Coord. Chem. Rev. 1995,144, 69.  27  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  (26)  Hidai, M ; Mizobe, Y . Chem. Rev. 1995, 95, 1115.  (27)  Gambarotta, S. J. Organomet. Chem. 1995, 500, 117.  (28)  Lehninger, A . L.; Nelson, D. L.; Cox, M . M . Principles of Biochemistry, Pt. 2. 2nd Ed, 1993.  (29)  Howard, J. B.; Rees, D. C. Chem. Rev. 1996, 96, 2965.  (30)  Burgess, B. K . ; Lowe, D. J. Chem. Rev. 1996, 96, 2983.  (31)  Kastner, J.; Hemmen, S.; Blochl, P. E. J. Chem. Phys. 2005, 123, 074306/1.  (32)  Postgate, J. Modern Coordination Chemistry 2002, 233.  (33)  Appl, M . Ammonia:  (34)  Haber, F. Nobel Lectures, Including Presentation  Principles and Industrial Practice, 1999. Speeches and Laureates'  Biographies; Elsevier Pub. Co. for the Nobel Foundation: Amsterdam, 1918. (35)  Bosch, C. Nobel Lectures, Including Presentation  Speeches and Laureates'  Biographies; Elsevier Pub. Co. for the Nobel Foundation: Amsterdam, 1931. (36)  Allen, A . D.; Senoff, C. W. Chem. Commun. 1965, 621.  (37)  Allen, A. D.; Bottomley, F.; Harris, R. O.; Reinsalu, V . P.; Senoff, C. V. J. Am. Chem. Soc. 1967, 89, 5595.  (38)  Sutton, L . E.; Editor Tables of Interatomic Distances and Configuration  in  Molecules and Ions: Supplement 1956-1959 (Chemical Society (London) Special Publication  No. 18), 1965.  (39)  Stoicheff, B. P. Can. J. Phys. 1954, 32, 630.  (40)  Manriquez, J. M . ; Bercaw, J. E. J. Am. Chem. Soc. 1974, 96, 6229.  (41)  Pool, J. A.; Lobkovsky, E.; Chirik, P. J. Nature 2004, 427, 527.  (42)  Yamamoto, A . ; Pu, L. S.; Kitazume, S.; Ikeda, S. J. Am. Chem. Soc. 1967, 89,  3071. (43)  Archer, L . J.; George, T. A . Inorg. Chem. 1979, 75, 2079.  (44)  Perthuisot, C ; Jones, W. D. New J. Chem. 1994,75, 621.  (45)  Olivan, M . ; Caulton, K . G. Inorg. Chem. 1999, 38, 566.  (46)  Amoroso, D.; Yap, G. P. A . ; Fogg, D. E. Can. J. Chem. 2001, 79, 958.  (47)  Ernst, M . F.; Roddick, D. M . Organometallics 1990, 9, 1586.  (48)  Bianchini, C ; Peruzzini, M . ; Zanobini, F. Organometallics  28  1991,10, 3415.  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  (49)  George, T. A . ; Rose, D. J.; Chang, Y.; Chen, Q.; Zubieta, J. Inorg. Chem. 1995, 34, 1295.  (50)  Fryzuk, M . D.; Kozak, C. M . ; Bowdridge, M . R.; Patrick, B. O.; Rettig, S. J. J. Am. Chem. Soc. 2002,124, 8389.  (51)  Papenfuhs, B.; Dirnberger, T.; Werner, H. Can. J. Chem. 2006, 84, 205.  (52)  Cummins, C. C. Chem. Commun. 1998, 1777.  (53)  Laplaza, C. E.; Cummins, C. C. Science 1995, 268, 861.  (54)  Cui, Q.; Musaev, D. G.; Svensson, M . ; Sieber, S.; Morokuma, K. J. Am. Chem. Soc. 1995, 777,12366.  (55)  Mendiratta, A . ; Cummins, C. C ; Kryatova, O. P.; Rybak-Akimova, E. V . ; McDonough, J. E.; Hoff, C. D. J. Am. Chem. Soc. 2006,128, 4881.  (56)  Clentsmith, G. K . B.; Bates, V . M . E.; Hitchcock, P. B.; Cloke, F. G. N . J. Am. Chem. Soc. 1999, 121, 10444.  (57)  Yandulov, D. V.; Schrock, R. R. J. Am. Chem. Soc. 2002, 124, 6252.  (58)  Yandulov, D. V . ; Schrock, R. R. Science 2003, 301, 76.  (59)  Fryzuk, M . D.; Haddad, T. S.; Mylvaganam, M . ; McConville, D. H.; Rettig, S. J. J. Am. Chem. Soc. 1993, 115, 2782.  (60)  Fryzuk, M . D.; Haddad, T. S.; Rettig, S. J. J. Am. Chem. Soc. 1990,112, 8185.  (61)  Walstrom, A.; Pink, M . ; Tsvetkov, N . P.; Fan, H.; Ingleson, M . ; Caulton, K . G. J. Am. Chem. Soc. 2005,127, 16780.  (62)  Cohen, J. D.; Fryzuk, M . D.; Loehr, T. M . ; Mylvaganam, M . ; Rettig, S. J. Inorg. Chem. 1998,57,112.  (63)  Fryzuk, M . D.; Mylvaganam, M . ; Zaworotko, M . J.; MacGillivray, L . R. Polyhedron 1996,15, 689.  (64)  Cohen, J. D.; Mylvaganam, M . ; Fryzuk, M . D.; Loehr, T. M . J. Am. Chem. Soc. 1994, 116,9529.  (65)  Fryzuk, M . D.; Williams, H . D.; Rettig, S. J. Inorg. Chem. 1983, 22, 863.  (66)  Fryzuk, M . D.; Williams, H . D. Organometallics 1983, 2, 162.  (67)  Fryzuk, M . D.; Love, J. B.; Rettig, S. J. Chem. Commun. 1996, 2783.  (68)  Fryzuk, M . D.; Corkin, J. R.; Patrick, B. O. Can. J. Chem. 2003, 81, 1376.  (69)  Fryzuk, M . D.; Love, J. B.; Rettig, S. J.; Young, V . G. Science 1997, 275, 1445.  29  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  (70)  Fryzuk, M . D.; Kozak, C. M . ; Patrick, B. O. Inorg. Chim. Acta 2003, 345, 53.  (71)  Johnson, S. A., Ph. D. thesis, University of British Columbia, 2000.  (72)  Morello, L.; Yu, P.; Carmichael, C. D.; Patrick, B. O.; Fryzuk, M . D. J. Am. Chem. Soc. 2005,127, 12796.  (73)  MacLachlan, E. A.; Fryzuk, M . D. Organometallics 2005, 24, 1112.  (74)  Fryzuk, M . D.; MacKay, B. A.; Johnson, S. A.; Patrick, B. O. Angew. Chem. Int. Ed. 2002, 41, 3709.  (75)  MacKay, B. A.; Johnson, S. A.; Patrick, B. O.; Fryzuk, M . D. Can. J. Chem. 2005, 55,315.  (76)  MacKay, B. A.; Patrick, B. O.; Fryzuk, M . D. Organometallics 2005, 24, 3836.  (77)  Herrmann, W. A . ; Kocher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2162.  (78)  Regitz, M . Angew. Chem., Int. Ed. Engl. 1996, 35, 725.  (79)  Igau, A.; Grutzmacher, H.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 1988, 110, 6463.  (80)  Bourissou, D.; Guerret, O.; Gabbaie, F. P.; Bertrand, G. Chem. Rev. 2000,100, 39.  (81)  Schuster, G. B . Adv. Phys. Org. Chem. 1986, 22, 311.  (82)  Sander, W.; Bucher, G.; Wierlacher, S. Chem. Rev. 1993, 93, 1583.  (83)  Wanzlick, H . W.; Kleiner, H . J. Angew. Chem., Int. Ed. 1961, 73, 493.  (84)  Wanzlick, H . W.; Esser, F.; Kleiner, H . J. Ber. 1963, 96, 1208.  (85)  Moss, R. A. Acc. Chem. Res. 1980,13, 58.  (86)  Moss, R. A. Acc. Chem. Res. 1989, 22, 15.  (87)  Bethell, D. Adv. Phys. Org. Chem. 1969, 7, 153.  (88)  Zimmerman, H . E.; Paskovich, D. H. J. Am. Chem. Soc. 1964, 86, 2149.  (89)  Tomioka, H.; Hirai, K.; Fujii, C. Acta Chem. Scand. 1992, 46, 680.  (90)  Terazima, M . ; Tomioka, H.; Hirai, K.; Tanimoto, Y.; Fujiwara, Y.; Akimoto, Y . J. Chem. Soc, Faraday Trans. 1996, 92, 2361.  (91)  Tomioka, H.; Nakajima, J.; Mizuno, H.; Sone, T.; Hirai, K. J. Am. Chem. Soc. 1995,117, 11355.  (92)  Harrison, J. F.; Liedtke, R. C ; Liebman, J. F. J. Am. Chem. Soc. 1979,101, 7162.  (93)  Harrison, J. F. J. Am. Chem. Soc. 1971, 93, 4112.  30  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  (94)  Bauschlicher, C. W., Jr.; Schaefer, H . F., Ill; Bagus, P. S. J. Am. Chem. Soc. 1977, 99,7106.  (95)  Feller, D.; Borden, W. T.; Davidson, E. R. Chem. Phys. Lett. 1980, 77, 22.  (96)  Schoeller, W. W. Tetrahedron Lett. 1980, 21, 1505.  (97)  Schoeller, W. W. Tetrahedron Lett. 1980, 21, 1509.  (98)  Schoeller, W. W. J. Chem. Soc, Chem. Commun. 1980, 124.  (99)  Pauling, L . J. Chem. Soc, Chem. Commun. 1980, 688.  (100)  Modarelli, D. A . ; Morgan, S.; Platz, M . S. J. Am. Chem. Soc. 1992,114, 7034.  (101)  Richards, C. A., Jr.; Kim, S.-J.; Yamaguchi, Y.; Schaefer, H . F., Ill J. Am. Chem. Soc. 1995, 777, 10104.  (102)  Myers, D. R.; Senthilnathan, V . P.; Platz, M . S.; Jones, M . , Jr. J. Am. Chem. Soc. 1986,108, 4232.  (103)  Baceiredo, A.; Bertrand, G.; Sicard, G. J. Am. Chem. Soc. 1985, 707, 4781.  (104)  Igau, A.; Baceiredo, A.; Trinquier, G.; Bertrand, G. Angew. Chem., Int. Ed. 1989, 707,617.  (105)  Goumri-Magnet, S.; Kato, T.; Gornitzka, H.; Baceiredo, A . ; Bertrand, G. J. Am. Chem. Soc. 2000, 722, 4464.  (106) Ilia, O.; Gornitzka, H.; Branchadell, V.; Baceiredo, A.; Bertrand, G.; Ortuno, R. M . Eur. J. Org. Chem. 2003, 3147. (107)  Ilia, O.; Gornitzka, H.; Baceiredo, A.; Bertrand, G.; Branchadell, V.; Ortuno, R. M . J. Org. Chem. 2003, 68,1101.  (108)  Gillette, G. R.; Igau, A.; Baceiredo, A.; Bertrand, G. New J. Chem. 1991,15, 393.  (109)  Goumri-Magnet, S.; Polishchuk, O.; Gornitzka, H.; Marsden, C. J.; Baceiredo, A.; Bertrand, G. Angew. Chem. Int. Ed. 1999, 38, s3727.  (110)  Dixon, D. A.; Dobbs, K . D.; Arduengo, A. J., Ill; Bertrand, G. J. Am. Chem. Soc. 1991, 77J, 8782.  (111)  Kato, T.; Gornitzka, H.; Baceiredo, A.; Savin, A.; Bertrand, G. J. Am. Chem. Soc.  2000, 722, 998. (112)  Cattoeen, X . ; Sole, S.; Pradel, C.; Gornitzka, H.; Miqueu, K.; Bourissou, D.; Bertrand, G. J. Org. Chem. 2003, 68, 911.  31  References begin on page 27.  Chapter One: Dinitrogen Chemistry and Ligand Design  113  Solet, S.; Gornitzka, H.; Schoeller, W. W.; Bourissou, D.; Bertrand, G. Science 2001,292, 1901.  114  Merceron, N . ; Miqueu, K.; Baceiredo, A.; Bertrand, G. J. Am. Chem. Soc. 2002, 124, 6806.  115  Merceron-Saffon, N . ; Baceiredo, A.; Gornitzka, H.; Bertrand, G. Science 2003, 301, 1223.  116  Wanzlick, H . W.; Schikora, E. Angew. Chem. 1960, 72, 494.  117  Denk, M . K.; Hatano, K.; Ma, M . Tetrahedron Lett. 1999, 40, 2057.  118  Arduengo, A . J., Ill; Harlow, R. L.; Kline, M . J. Am. Chem. Soc. 1991,113, 361.  119  Kuhn, N . ; Kratz, T. Synthesis 1993, 561.  120  Enders, D.; Breuer, K.; Raabe, G.; Runsink, J.; Teles, J. H.; Melder, J.-P.; Ebel, K.; Brode, S. Angew. Chem., Int. Ed. Engl. 1995, 34, 1021.  121  Fischer, E. O.; Maasboel, A. Angew. Chem. 1964, 76, 645.  122  Taylor, T. E.; Hall, M . B. J. Am. Chem. Soc. 1984, 106, 1576.  123  Schrock, R. R. J. Am. Chem. Soc. 1974, 96, 6796.  124  Despagnet, E.; Miqueu, K.; Gornitzka, H.; Dyer, P. W.; Bourissou, D.; Bertrand, G . J . Am. Chem. Soc. 2002,124, 11834.  125  Canac, Y.; Conejero, S.; Donnadieu, B.; Schoeller, W. W.; Bertrand, G. J. Am. Chem. Soc. 2005,127, 7312.  126  Lavallo, V . ; Mafhouz, J.; Canac, Y.; Donnadieu, B.; Schoeller, W. W.; Bertrand, G. J. Am. Chem. Soc. 2004, 126, 8670.  127  Cattoeen, X . ; Gornitzka, H.; Bourissou, D.; Bertrand, G. J. Am. Chem. Soc. 2004, 126, 1342.  128  Wanzlick, H . W.; Schoenherr, H. J. Angew. Chem., Int. Ed. Engl. 1968, 7, 141.  129  Oefele, K. J. Organomet. Chem. 1968,12, P42.  130  Arduengo, A . J., Ill; Krafczyk, R. Chem. Z. 1998, 32, 6.  131  Dullius, J. E. L.; Suarez, P. A . Z.; Einloft, S.; de Souza, R. F.; Dupont, J.; Fischer, J.; De Cian, A . Organometallics 1998, 77, 815.  132  Arduengo, A . J., Ill Acc. Chem. Res. 1999, 32, 913.  133  Abernethy, C. D.; Codd, G. M . ; Spicer, M . D.; Taylor, M . K . J. Am. Chem. Soc. 2003,725,1128.  32  References begin on page 2 7.  Chapter One: Dinitrogen Chemistry and Ligand Design  (134) Kernbach, U . ; Ramm, M . ; Luger, P.; Fehlhammer, W. P. Angew. Chem., Int. Ed. Engl. 1996,55,310. (135) Herrmann, W. A.; Munck, F. C ; Arms, G. R. J.; Runte, O.; Anwander, R. Organometallics 1997,16, 682. (136)  Oldham, W. J., Jr.; Oldham, S. M . ; Smith, W. H.; Costa, D. A.; Scott, B. L.; Abney, K. D. Chem. Commun. 2001, 1348.  (137) Kuhn, N . ; Kratz, T.; Blaeser, D.; Boese, R. Inorg. Chim. Acta 1995, 238, 179. (138)  Grubbs, R. H. Adv. Synth. Catal. 2002, 344, 569.  (139)  Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402.  (140) Marko, I. E.; Sterin, S.; Buisine, O.; Mignani, G.; Branlard, P.; Tinant, B.; Declercq, J.-P. Science 2002, 298, 204. (141) Muehlhofer, M . ; Strassner, T.; Herrmann, W. A . Angew. Chem. Int. Ed. 2002, 41, 1745. (142) Viciu, M . S.; Nolan, S. P. Top. Organomet. Chem. 2005,74, 241. (143) Lee, H . M . ; Zeng, J. Y . ; Hu, C.-H.; Lee, M.-T. Inorg. Chem. 2004, 43, 6822. (144) Peris, E.; Mata, J.; Loch, J. A . ; Crabtree, R. H . Chem. Commun. 2001, 201. (145)  Loch, J. A.; Albrecht, M . ; Peris, E.; Mata, J.; Faller, J. W.; Crabtree, R. H . Organometallics 2002, 21, 700.  33  References begin on page 27.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(ll) and Ti(II) reagents  Chapter Two  Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents 2.1.  Introduction*  The conversion of N  2  to ammonia or to certain organic nitrogen-containing  products requires the activation and cleavage of the N=N triple bond. As was highlighted in chapter 1, several early transition metal complexes are capable of performing these kinds of transformations. In some cases, further functionalization of the cleaved nitrogen atoms is possible, forming new element-nitrogen bonds. In each of these examples, an ancillary ligand plays an important role in stabilizing the various transition metal oxidation states necessary for N - N bond reduction. Transition metal complexes employing amidophosphine ancillary ligands have been examined extensively in the Fryzuk group for the cleavage and functionalization of coordinated dinitrogen. For example, a diamidodiphosphine ligand [ P 2 N 2 ] (where [ P 2 N 2 ] = ( P h P ( C H S i M e 2 N S i M e C H 2 ) 2 P P h ) ) has been effectively used to stabilize a dinuclear 2  2  dinitrogen complex of niobium ( 2 . 1 ) .  1  Thermolysis of  2.1  promotes N - N bond cleavage  to generate a reactive molecular nitride, which immediately reacts with the [P2N2] ancillary ligand to yield 2 . 2 (Scheme 2.1). The formation of 2 . 2 provides a unique *A version of this chapter has been accepted for publication {Proc. Natl. Acad. Sci. USA). 34  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  example of N - N bond cleavage followed by nitrogen atom insertion into the backbone of one of the [P2N2] macrocycles to form a bimetallic bridging nitride complex.  The stabilization of early transition metal dinitrogen complexes has also been investigated in the Fryzuk group using a diamidophosphine [NPN] ancillary ligand (where [NPN] = [(PhNSiMe CH )2PPh] '). 2  2  2  For example, reduction of a titanium  dichloride complex (2.3) employing a [NPN] ancillary ligand with 2.2 equivalents of KCs under 4 atmospheres of nitrogen yields a dinuclear titanium dinitrogen complex (Scheme 1  2  2.2).  3  This species was only identified by H and  1  P N M R spectroscopy and mass  spectrometry. Thus far, the solid state structure of this dinitrogen complex has yet to be determined. This complex slowly rearranges in solution to form the bis(phosphinimide) titanium (III) dimer 2.4. The formation of 2.4 occurs as a result of complete N - N bond cleavage, followed by nitrogen atom functionalization by the [NPN] ancillary ligand to yield a new N-P bond.  35  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(ll) reagents  Ph  Ph  Ph  Ph  Me Si'' KI  \  V N Me Sr  ci  2  2  MezSj'i  ji(n-N )Ti  |SiMe  2  ~~P.  \  Ph  Ph  V£i^SiMe \ Ph Ph  2  2  2e"  2.3  23  Ph \  Ph.  Ph.  \"H  P  \  VH  SiMe,  /N^ / X // 2 Me Siy ^ T i ' T i ^ N / Me Si, V Ph N Ph -P  29  Ph  Ph  SiMe  _SiMe iMe  2  2  2  2  \Ph  I  Ph  Ph  Ph  Ph v'''N  P==^X r / ^\,SiMe / ^ // 2 Me Si/ * " T i ^ Ti^'N/ P h  2 e"  Ph  2  SiMe  2  Me,sA  N  \ Ph  Ph  I  Ph  2.4  Scheme 2.2.  The diamidophosphine ligand [NPN] has also been used to stabilize a novel sideon end-on coordinated tantalum dinitrogen complex (2.5) (Scheme 2.3).  3  The synthesis  of this reduced dinitrogen complex is remarkable because it is formed upon exposure of a tetrahydride tantalum derivative to N , a result that is not proliferated by the use of strong 2  reducing reagents such as KCg. This dinitrogen complex has been shown to exhibit a wide range of reactivity patterns, which include reactions with electrophiles,  adduct  formation with Lewis acids, and displacement of the N moiety by terminal alkynes. 4  5  2  36  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  4  atm N  2  Et 0 2  2.5 Scheme 2.3.  The addition of simple main group hydride reagents (E-H) to the tantalumdinitrogen complex (2.5) has also been studied. These hydride addition reactions feature several common outcomes and are summarized in Scheme 2.4.  In every case, E - H  addition occurs in a 1,2-addition manner across the exposed end of the coordinated dinitrogen moiety to form, in some cases, an isolable intermediate (2.6). This leads to elimination of H2, N - N bond cleavage, and subsequent rearrangement to yield 2.7, a tantalum nitride intermediate. The addition of a second equivalent of E-H reagent to this complex leads to different outcomes, which are dependent on the hydride source. For example, the addition of a B - H reagent leads to ancillary ligand degradation (2.8), limiting the overall, usefulness of these stoichiometric transformations.  6,7  However, the  addition of a Si-H reagent results in a clean conversion to the bis(silylimide) 2.9, which was observed for the addition of butylsilane.  8  37  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(ll) reagents  2.9  2.8  Scheme 2.4.  The extension of this E - H addition chemistry to include transition metal reagents was of particular interest. This would present a unique opportunity to functionalize a coordinated dinitrogen unit with a transition metal atom. In this chapter, the reaction of 2.5 with several zirconium-hydride reagents is examined.  What results is an  unanticipated reaction that involves N - N bond cleavage without zirconium-hydride addition, or H elimination from 2.5. 2  2.2.  AttemptedHydrozirconation  of 2.5  Schwartz's reagent or zirconocene chloro-hydride is known to add in a 1,2addition fashion across the multiple bonds of alkenes, alkynes, ketones, aldehydes, and  38  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(ll) and Ti(II) reagents  nitriles. Given the success of main group hydride additions across the Ta-N bond of 2.5, 9  a similar process was envisioned that would yield a terminal tantalum hydride moiety and a new Zr-N bond. Stirring a THF solution of sparingly soluble [Cp2Zr(Cl)H] with 2.5 x  for 2 weeks generates an intense purple solution from which purple crystals of 2.10 are isolated in 35% yield (Equation 2.1). . The *H N M R spectrum reveals a C symmetric s  species in solution with one single Cp resonance at 5.38 ppm, four inequivalent silyl methyl resonances, and bridging hydrides at 11.4 ppm.  Surprisingly, no terminal  tantalum hydride resonances are observed indicating that hydrozirconation to form a species similar to 2.6 (Scheme 2.4) had not occurred. The P { ' H } N M R spectrum 31  features two singlets at 7.3 and 46.7 ppm with the downfield resonance split into a doublet ( ' j p = 34.9 Hz) when N-labelled 3.5 is used. Similar coupling is also observed 15  N  in the N{'H} spectrum with the resonance located at -185.1 ppm split into a doublet. A 15  second  1 5  N resonance is observed at 228.4 ppm. These two resonances are not mutually  coupled, implying that N - N bond cleavage has occurred.  . Ph. D  FV'M  M  ^ ^ T a ^ ( \ t I I  N  Ph \ \  Na'  o  P^  ,  -  \  Ph-M  I ^ * VN^SiMe IN N ^ •<•/„. „. S  N  u  Ph.  i  M  e  [Cp ZrH(CI)] THF 2  m  T  2  Ph  P  h  C  Ph  ^  N  2  X  r  N  ,H  Me sr ^. Me Si< f\ / \ V f N ^ P ^ Ni^v^ ^ // 2  '  Ph /  > iMe, J , JJ  n -n  S  T  \ N  2  /  (  2  A  )  f  P :  Ph 2.5  2.10  The solid state molecular structure of 2.10 was determined by an X-ray diffraction experiment. A n ORTEP depiction is shown in Figure 2.1 with selected bond lengths and angles given in Table 2.1 and crystallographic details reported in appendix A . The addition of Schwartz's reagent to 2.5 appears to yield an N - N bond cleaved product in which a zirconocene fragment has inserted between the two nitrogen atoms. No bridging hydrides are observed in the solid state molecular structure; however, these ligands are successfully modeled using X H Y D E X  1 0  and their presence confirmed by *H N M R  spectroscopy. A Ta-Ta bond interaction is observed with a Tal-Ta2 bond distance of  39  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(ll) and Ti(II) reagents  2.7007(6) A , which is similar to other Ta(IV)-Ta(IV) dinuclear complexes.  11  The  phosphinimide P=N bond distance of 1.595(9) A is also typical of other reported group 5 phosphinimide complexes. '  A bridging zirconium nitride species is also observed.  While the formation of this moiety is uncommon, the Zrl-N2 bond length (2.040(9) A ) is shorter than other bridging zirconium nitrides which range from 2.21 to 2.35 A . " 1 4  1 6  The formation of the phosphinimide group in 2.10 is presumably a result of the intramolecular attack of one of the ancillary phosphine donors at an intermediate nitride species. Such an event has been reported earlier in the Fryzuk group in the formation of dinuclear titanium phosphinimide complexes and during the thermolysis of a preformed niobium dinitrogen complex. ' The intermolecular attack of phosphines on metal nitride species also has precedence and is analogous to the formation of 2.10.  Figure 2.1.  17-19  ORTEP view of [NP(N)N]Ta(Li-H) (p -N)(TarNPN])(ZrCp ) (2.10) depicted with 50% ellipsoids; all hydrogen atoms, silyl methyl and phenyl ring carbon atoms except ipso carbons have been omitted for clarity. 2  40  J  2  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(ll) reagents  Table 2.1.  Selected bond distances ( A ) and angles (deg) for ((NP(N)N]Ta(u.-H) (u.N)(Ta[NPN])(ZrCp ) (2.10). 2  2  Bond Angles Nl-Tal-N2 Pl-Nl-Tal Nl-Zrl-N2 Tal-N2-Ta2 N3-Tal-N4 N5-Ta2-N6  Bond Lengths Tal-Ta2 2.7007(6) N1--N2 2.925(9) 1.595(9) Pl-Nl 2.102(9) Tal-Nl 2.139(8) Tal-N2 Ta2-N2 1.935(9) Zrl-Nl 2.146(9) 2.040(9) Zrl-N2 Tal-N3 2.054(9) 2.102(9) Tal-N4 2.112(10) Ta2-N5 2.119(9) Ta2-N6 2.624(3) Ta2-P2 Tal-Zrl 3.0319(11)  Surprisingly, the addition of [Cp Zr(Cl)H] 2  87.2(3) 121.5(5) 88.6(3) 82.9(3) 107.0(4) 105.6(4)  to 2.5 does not result in  x  hydrozirconation of the Ta-N bond. In this reaction, the fate of the hydride and chloride ligands derived from [Cp Zr(Cl)H] is not clear. Careful examination of the ' H N M R 2  x  spectrum during the reaction reveals the presence of H (4.54 ppm in CeD6), although this 2  was not quantified. To probe the origin of H formation, the addition of [Cp ZrH ] to 2.5 2  2  2  2  was examined and found to yield 2.10 in excellent yield (90% by N M R spectroscopy) in addition to H liberation. The evolution of H was further examined with the reaction of 2  2  the deuterated nitrogen complex ([NPN]Ta) (|a-D) (u -r| :ri -N ) (c/ -2.5) with [Cp ZrH ] 1  2  2  J  2  2  2  2  2  2  and found to yield free H and the absence of a bridging tantalum-hydride signal at 11.4 2  ppm in the ' H N M R spectrum. Given this information, a rational interpretation of the mechanism likely involves an initial reaction of [Cp Zr(Cl)H] with the parent dinitrogen complex 2.5 by chloride 2  x  for hydride exchange, which generates [Cp ZrH ] along with some unknown tantalum 2  2  2  chloride species. This chloride for hydride exchange has been observed with the addition of several main group chloride reagents to 2.5 and would account for the low yield of 2.10 when the zirconocene chloro-hydride reagent was used.  20  To examine this  hypothesis, the addition of C p Z r C l to 2.5 was examined and found to yield the 2  2  41  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(Il) and Ti(H) reagents  phosphinimide product in 20% yield (by *H N M R spectroscopy). The low observed yield is consistent with a double chloride for hydride exchange that must occur to generate [Cp ZrH ] from C p Z r C l and 2.5. 2  2  2  2  2  The observation that free H is generated during the reaction of [Cp ZrH ] with 2  2  2  2  2.5 suggests that the zirconocene hydride reagent was simply a source of a Cp Zr(II) 2  species.  To probe this phenomenon, the reaction of a known Zr(II) precursor,  [Cp Zr(py)(Me3SiC=CSiMe3)], with 2.5 was investigated. 2  The formation of 2.10 is  nearly quantitative, which suggests that reductive elimination of H from [Cp ZrH ] 2  2  2  2  occurs to generate a Cp Zr(II) species, which can then react with 2.5 to form 2.10. To the 2  best of our knowledge, this reductive elimination of H from a Zr(IV) dihydride complex 2  is quite rare. '  21 22  Directed  by  these  experiments,  a  mechanism  for  the  cleavage  and  functionalization of the dinitrogen unit in 2.5 can be postulated (Scheme 2.5). The addition of [Cp Zr(Cl)H] or [Cp ZrH ] leads to generation of a Cp Zr(II) species in 2  x  2  2  2  2  solution, which can form a simple adduct (2.11) with the tantalum dinitrogen complex, 2.5. The two electrons from the zirconium centre can then cleave the N - N bond to form 2.12, in which the central atom of the metallocene has a formal M(IV) oxidation state. The nitride moiety in this complex can then undergo intramolecular attack with one of the phosphorus atoms on the [NPN] ancillary ligand to generate the final phosphinimide product 2.10.  42  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.10  2.12  Scheme 2.5. >  2.3.  Reduction and Functionalization of 2.5 with Cp2Ti(II)  The cleavage and functionalization of 2.5 with reduced group 4 transition metal derivatives represents a new procedure for the activation of dinitrogen. As an extension, the chemistry with a related titanocene(II) derivative [Cp2Ti(Me3SiC=CSiMe3)] was examined. The reaction with 2.5 proceeds smoothly in THF at room temperature to generate 2.13 in good yield, which was characterized by N M R spectroscopy and elemental analysis (Equation 2.2). Although no solid state molecular structure was determined, the spectroscopic data is quite similar to 2.10. A C symmetric species is s  observed in the *H N M R spectrum with equivalent silyl methyl resonances, one single Cp resonance at 5.20 ppm, and bridging hydrides at 12.4 ppm. The P { ' H } N M R spectrum 31  features two singlets at 8.6 and 46.4 ppm, with the latter resonance split into a doublet 43  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(Il) and Ti(II) reagents  ('JPN = 34 Hz) when N-2.5 is used. Two 15  1 5  N resonances are observed in the  15  N{'H}  N M R spectrum at 227.5 and -185.5 ppm with the latter resonance split into a doublet with identical coupling to what was observed in the P N M R spectrum. 3 1  (2.2)  2.4.  Conclusions  Investigation into the addition of Schwartz's reagent ([Cp2Zr(Cl)H] ) to the endx  on side-on dinitrogen complex 2.5 led to the unanticipated reduction of the dinitrogen moiety without Zr-H addition. This reaction facilitates insertion of a Cp Zr fragment into 2  the N - N bond of the dinitrogen ligand. The origin of this zirconocene fragment was probed by a series of experiments, which traced its formation to the elimination of dihydrogen from  [Cp2ZrH2]2  (formed in situ by hydride for chloride exchange). A n  independent reaction between 2.5 and [Cp2Zr(py)(Me SiC=CSiMe )] confirmed that a 3  3  Cp2Zr(II) species induces the N - N bond cleavage. This Cp2Zr(II) species promotes a two-electron inner-sphere reduction of the N - N bond to generate a transient nitride species, which is susceptible to intramolecular attack by a coordinated phosphine atom of the [ N P N ] ancillary ligand to generate the observed phosphinimide in addition to a trimetallic nitride species. This process represents a new way to cleave and functionalize coordinated dinitrogen.  44  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.5.  Experimental  2.5.1. General Considerations Unless otherwise stated, all manipulations were performed under an atmosphere of dry oxygen-free argon or nitrogen by means of standard Schlenk or glovebox techniques. Anhydrous hexanes and toluene were purchased from Aldrich, sparged with dinitrogen, and further dried by passage through a tower of silica followed by passage through a tower of Ridox (or Q-5) catalyst prior to use.  Diethyl ether, pentane, and  tetrahydrofuran were purchased anhydrous from Aldrich, sparged with nitrogen, and passed through an Innovative Technologies Pure-Solv 400 Solvent Purification System. Nitrogen gas was dried and deoxygenated by passage through a column containing activated molecular sieves and MnO. C6D6, C D 3 C 6 D 5 ,  and C 5 D 5 N were dried by refluxing with sodium/potassium alloy  in a sealed vessel under partial pressure, then trap-to-trap distilled, and freeze-pumpthawed several times. Deuterated tetrahydrofuran was dried by refluxing with molten potassium metal in a sealed vessel under vacuum, then trap-to-trap distilled, and freezepump-thaw-degassed several times. Unless otherwise stated, ' H , 15  3 1  P , ' H I ' ? } , ""Pi'H}, 3  N { ' H } , L i { ' H } N M R spectra were recorded on a Bruker AMX-400 instrument with a 7  5mm BBI probe operating at 400.0 M H z for *H. P N M R spectra were referenced to 3 I  either external or internal P(OMe)3 (8 141.0 ppm with respect to 85% H 3 P O 4 at 8 0.0 ppm).  Elemental analyses and mass spectrometry (EI/MS) were performed at the  Department of Chemistry at the University of British Columbia or the Department of Chemistry at the University of Windsor. IR spectroscopy was performed on a Nicolet 4700 FT-IR spectrometer.  2.5.2. Materials and Reagents A l l materials were purchased from an appropriate supplier and purified by published methods prior to use. [({NPN} Ta )(p-H)2(p-r| :n -N2)], 1  2  D) (p-n':ri -N )], 2  2  2  3  [Cp Zr(py)(Me SiC=CSiMe )], 2  3  2  2  3  23  and  3  [({NPN} Ta )(p2  2  [Cp Ti(Me SiC=CSiMe )] 2  3  24  3  were all prepared by literature procedures.  45  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.5.3. Synthesis and Characterization of Complexes 2.10 and 2.13 Synthesis of [N(^-P=N)N]Ta(^-H) (^-N(ZrCp ))Ta[NPN] (2.10) 2  2  a) using [Cp Zr(Cl)H] : 2  x  To a mixture of Schwartz's reagent, [Cp Zr(Cl)H] , (70 mg, 0.265 mmol) and 2.5 2  x  (334 mg, 0.265 mmol, 1 equivalent) in a 50 mL Erlenmeyer flask equipped with as stir bar was added 10 mL toluene and 10 mL THF in a glove box. The mixture was capped and stirred for 1 week at 15°C, after which the red-brown color of 2.5 was converted to a dark purple. The crude purple solid 2.10 was recovered on a frit after evaporation of solvents and trituration with hexanes. X-ray quality crystals were obtained from a cooled solution of THF. Yield = 137 mg, 35%. These were also used for N M R spectroscopy and elemental analysis. 'H{ P} NMR (C D ): 8 -0.32, -0.04, -0.02, 0.08 (s, 6H each, SiC//?), 1.17 ( A M X , J 31  =  2  6  11 Hz, J  6  = 36Hz, 4H, ?CH ), 2.19 ( A M X , J  2  = 15Hz, J  2  P H  2  2  H H  P H  = 43 Hz, 4H, ?CH ), 5.38 2  (s, 10H, rj -C H ), 6.48, 6.55, 6.74, 6.95, 6.99, 7.62 (d, t, 20 H total, N-C H ),  7.99, 8.26  5  5  5  6  (dd, 4H, o-?C H ), 6  7.08, 7.12, 7.17, 7.68, (d, t, 6H total, PC H ),  5  6  H H  5  5  11.66 (d, J p = 18 Hz, 2  H  TaflTa). C{ B] NMR (C D ): 8 0.2, 0.9, 1.0, 1.8 (SiCH ), 11.9, 20.4 (PCH ), 106.1 (tj -CjH ),  l3  l  5  6  6  3  2  5  113.1, 113.9, 114.7, 117.8, 124.7, 125.2 (NC U ), 123.2, 129.0, 135.4, 137.8 (P-C U ), 6  5  6  5  153.2, 155.9 (0-PQH5).  P{'H} NMR (C D ): 8 7.3 ppm (s), 46.7 ppm (s).  31  6  6  Anal. Calc'd for C 8H74N P Si4Ta Zr:.C 46.99; H 5.03; N 5.67. Found: C 47.12; H 5.21; 5  6  2  2  N5.51.  (b) using [Cp ZrH ]2: 2  2  To an intimate mixture of [Cp ZrH ] (16 mg, 0.036 mmol) and 2.5 (92 mg, 0.072 2  2  2  mmol) in a J-Young tube was added 2 mL dg-THF in a glove box. A sealed capillary tube containing a P(OMe) standard solution was added and the mixture was sealed and 3  1  31  rotated on a mechanical stirrer for 2 weeks at room temperature. The H and P N M R confirmed the exclusive formation of 2.10 in addition to unreacted 2.5 and H formation 2  (4.54 in rf -THF) (76% yield by P N M R after 2 weeks). A similar experiment with D 3 1  8  2  46  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.5 and  [Cp2ZrH2]2  c) u s i n g  Cp2ZrCh:  yielded 2.10 and no bridging hydride resonances in the H N M R . l  To an intimate mixture of C p Z r C l (24 mg, 0.081 mmol) and 2.5 (102 mg, 0.081 2  2  mmol) in a J-Young tube was added 2 mL C(,D(, in a glove box. A sealed capillary tube containing a P(OMe)3 standard solution was added and the mixture was sealed and rotated on a mechanical stirrer for 1 week at room temperature.  The ' H and P N M R 3 1  confirmed the formation of 2.10 (20% yield by P N M R after 2 weeks) in addition to H 3 1  2  formation (4.47 ppm in CeDe).  d) u s i n g  C p Z r ( p y ) ( M e S i O C S i M e ) : 2  3  3  To a stirred solution of 2.5 (350 mg, 0.28 mmol) in 20 mL toluene was added Cp Zr(py)(Me SiCsCSiMe ) (135 mg, 0.28 mmol) dissolved in 5 mL of toluene. The 2  3  3  dark brown solution immediately darkened and the solution stirred for 8 hours. The solvent was removed under vacuum, leaving a purple residue, which was triturated with pentanes until a purple solid was retained. The resulting precipitate was recovered on a glass frit. Yield = 370 mg, 90%.  Synthesis o f  / 5  /V -[N(p-P=N)N]Ta(p-H) (p-N(ZrCp ))Ta[NPN] 2  2  2  ( /V -2.10). 75  2  1 equivalent of Cp Zr(py)(Me3SiOCSiMe ) was allowed to react with 1 2  3  equivalent of 7V -1 in a manner similar to that outlined above for the synthesis of 2.10. /5  2  1 5  N N M R ( C D ) : 8 228.4 (d, J 6  6  P N  = 5 Hz), -185.1 (d, ' j  P N  = 35).  Synthesis o f[N(p-P=N)N]Ta(p-H) (p-N(TiCp ))Ta[NPN] 2  2  (2.13).  To a stirred solution of 2.5 (300 mg, 0.24 mmol) in 20 mL toluene was added C p T i ( M e S i O C S i M e ) (83 mg, 0.24 mmol) dissolved in 5 mL of toluene. The dark 2  3  3  brown solution immediately darkened and the solution stirred for 8 hours. The solvent was removed under vacuum, leaving a purple residue, which was triturated with pentanes to yield a purple solid. Yield = 276 mg, 80%. 'H{  3 1  P} N M R  10Hz, J 2  (C D ): 6  6  8  -0.45,  -0.01, 0.07, 0.11 (s,  = 36H.z, 4 H , ?CH ), 2.05 ( A M X , J 2  P H  2  47  6H  each, SiCHj), 1.50 ( A M X , J 2  = 15Hz, J 2  H H  P H  H H  =  = 42 Hz, 4 H , ?CH ), 5.20 2  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  (s, 8H, n -C H ), 6.62-7.24 (m, 26H total, -AiH), 9.32 (dd, 4H, o-?C H ), 5  5  5  6  5  12.40 (d,  2  J p H  = 17 Hz, TaT/Ta). 13  C{'H} N M R ( C D ) : 8 0.2, 0.9, 1.1, 1.8 (SiCH ), 12.1, 20.6 (PCH ), 104.5 (n - C H ) , 5  6  6  3  2  5  5  112.5, 113.2, 113.5, 118.5, 123.6, 126.2 ( N Q H J , 122.9, 129.6, 136.9, 139.4 ( P - C H ; , 5  6  5  155.6, 156.1 (0-PQH5). 31  P{'H} N M R ( C D ) : 8 8.6 ppm (s), 46.4 ppm (s). 6  6  Anal. Calc'd for C58H74N P Si Ta Ti: C 48.40; H 5.18; N 5.84. Found: C 48.23; H 5.10; 6  2  4  2  N5.49.  Synthesis of /V -[N(n-P=N)N]Ta(^H) (ji-N(TiCp ))Ta[NPN] ( /V -2.13). /5  /5  2  2  2  2  1 equivalent of C p T i ( M e S i O C S i M e ) was allowed to react with 1 equivalent of 2  3  3  N2-2.5 in a manner similar to that outlined above for the synthesis of 2.13.  l5  ^ N j ' H } N M R ( C D ) : 8 227.5 (d, J 6  6  P N  = 5 Hz), -185.5 (d, ' J P N = 34 Hz).  48  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  2.6.  References  (1)  Fryzuk, M . D.; Kozak, C. M . ; Bowdridge, M . R.; Patrick, B . O.; Rettig, S. J. J. Am. Chem. Soc. 2002,124, 8389.  (2)  Morello, L . ; Y u , P.; Carmichael, C. D.; Patrick, B . O.; Fryzuk, M . D. J. Am. Chem. Soc. 2005, 127, 12796.  (3)  Fryzuk, M . D.; Johnson, S. A.; Patrick, B. O.; Albinati, A . ; Mason, S. A . ; Koetzle, T. F. J. Am. Chem. Soc. 2001,123, 3960.  (4)  Studt, F.; MacKay, B. A . ; Johnson, S. A . ; Patrick, B. O.; Fryzuk, M . D.; Tuczek, F. Chem. Eur. J. 2005, 11, 604.  (5)  Shaver, M . P.; Johnson, S. A.; Fryzuk, M . D. Can. J. Chem. 2005, 83, 652.  (6)  MacKay, B . A . ; Johnson, S. A . ; Patrick, B. O.; Fryzuk, M . D. Can. J. Chem.  2005, 83, 315. (7)  Fryzuk, M . D.; MacKay, B. A . ; Johnson, S. A . ; Patrick, B. O. Angew. Chem. Int. Ed. 2002, 41, 3709.  (8)  Fryzuk, M . D.; MacKay, B. A.; Patrick, B. O. J. Am. Chem. Soc. 2003,125, 3234.  (9)  Bertelo, C. A . ; Schwartz, J. J. Am. Chem. Soc. 1976, 98, 262.  (10)  Orpen, A . G. Dalton Trans. 1980, 2509.  (11)  Shaver, M . P.; Fryzuk, M . D. Organometallics 2005, 24, 1419.  (12)  Yue, N . ; Hollink, E.; Guerin, F.; Stephan, D. W. Organometallics 2001, 20, 4424.  (13)  Courtenay, S.; Stephan, D. W. Organometallics 2001, 20, 1442.  (14)  Bai, G.; Mueller, P.; Roesky, H . W.; Uson, I. Organometallics 2000,19, 4675.  (15)  Banaszak Holl, M . M . ; Wolczanski, P. T. J. Am. Chem. Soc. 1992,114, 3854.  (16)  Abarca, A . ; Martin, A . ; Mena, M . ; Yelamos, C. Angew. Chem. Int. Ed. 2000, 39, 3460.  (17)  Bennett, B. K.; Saganic, E.; Lovell, S.; Kaminsky, W.; Samuel, A . ; Mayer, J. M . Inorg. Chem. 2003, 42, 4127.  (18)  Betley, T. A.; Peters, J. C. J. Am. Chem. Soc. 2004,126, 6252.  (19)  Seymore, S. B.; Brown, S. N . Inorg. Chem. 2002, 41, 462.  (20)  Johnson, S. A . , PhD Thesis, University of British Columbia, 2000.  (21)  Chirik, P. J.; Henling, L. M . ; Bercaw, J. E. Organometallics 2001, 20, 534.  49  References begin on page 49.  Chapter Two: Promoting Dinitrogen Cleavage and Functionalization with Zr(II) and Ti(II) reagents  (22)  Edelbach, B. L . ; Rahman, A . K . F.; Lachicotte, R. J.; Jones, W. D. Organometallics 1999, 18, 3170.  (23)  Nitschke, J. R.; Zuercher, S.; Tilley, T. D. J. Am. Chem. Soc. 2000,122, 10345.  (24)  Varga, V . ; Mach, K . ; Schmid, G.; Thewalt, U.J. Organomet. Chem. 1994, 475, 127.  50  References begin on page 49.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Chapter Three  Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes 3.1  Introduction *  N-Heterocyclic carbenes have become popular ligands in coordination chemistry and in homogeneous catalysis. In particular, late transition metal complexes employing N H C ligands show strong metal carbene bonds and slow dissociation rates, properties that furnish robust and versatile catalysts. " 1  5  However, the use of these ligands in early  transition metal chemistry has little precedent.  Coordination of neutral donors, such as  NHCs, to d° metal centres often results in complexes that display enhanced lability of the neutral ligand since back donation from the metal to ligand is not possible. In an effort to examine this tendency, NHCs with pendant anionic donors have been synthesized, in anticipation that this modification would anchor the ligand to the metal centre and enable the strength of the metal-carbene bond to be monitored. The first systematic study of the lability of E T M and lanthanide N H C complexes was performed utilizing an amido-functionalized N H C ligand.  6  Aminolysis reactions  involving a lithium bromide adduct of this bidentate ligand and M(N(SiMe3)2)3 (M=Y, *A portion of this chapter has been published (Spencer, L . ; Winston, S.; Fryzuk, M . D . Organometallics 2004,25,3372). 51  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  samarium and yttrium, the lability of the N H C donor was investigated and found to dissociate from the metal centre in the presence of M e  2  NCH2CH NMe2 2  and P h P = 0 . 3  M = Y, Sm, Nd, Ce Scheme  ETM  3.1  alkoxide-functionalized N H C complexes have also been reported. '  Uranium(IV) complexes bearing this ancillary ligand display a unique example of a metal complex with a free unbound N H C donor (Scheme 3.2).  7  This donor is capable of  reacting with other Lewis acids to generate simple acid-base adducts. Further reactivity of the uranium-bound carbenes was observed with the addition of other metal fragments, such as Mo(CO) , and functional groups like B H . Although this may be useful for the 4  3  introduction of molecules into the coordination sphere of the uranium(IV) metal, these results provide further proof of the hemilabile nature of NHCs when coordinated to electropositive metals.  52  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Scheme 3.2  Interest in N H C ligands with pendant anionic groups is not limited to bidentate examples. A tridentate carbene donor system has been reported employing two anionic phenoxide donors with a centrally disposed N H C unit (Scheme 3.3).  Preliminary  research with titanium derivatives has been reported with no mention of N H C dissociation. Although this aspect was not addressed, it seems likely that the central disposition of the N H C in this tridentate binding motif might anchor the N H C donor to an electropositive metal centre.  53  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  'Bu  'BU  Scheme  3.3  In light of these results, a tridentate donor system was designed that would incorporate an N H C flanked by two anionic amido arms. It was anticipated this pincer architecture would render the carbene stable to dissociation because of its central position between two anionic donors. This design creates a ligand which will be abbreviated by the formula ^ [ N C N ] , where A r refers to an aryl substituent on the amido donor and [NCN] refers to the diamido-NHC ligand. Ar  The synthesis and coordination of this  [NCN] ligand to group 4 transition metals is the subject of discussion in this chapter.  3.2.  Synthesis of [NCN]H2 Ar  and Lithium Derivatives  To construct a N H C with two pendant amine arms, the reduction of several bis(amide) imidazolium chloride precursors was examined. Addition of substituted 2chloroacetamides to imidazole produces 3.1-3.3 in reasonable yields (Scheme 3.4). The 13  C { ' H } N M R spectrum of 3.1 features an amide resonance at 170.5 ppm, in addition to  54  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes appropriate imidazolium and aryl resonances. Reduction of the amide derivative 3.1 with borane-dimethylsulfide gives the desired bis(amino)-imidazolium chloride in reasonable yield. Both ' H and C { ' H } N M R spectra are consistent with the expected product (3.4) 13  as evidenced by the disappearance of the amide  C resonance in the  1J  C{'H} N M R  spectrum. The H N M R spectrum shows two multiplets for the newly formed ethylene !  spacers and an amino - N H resonance at 5.74 ppm.  2 ArNHCOCH CI 2  p-dioxane, NEt , A  N^^NH  3  -[HNEt ]CI  W  3  CI  O'  NH  0  /  \Ar  Ar 4.4 B H - S M e THF 3  Ar = 4 - M e C H 6  2  O  HN  3.1  4  2,4,6-Me C H 3  2,6- Pr C H  6  2  2  Ar  6  3.2 3.3  i  3  Ar  Ar = 4 - M e C H 6  3.4  4  Scheme 3.4.  Incorporation of more sterically demanding aryl amido groups required a different synthetic approach.  Unfortunately, the reduction of bis(amide) imidazolium chlorides  (3.2, 3.3) with borane was unsuccessful, leading only to decomposition of the starting materials.  Introduction of mesityl (2,4,6-Me3CeH ) and 2,6-diisopropyl (2,6-'Pr C6H3) 2  2  groups was accomplished by melting the appropriately substituted imidazole and N substituted 2-chloroethylamine. This provided the imidazolium chlorides 3.5 and 3.6 in near quantitative yield (Equation 3.2). The ' H and C { ' H } N M R spectra of 3.5 and 3.6 l3  are similar to 3.4 with the presence of symmetrical ethylene spacer and amino groups.  55  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  ArNHCH CH CI 2  2  +  ArHN  N  150°C  N  NvJS^N  (3.2)  \=J  Ar = 2,4,6-Me C H 3  6  2,6-^20^3  2  3.5 3.6  X-ray quality crystals of 3.5 were grown from C H 3 C N and analyzed by X-ray crystallography.  A n ORTEP depiction of the solid state molecular structure of 3.5 is  shown in Figure 3.1.  Relevant bond lengths and angles are listed in Table 3.1, and  crystallographic details are located in appendix A. The presence of a chloride counterion confirms the synthesis of an imidazolium moiety. In addition, a C l - N l bond length of 1.326(4) and N1-C1-N2 bond angle of 109.4(3)° is observed, typical of other reported imidazolium compounds. " 9  Figure 3.1.  11  ORTEP view of [ N C H N ] H - C l (3.5) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  2  56  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Table 3.1.  Selected Bond Distances (A) and Bond Angles (°) for and [ N C N ] H , (3.8).  Mes  [ N C N ] H - C l (3.5) 2  Mes  2  Bond Lengths (3.5) Cl-Nl 1.326(4) C1-N2 ' 1.325(4)  Bond Angles (3.5) N1-C1-N2 109.4(3)  Bond Lengths (3.8) Cl-Nl 1.365(3)  Bond Angles (3.8) N1-C1-N3 102.2(2)  Deprotonation of imidazolium halide precursors 3.4-3.6 with KN(SiMe3)  2  proceeds cleanly to give NHCs 3.7-3.9 in near quantitative yield (Equation 3.3). Both H !  and  13  C { ' H } N M R spectra of 3.7 and 3.8 are consistent with a symmetrical molecule.  The presence of a carbene moiety is signified by the absence of the resonance attributed to the iminium proton (at C ) , an upfield shift in the heterocycle protons in the C4 5 2  positions, and a weak carbene moiety.  1 3  ;  C resonance at 211.4 ppm (3.7) and 215.0 (3.8) ppm for the  Deprotonation of 3.6 with one equivalent of KN(SiMe3) at -30°C 2  resulted in the isolation of a highly soluble yellow oil. Although H N M R spectroscopy !  of the oily product confirmed the presence of 3.9, other unidentifiable resonances were present.  Given this observation, the highly soluble carbene 3.9 was generated in situ  from 3.6 and used as a THF solution for further reactions.  -NKN(SiMe ) 3  2  (3.3)  >  THF  *  - HN(SiMe ) 3  NH  2  HN  - KCI Ar  Ar  Ar = 4 - M e C H 6  3.7  4  2,4,6-Me C H 3  6  2,6- Pr C H i  2  6  3  2  3.8 3.9  Colourless crystals of 3.8 were grown from a saturated hexane solution and were analyzed by X-ray diffraction.  A n ORTEP depiction of the solid state molecular  structure of 3.8 is given in Figure 3.2. Relevant bond lengths and angles are listed in  57  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Table 3.1, and crystallographic details are located in appendix A . The N1-C1-N3 bond angle is 102.2(2)°, significantly smaller than the imidazolium chloride precursor 3.5, which is consistent with other reported systems. " 9  Figure 3.2.  11  ORTEP view of [ N C N ] H , (3.8) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  2  Metathesis reactions with Li2[NPN] have successfully been used in the Fryzuk group in the synthesis of [NPN] metal complexes.  12  Along this line, the synthesis of  Li [NCN] was investigated. The addition of two equivalents of fl-BuLi to 3.7 and 3.8 2  yielded L i  tol 2  [NCN]  (3.10) and L i  Mes 2  [NCN]  (3.11), respectively (Equation 3.4).  Unfortunately, the low solubility of these complexes has prevented a solid state molecular structure determination; however, the ' H N M R spectra of both species in dspyridine shows broad resonances indicative of the desired products. For example, the H !  N M R spectrum of 3.10 reveals two multiplets assigned to the ethylene spacers, one signal for aryl-methyl and imidazole environments, and two doublets for the para-substituted aryl ring. The ^ C j / H } N M R spectrum shows a weak resonance at 189.9 ppm, which is similar to other reported L i - N H C compounds.  58  6  Additionally, a broad L i resonance is 7  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  observed at 2.86 ppm in the L i N M R spectrum. Reasonable structures are shown in 7  Equation 3.4 and based on the analogy of the arrangement of lithium ions observed in the dianionic diamidophosphine Li2[NPN].  12  r\  ,N  + NH  -30°C -2BuH  HN.  \  Ar  PhMe,  2 n-BuLi  (3.4) \  ^\Li//,  / # <  Ar  Ar  Ar Ar = 4-MeC H 6  3.10  4  Ar = 2,4,6-Me C H 3  3.3.  6  2  3.11  Attempted Syntheses of an [NCN] Ligand with an Aryl Backbone Ar  The substitution of the ethylene backbone for an aryl-derived spacer could impose a rigid six-membered metallacycle and potentially force a meridional geometry upon coordination of the ligand to a transition metal. With this in mind, the syntheses of appropriately substituted imidazolium (3.12) and imidazolinium (3.13) derivatives (Figure 3.3) were investigated.  'NH  HN'  A/  "NH  A/  Ar 3.12  Figure 3.3.  HN' Ar  3.13  Imidazolium (3.12) and imidazolinium (3.13) candidates with an aryl backbone.  The synthesis of 3.12 could be envisioned from the ring closure of an appropriately substituted diimine with paraformaldehyde (Scheme 3.5).  This type of 13  reaction has found success in the synthesis of other imidazolium complexes.  59  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Unfortunately, the synthesis of a substituted diimine precursor has proven to be problematic. The reaction between N-phenyl-orr/zo-phenylenediimine with glyoxal was examined and found to yield a bis(benzimidazole) derivative.  Substitution of benzil or  14  2,3-butanedione for glyoxal was also investigated in an attempt to prevent the formation of benzimidazole derivatives. However, no reaction was observed between /Y-phenylor/Tzo-phenylenediimine and these glyoxal derivatives using experimental conditions that have been successful in the synthesis of diimines.  13  Ph  \ / Ph Ph  Ph 3 / | 2  Scheme  3.5.  The synthesis of N-substituted diamines was also examined with a goal to ring close these compounds to generate the imidazolinium complex 3.13. A precursor to 3.13, a  substituted  tetraamine  nitrofluorobenzene  (3.14),  was  synthesized  and 1,2-ethylenediamine  in  (Scheme 3.6).  several 15  steps  from  2-  Palladium catalyzed  coupling of the aniline 3.14 with two equivalents of mesityl bromide produced the desired mesityl-substituted tetraamine 3.15 in an overall yield of 86%.  60  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  +  1/2  /  HoN  \  NH  DMA ^ NH  2  HN  K2CO3  100°C  N0  2  0 N 2  H NNH -H 0 2  2  2  .Graphite, EtOH  NH  HN  .NH  Pd (dba) , rac-BlNAP 2  HN.  3  2 MesBr, Na0 Bu 4  NH / Mes  HN \ Mes  3.15  Scheme 3.6. Ring closure of the tetraamine  with triethylorthoformate  and ammonium  tetrafluoroborate was anticipated to yield the imidazolinium tetrafluoroborate derivative 3.13.  !  H and C { ' H } N M R spectroscopy showed an asymmetric compound in solution 13  with inequivalent ethylene spacer, aryl, and imidazole resonances, in addition to an imidazolinium resonance at 10.04 ppm in the *H N M R spectrum. spectroscopic  evidence,  the  formation  of  the  asymmetric  Given this  benzimidazolium  tetrafluoroborate compound 3.16 is postulated (Scheme 3.7).  61  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Mes  3.16  Scheme 3.7.  3.4.  Synthesis of Group 4 [NCN] Amido, Chloride, and Alkyl Complexes The coordination of the [NCN] ancillary ligand onto group 4 transition metals can  be easily achieved by either amine or alkyl elimination reactions. For example, treatment of a THF solution Zr(NEt )4 with 3.7 proceeded smoothly at room temperature to afford 2  t0  '[NCN]Zr(NEt )2 (3.17) in high yield (Equation 3.5). Complex 3.17 was characterized 2  by ' H and C { ' H } N M R spectroscopy and shows equivalent N E t moieties along with 13  2  equivalent amido side arms of the '[NCN] unit; on the basis of this data a C t0  2 v  symmetry  can be assigned to this five-coordinate complex. The C { ' H } N M R spectrum shows a 13  resonance at 188.8 ppm indicative of a metal-carbene moiety. The aminolysis reactions of 3.8 and 3.9 with Zr(NEt )4 yielded no reaction at room temperature and when heated 2  provided a mixture of intractable materials. The absence of a reaction may be attributed to the increase in steric bulk at the amido nitrogen position on the [NCN] architecture. Incorporation of the bulkier  Mes  [ N C N ] and ' [ N C N ] ancillary ligands on zirconium was D  PP  achieved by aminolysis reactions with Zr(NMe )4. These reactions occurred immediately 2  at room temperature to provide the desired [NCN]Zr(NMe ) products 3.18 and 3.19. Ar  2  62  2  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  These aminolysis reactions have also been used with T i ( N M e 2 ) 4 and H f ( N M e 2 ) 4 to give 3.20 and 3.21, respectively.  (3.5)  RN 2  M M M M M  NR  A  r  2  3.17 = Zr, Ar = 4-MeC H , R = Et = Zr, Ar = 2,4,6-Me C H , R = Me 3.18 3.19 = Zr, Ar = 2,6- Pr C H , R = Me 3.20 = Ti, Ar = 4-MeC H , R = Me = Hf, Ar = 2,4,6-Me C H , R = Me 3.21 6  4  3  6  3  6  2  6  4  2  i  3  6  2  X-ray quality crystals of 3.17 were grown from E t 2 0 and the solid state molecular structure was determined by X-ray crystallography. A n ORTEP depiction of 3.17 is shown in Figure 3.4.  Relevant bond lengths and angles are listed in Table 3.2, and  crystallographic details are located in appendix A . The ligand assumes a quasi-planar orientation to produce a distorted trigonal pyramidal metal centre.  One of the six-  membered chelating rings of [NCN] is nearly planar, with a N l - C l - Z r l - N 3 torsion angle of -0.8°. However, the other six-membered chelate ring is distorted from planarity as noted by the N 2 - C l - Z r l - N 4 torsion angle of 34.2°. The Z r l - C l bond length of 2.421(6) A is slightly shorter than previously characterized lengths of Zr-based N H C compounds (2.432(3)-2.456(3) A ) ,  1 6 , 1 7  most likely a result of the ligand architecture that pulls the  carbene donor closer to the metal. The Zr-N amido bond lengths average to 2.113(6) A and are comparable to other Zr-amide complexes. " 18  63  21  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  ellipsoids; all hydrogen atoms have been omitted for clarity. Table 3.2.  Selected Bond Distances ( A ) and Bond Angles (°) for [NCN]Zr(NEt )2, tol  2  (3.17). Bond Angles 141.7(4) N3-Zrl-N4 75.0(2) N3-Zrl-Cl 77.9(2) N4-Zrl-Cl 147.2(4) N5-Zrl-Cl N6-Zrl-Cl 104.1(3) N5-Zrl-N6 108.6(3) -0.8 Nl-Cl-Zrl-N3 34.2° N2-Cl-Zrl-N4  Bond Lengths Zrl-Cl Zrl-N3 Zrl-N4 Zrl-N5 Zrl-N6  2.421(6) 2.190(6) 2.169(5) 2.058(6) 2.036(6)  The reaction of 3.8 with T i ( N M e 2 ) 4 does not produce the expected bis(amide) titanium complex.  The *H and  13  C{'H} N M R spectra showed a product with C  s  symmetry (3.22) in solution with four multiplets observed for the ethylene spacers, two doublets for the imidazole groups, two distinct aryl signals, two aryl-methyl signals, and a broad resonance attributed to the N M e 2 groups. This suggests that the [NCN] ligand is present in the amide-amine configuration shown in Equation 3.6.  64  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  /  Ar  (3.6) Hr^NMe Ti / \ Me N 2 N  M  H 2  e  2  Ar = 2 , 4 , 6 - M e C H 3  6  2  3.22  The solid state molecular structure of 3.22 was determined by an X-ray diffraction experiment from crystals grown from an E t 0 solution (Figure 3.5). 2  Relevant bond  lengths and angles are listed in Table 3.3, and crystallographic details are located in appendix A .  The ligand coordinates in an amide-amine donor configuration on a  distorted trigonal bipyramidal titanium metal centre. The Ti-N amide bond lengths are typical of other reported titanium amide complexes " length.  16-28  as is the T i l - C I N H C bond  Although introduction of the [NCN] ligand is incomplete, the formation of a  new Ti-C N H C bond was encouraging.  Thus far, all attempts to promote the  coordination of the other pendant amine donor by thermolysis have been unsuccessful.  Figure 3.5.  ORTEP view of [ N C N H ] T i ( N M e ) (3.22) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  2  65  3  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Table 3.3.  Selected Bond Distances ( A ) and Bond Angles (°) for [ N C N H ] T i ( N M e ) , (3.22).  Mes  2  3  Bond Angles 82.18(6) N3-TH-C1 88.37(6) N5-Til-Cl 177.91(6) N7-TH-C1 123.09(6) N3-Til-N5 97.37(6) N3-TU-N7  Bond Lengths 2.3382(18) Til-Cl 1.9983(14) Til-N3 1.9650(15) Til-N5  Coordination of both amide donors to form  Mes  [ N C N ] T i ( N M e 2 ) 2 was achieved by  a metathesis reaction between the dilithiated [NCN] derivative 3.11 and C l 2 T i ( N M e 2 ) 2 (Equation 3.7).  This reaction proceeded immediately in toluene to give a dark red  product in 68% yield.  In solution, the ' H N M R spectrum is consistent with a  symmetrical species in solution with diagnostic C and ' H resonances expected for 3.23. 1 3  Although elemental analysis studies agree with the formation of 3.23, attempts to grow crystals suitable for X-ray diffraction study have been unsuccessful.  Ar = 2 , 4 , 6 - M e C H 3  6  2  3.23  Treatment of the group 4 bis(amide) metal complexes with excess MesSiCl in toluene gave the metal dichloride complexes in quantitative yield (3.24-3.29) (Equation 3.8). These complexes are extremely insoluble in many common organic solvents, which may indicate a dimeric structure in the solid state. " 29  32  Although no solution  spectroscopic data could be obtained, the empirical formulae of 3.24-3.29 were confirmed by mass spectrometry and elemental analysis. The addition of pyridine to a suspension of 3.24 in toluene resulted in the isolation of the pyridine adduct 3.30. Complex 3.30 is soluble in many common organic solvents, which has allowed full  66  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  characterization by spectroscopic and X-ray diffraction studies. The N M R data for 3.30 clearly show the presence of resonances for coordinated pyridine along with ligand resonances. The Zr-carbene carbon in 3.30 appears as a weak singlet at 187.9 ppm in the 13  C{'H} N M R spectrum.  CT )-^CT ; ^ \ . N  .". M  / A  / V RN  r  2  NR  . / N  - 2 Me SiNR ^ 3  \ . N  2  J  \  A  r  A  / r  ., M  /  T  / V  N  \  CI* CI = Zr, Ar = 4-MeC H = Zr, Ar = 2,4,6-Me C H = Zr, Ar = 2,6- Pr C H = Ti, Ar = 4-MeC H = Ti, Ar = 2,4,6-Me C H = Hf, Ar = 2,4,6-Me C H A  2  M M M M M M  6  r  4  3  6  6  2  2  i  3  6  4  3  3  6  6  2  2  3.24 3.25 3.26 3.27 3.28 3.29  Crystals of 3.30 were grown from a concentrated benzene solution and analyzed by single-crystal X-ray diffraction. A n ORTEP depiction of 3.30 is given in Figure 3.6 with relevant bond lengths and angles listed in Table 3.4, and crystallographic details located in appendix A . In the solid state, the zirconium centre is coordinated by the tridentate [NCN] ligand in addition to pyridine. The two chlorides adopt a mutually cis tol  position with the [NCN] ligand in a meridional orientation to generate a pseudooctahedral arrangement around the central Zr atom. Both of the six-membered chelating rings of [NCN] are nearly planar, with N 2 - C l - Z r l - N 4 and N l - C l - Z r l - N 3 torsion angles of 1.2° and 7.5°, respectively; however, each ring has the carbon a to the amido donor sitting above or below in the solid state. The Zr-C carbene bond length is similar to 3.17 but still shorter than previously characterized lengths of Zr-based N H C compounds.  17  The Zr-N amido bond lengths average to 2.138(4) A and are comparable to other Zramide complexes. " '  The Zr-Cl bond distances are not unusual as is the Zr-N bond  length of the pyridine donor (2.398(5) A).  67  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Figure 3.6.  ORTEP view of [NCN]ZrCl (py) (3.30) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 3.4.  Selected Bond Distances (A) and Bond Angles (°) for [NCN]ZrCl (py), (3.30).  tol  2  tol  2  Bond Angles N3-Zrl-N4 N5-Zrl-Cl N4-Zrl-Cll Cll-Zrl-Cll N2-Cl-Zrl-N4 Nl-Cl-Zrl-N3  Bond Lengths Zrl-Cl Zrl-N3 Zrl-N4  2.391(5) 2.167(4) 2.109(4)  155.27(16) 84.02(18) 94.77(14) 170.38(14) 1.2 7.5  Given the ease of N H C dissociation in reported amide-NHC E T M complexes, ' '  6 7 34  the aspect of carbene lability in  tol  [NCN]ZrCl (py) was investigated. 2  accomplished in two ways: in the first, the  13  This was  C{*H} N M R spectrum of 3.24 in dy  pyridine, a strongly coordinating solvent, was measured. This spectrum is compared to that obtained in non-coordinating ^-benzene. In particular the chemical shift of the N heterocyclic carbene carbon resonance was monitored. In ^-pyridine this resonance is  68  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  observed at 181.0 ppm while in ^-benzene, it appeared at 187.9 ppm; the free carbene resonance observed for 3.7 is found at 211.4 ppm in ^-benzene. A second experiment involved the addition of 10 equivalents of M e 2 N C H 2 C H 2 N M e 2 to a ^-benzene solution of 3.24; in this case no change in the C { ' H } N M R resonance of the carbene carbon is 13  observed. Both of these experiments are consistent with the carbene carbon atom of the N H C in the [NCN] ancillary ligand remaining bound to the Zr centre, confirming that the flanking amido donors do anchor the N H C to the Zr(IV) centre. The preparation of dialkyl zirconium complexes was performed by both alkylation and protonolysis methods. For example, the reaction of Zr(CH SiMe3)4 with 2  3.7 produced the desired product 3.31 via SiMe4 elimination (Scheme 3.8). This complex was also synthesized from the reaction of dichloride 3 . 2 4 and two equivalents of LiCH2SiMe3; however, a better yield was obtained via the alkane elimination method at 30°C. ' H and C { ' H } N M R spectroscopy showed the presence of the desired dialkyl 13  groups in addition to expected ligand resonances. For example, the ' H N M R spectrum of 3.32 features equivalent zirconium-methyl groups with a single resonance at 0.62 ppm, in addition to equivalent amido side arms of the [NCN] unit. The C { ' H } N M R spectrum tol  13  shows a resonance at 39.7 ppm, which is characteristic of a zirconium-methyl moiety.  69  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Zr(CH R) 2  4  PhMe, -30°C - 2 CH R 3  R = SiMe-,, Ph  2 RMgCI or 2 LiCH SiMe Et 0, -30°C 2 MgCI /2 LiCI ?  Ar=tol; R=CH SiMe Me CH Ph Ar=Mes; R=Me CH Ph 2  3/  2  2  2  2  3  3.31  3.32 3.33 3.34 3.35  Scheme 3.8.  The X-ray diffraction study of a single crystal of 3.31 revealed a distorted trigonal bipyramidal geometry around the zirconium metal centre. A n ORTEP depiction of the solid state molecular structure of 3.31 is shown in Figure 3.7. Relevant bond lengths and angles are listed in Table 3.5, and crystallographic details are located in appendix A. The zirconium-carbene bond length ( Z r l - C l ) is 2.415(3) A , which is slightly longer than that found in 3.31 but still shorter than the corresponding bond distances reported for N H C zirconium complexes of the type trans-TxCi^  70  (L = NHC).  17  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic  Figure  Table  3.7.  3.5.  Carbene  Complexes  ORTEP view of [NCN]Zr(CH SiMe3)2 (3.31) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity. lol  2  Selected Bond Distances ( A ) and Bond Angles (°) for rNCN]Zr(CH SiMe ) , (3.31).  tol  2  3  2  Bond Angles 148.73(9) N3-Zrl-N4 78.23(9) N3-Zrl-Cl 76.27(9) N4-Zrl-Cl 115.29(10) C24-Zrl-Cl  Bond Lengths 2.415(3) 2.173(2) 2.135(2) 2.238(3) 2.254(3)  Zrl-Cl Zrl-N3 Zrl-N4 Zrl-C23 Zrl-C24  Alkylation of the hafnium dichloride 3.29 by Grignard reagents was the optimal method for the synthesis of dialkyl products 3.36-3.39 (Equation 3.9). In solution, the dialkyl products possess C N M R spectra.  2 v  symmetry with diagnostic  1 3  C and 'H resonances in the  For example, the 'H N M R spectrum of 3.36 shows equivalent 'H  resonances for hafnium-methyl groups at 0.12 ppm, in addition to appropriate ethylene spacer, aryl and imidazole resonances.  71  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  An ORTEP depiction of the solid state molecular structure of 3.38 is shown in Figure 3.8 and was determined from an X-ray diffraction experiment from crystals grown from E t 2 0 . Relevant bond lengths and angles are listed in Table 3.6, and crystallographic details are located in appendix A . The ligand assumes a puckered orientation with respect to a distorted trigonal bipyramidal metal centre. The mesitylamido donors are pseudo trans oriented with N4-Hfl-N3 being 151.49(8)°. The hafnium-carbene bond length (2.387(3) A ) is similar to the previously reported zirconium [NCN] complexes as are Hf-N amido (avg. 1.361(3) A ) and Hf-C 2.250(3) A ) alkyl bond lengths.  72  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Figure 3.8.  ORTEP view of [ N C N ] H f B u (3.39) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 3.6.  Selected Bond Distances (A) and Bond Angles (°) for  Mes  2  Mes  [ N C N ] H f Bu , 2  (3.38).  Bond Angles N3-HT1-N4 151.49(8) 80.30(9) N3-Hfl-Cl N4-Hfl-Cl 80.30(9) 118.02(9) C30-Hfl-Cl 134.32(9) C26-Hfl-Cl  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N4  2.385(3) 2.101(2) 2.126(2)  '  The hafnium dialkyls possess excellent thermal stability. For example, the H N M R spectrum of 3.39 remains unchanged after heating a CeD6 solution at 60°C for several weeks.  One exception is the diethyl complex  Mes  [ N C N ] H f ( C H C H ) (3.37), 2  3  2  which decomposes at room temperature to give the metallated species 3.40 and ethane (identified by ' H N M R spectroscopy) (Equation 3.10). The ' H N M R spectrum of 3.40 shows a C\ symmetric species in solution with five inequivalent aryl-methyl resonances. There are two doublets at 1.00 and 2.51 ppm indicative of two diastereotopic protons on  73  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  the metallated - C H 2 resonance, consistent with a previously described metallated mesityl group.  35  Furthermore, two multiplets at -0.10 and 0.10 ppm can be assigned to the  diastereotopic protons of the remaining - H f C i ^ group, an observation previously made with a similarly metallated - H f C H C H 3 system.  36  2  Further proof of ortho-methyl bond  activation is observed with a downfield shifted Hf-C C resonance at 72.9 ppm, a 1 3  chemical shift similar to that found for the benzylic carbons of the hafnium dibenzyl derivative 3.38.  25°C (3.10) -H3CCH3  Mes  p  u  p i _ i ^  V w r w Mes  Mes H CCH //  3  3.37  2  \  3.40  The decomposition of the deuterated diethyl complex  Mes  [NCN]Hf(CD CD ) 2  3  2  (d10-3.37) provides information on the mechanism of this metallation. Decomposition of dio-3.37 results in the liberation of tfVethane (CD3CD3: identified by GC-MS), which suggests that p-hydrogen transfer has occurred to give a reactive n -ethylene intermediate (Scheme 3.9). This intermediate is not observed in solution but readily undergoes C - H bond activation with a neighboring mesityl-methyl group to give the mono-protonated product, c^-3.40. The residual ' H resonance is observed in the ' H N M R spectrum as a broad singlet at 1.5 ppm integrating to one proton. Attempts to trap the n -ethylene 2  intermediate with PMe3 or pyridine were unsuccessful.  74  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  S c h e m e 3.9.  3.5  Conclusions  The synthesis of a potentially dianionic, tridentate N H C ligand system has been described. Incorporation of this ligand on group 4 transition metal was accomplished by protonolysis reactions with  M(NMe2)4  and alkane elimination reactions with Zr(CHiR)4  (R = Ph, SiMe3) to generate bis(amide) and dialkyl derivatives, respectively.  The  bis(amide) complexes were converted to dichloro or other dialkyl complexes by straightforward procedures. Hafnium dialkyl complexes display excellent stability, with one exception: the hafnium diethyl complex 3.37 undergoes a facile P-hydrogen transfer reaction at room temperature to yield a metallated hafnium species.  The addition of  strong donors, such as pyridine and M e 2 N C H 2 C H 2 N M e 2 , to group 4 metal complexes containing the [NCN] ancillary ligand did not show any N H C dissociation.  This  confirms that the flanking amido donors anchor the N H C to the group 4 metal centre.  75  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  The following chapters will investigate the application of these group 4 complexes and extend the coordination chemistry of the [NCN] ligand to include high oxidation state metals such as tantalum.  76  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes 3.6.  Experimental  Section  3.6.1. General Considerations  Unless otherwise stated, general procedures were performed as described in Section 2.5.1.  3.6.2. Materials and Reagents A l l chemicals were purchased from a chemical supplier and used as received. 4MeC H NHC(0)CH Cl,  37  Pr C H NHC(0)CH Cl,  39  6  i  2  6  4  3  3  2  CD CD MgBr 3  2,4,6-Me C H NHC(0)CH2Cl,  2  (H NC H NHCH ) 2  6  4  2  6  (3.14),  15  2  were all prepared by literature methods.  41  2  2,6-  38  2  was prepared by a modification of literature procedure.  Zr(CH SiMe ) 2  3  and  40 4  2,4,6-Me C H NHCH CH Cl 3  6  2  2  2  42  3.6.3. Synthesis and Characterization of Complexes 3.1 - 3.40 Synthesis Dipp  of  tol  [NCHN] H Cl co  2  Mes  (3.1),  [NCHN] H Cl  (3.2),  co  2  and  [NCHN] H -Cl (3.3). co  2  The following procedure is representative of the synthesis of 3.1-3.3. To a 500 mL Schlenk flask was added imidazole (1.85 g, 27.1 mmol), 4 - M e C H N H C ( 0 ) C H C l 6  4  2  (10.0 g, 54.5 mmol), and N E t (8.35 mL, 60.0 mmol). The white slurry was dissolved in 3  300 mL />dioxane and heated to reflux overnight. After cooling to room temperature, the solvent was removed in vacuo and 100 mL CH C1 added to yield a white slurry. This 2  2  white suspension was filtered and washed with several portions of C H C 1 until the 2  washings became clear.  2  The colourless microcrystalline solid was dried in vacuo  overnight and found to contain one equivalent of C H C 1 as determined by the H N M R !  2  2  spectrum. Yield = 7.60 g, 58%. 3.1: *H NMR (</ -DMSO): 5 2.24 (s, 6 H , -C// ), 5.32 (s, 4 H , -CH ), 7.12 (d, J=8 Hz, 4 H , 6  3  2  -ArH), 7.52 (d, J=8 Hz, 4 H , -ArH), 7.80 (s, 2H, -imidfl), 9.24 (s, 1H, -NC//N), 10.90 (s, 2H, -C(0)N/7).  77  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  C{ W} NMR (</ -DMSO): 5 21.1 (-CH ), 55.4 (-CH ), 119.5 (-ArC), 125.3 (-imidQ,  n  l  6  3  2  129.8 (-ArC), 132.7 (-ArC), 134.8 (-ArC), 144.6 (-NCHN), 170.5 (-C(O)NH). Anal. Calcd for C22H25CI3N4O2: C, 54.61; H , 5.21; N , 11.58. Found: C, 54.45; H , 5.02; N , 11.22. 3.2: 'H NMR (</ -DMSO): 8 2.26 (s, 12H, -o-ArCH ), 2.36 (s, 6H, -p-ArCH ), 5.12 (s, 6  3  3  4H, -CH ), 7A3 (s, -4H, -Ar//), 7.65 (s, 2H, -imid//), 9.10 (s, 1H, -NC//N), 10.54 (s, 2H, 2  -C(0)N//). C{'H} NMR (rf -DMSO): 8 21.4 (-CH ), 22.3 (-CH ), 57.2 (-CH ), 121.2 (-ArQ, 123.8  I3  6  3  3  2  (-imidC), 130.2 (-ArQ, 131.9 (-ArQ, 133.7 (-ArQ, 145.1 (-NCHN), 172.4 (-C(O)NH). Anal. Calcd. For C 5 H i N 0 2 : C, 71.57; H , 7.45; N , 13.35. Found: C, 71.44; H , 7.10; N , 2  3  4  13.46. 3.3: 'H NMR (rf -DMSO): 8 1.42 (d, J = 9 Hz, 24H, -CH(C// ) ), 3.78 (sept, J = 9 Hz, 6  3  3  4H, -C//(CH ) ), 5.24 (s, 4H, - C ( 0 ) C / / ) , 7.52-7.60 (m, 6H, -ArH), 7.83 (s, 2H, -imid//), 3  2  2  9.56 (s, 1H, -NC//N), 10.34 (s, 2H, -C(0)N//). C{'H} NMR (rf -DMSO): 8 18.5 (-CH ), 39.5 (-CH), 55.8 (-NCH ), 120.8 (-imidQ,  13  6  3  2  124.8 (-ArQ, 131.3 ( - A r Q , 133.4 ( - A r Q (-ArQ, 139.5 (-ArQ, 143.0 (-NCHN), 175.2 (C(O)NH). Anal. Calcd. For C i H C l N 0 2 : C, 69.06; H , 8.04; N , 10.39. Found: C, 69.30; H , 8.31; 3  4  43  N , 10.28.  Synthesis of [NCHN]H Cl (3.4) tol  2  A 250 mL Schlenk flask containing a magnetic stirbar was charged with 3.1CH2CI2  (lO.lg, 20.8 mmol) and THF (100 mL) was added. B H - S M e (5.0M in E t 0 , 3  2  2  18.3 mL) was added, and the white suspension was heated to reflux for 16 h with stirring. Vigorous gas evolution was noted as soon as heating commenced.  The solvent was  removed under reduced pressure leaving a white residue. Aqueous HCI (1M, 45.7 mL, 45.7 mmol) was added and the suspension refluxed for 1 h. After cooling to room temperature, solid NaOH (7.3 g, 0.18 mol) was added to the clear solution, which caused a white solid to precipitate. Addition of  CH2CI2  white solid. The solid was filtered, washed with  78  (50 mL) caused further precipitation of a CH2CI2  (3 x 20 mL), and dried in vacuo  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  overnight to give a white powder.  The solid was recrystallized from MeOH giving  colorless crystals. Yield = 3.70 g, 48%.  'H NMR (DMSO-rf ): 5 2.13 (s, 6H, -C// ), 3.40 (t, J = 5 Hz, 4H, - C / / 6  3  2  NAT),  4.28 (t,  5 Hz, 4H, -C/fcNimid), 5.74 (br s, 2H, -Ni/), 6.50 (d, J = 8 Hz, 4H, -Ar//), 6.88 (d,  J  J =  =8  Hz, 4H, -Ar//), 7.78 (s, 2H, -imid//), 9.16 (s, 1H, -imid//). C{'H} NMR (DMSO-</ ): 8 28.5 (-CH ), 50.5 (-CH N), 52.1 (-CH N), 115.3 (-ArQ,  13  6  3  2  2  125.2 (-ArQ, 126.1 (-ArQ, 130.0 (-imidQ, 138.6 (-NCHN), 140.5 (-ArQ. EI-MS: 370 [M ]. +  Anal. Calcd. for C i H C l N : C, 68.00; H , 7.34; N , 15.10. Found: C, 67.82; H , 7.10; N , 2  2 7  4  15.13.  Synthesis of 2,4,6-Me C H NHC(0)CH (imid) and 2,6- Pr C H NHC(0)CH2(iniid) i  3  The  6  following  2  2  procedure  is  3  representative  6  2  of the  Me C H NHC(0)CH (imid) and 2,6- Pr C H NHC(0)CH (imid). i  3  6  2  2  3  6  2  2  synthesis  of  2,4,6-  N a H (3.8 g, 158.3  mmol) and imidazole (9.73 g, 142.9 mmol) were combined in D M F (75 mL) and stirred for 30 minutes at 50 °C to give a clear brown solution. 2,4,6-Me C H NHC(0)CH Cl 3  6  2  2  (28.2 g, 142.9 mmol) was added portionwise over a period of 30 minutes to give an opaque solution. After stirring for 12 hours, water (20 mL) was added and all solvents were removed under reduced pressure. The resulting brown residue was acidified with 2 M HC1 (250 mL) and washed with E t 0 (3 x 150 mL). The aqueous solution was made 2  basic with excess NaOH and extracted with CH C1 (3 x 250 mL). The CH C1 was 2  2  2  2  removed to give a white crystalline material, which was washed with hexanes. Yield = 28.0 g, 86%. 2,4,6-Me C H NHC(0)CH (imid): H NMR (CDC1 ): 8 2.12 (s, 6H, -o-ArC// ), 2.25 l  3  6  2  2  3  3  (s, 3H, -/>ArC// ), 4.75 (s, 2H, -NC// ), 6.80 (s, 2H, -Ar//), 7.05 (s, 1H, -imid//), 7.10 (s, 3  2  1H, -imid//), 7.60 (s, 1H, -NC//N). C{'H} NMR (CDC1 ): 8 18.2 (-CH ), 20.5 (-CH ), 57.0 (-NCH ), 123.0 (-imidQ,  13  3  3  3  2  123.2 (-imidQ, 128.5 (-ArQ, 130.5 (-ArQ, 130.7 (-ArQ, 135.1 (-NCHN), 140.1 (-ArQ, 178.1 (-C(O)). Anal. Calc. for C i H N 0 : C, 69.11; H , 7.04; N , 17.27. Found: C, 69.00; H , 7.01; N , 4  1 7  3  17.10.  79  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  2 , 6 - P r C H N H C ( 0 ) C H ( i m i d ) : ' H N M R (CDC1 ): 5 1.16 (d, J=7 Hz, -CH(C// ) ), i  3  6  2  3  2  3  2  2.86 (sept, J=7 Hz, -C//(CH ) ), 4.87 (s, 2H, -C(0)C// ), 7.10 (s, 1H, -imid//), 7.15 (d, 3  2  2  J=8 Hz, 2H, - A r / / ), 7.21 (s, 1H, -imid//), 7.29 (t, J=8 Hz, 1H, -Ar//), 7.64 (s, 1H, imid//). 1 3  C { ' H } N M R (CDC1 ): 8 21.3 (-CH ), 36.4 (-CH), 58.7 (-NCH ), 124.1 (-imidQ, 124.6 3  3  2  (-imidQ, 127.2 (-ArQ, 130.9 (-ArQ, 131.8 (-ArQ, 137.1 (-NCHN), 142.3 (-ArQ, 174.7 (-C(O)). Anal. Calcd. for C , H N 0 C, 71.55; H , 8.12; N , 14.72. Found: C, 71.23; H , 7  2 3  3  N,  7.93;  14.55.  Synthesis o f 2 , 4 , 6 - M e C H N H C H C H ( i m i d ) 3  The  6  following  2  2  procedure  Me C H NHCH CH (imid) 3  6  2  2  is  and  2  and  2  2,6- Pr C H HCH2CH (imid) i  3  representative  of  6  2  2  the  synthesis  2,6- Pr C H HCH CH (imid). i  3  6  2  2  2  of  2,4,62,4,6-  Me C H NHCOCH (imidazole) (13.0 g, 56.8 mmol) and B H - S M e (25.0 mL,125.0 3  6  2  2  3  2  mmol, 5.0 M in Et 0) were combined in THF (500 ml) and refluxed overnight. The THF 2  was removed under reduced pressure and 2 M HCI (63 mL, 2.2 equivalents) was added to the white residue. The solution was made basic with excess NaOH (8 equivalents) and extracted with  C H 2 C I 2 (3  x 250 mL).  The  CH2CI2  was removed, and the clear oil  recrystallized with boiling hexanes. Yield = 9 . 8 g, 80%. 2,4,6-Me C6H NHCH CH (imid): 2  3  2  ]  2  H N M R (rf -DMSO):  8 2.03  6  (s, 6 H , -o-ArC// ), 3  2.15 (s, 3 H , -/>ArC// ), 3.19 (t, J = 8 Hz, - N C / / ) , 3 . 6 8 (t, J = 8 Hz, 1H, -NH), 4.13 (t, J= 3  2  8 H z , - N C / / ) , 6.80 (s, 2H, -ArH), 6.85 (s, 1H, -imid//), 7.20 (s, 1H, -imid//), 7.64 (s, 1H, 2  -NC//N). ' ^ { ' H } N M R ( r f - D M S O ) : 8 18.9 (-CH ), 22.1 (-CH ), 48.4 (-NCH ), 48.9 (-NCH ), 6  3  3  2  2  121.0 (-imidQ, 121.6 (-imidQ, 126.4 (-ArQ, 128.8 (-ArQ, 129.0 ( - A r Q , 134.2 (NCN), 142.1 (-ArQ. Anal. Calc. for C i H , N : C, 4  9  3  73.33;  H,  8.35;  N , 18.32. Found: C, 73.05; H , 8.09; N ,  18.15. 2,6- Pr C H HCH CH (imid):  ' H N M R (rf -DMSO):  i  3  6  2  2  2  6  8 1.10  (d, J=7 Hz, - C H ( C / / ) ) , 3  2  2.95 (sept, J = 7 Hz, -C//(CH ) ), 3.03 (t, J = 8 Hz, - N C / / ) , 3.98 (t, J = 8 Hz, 3  2  Ar  80  2  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  N  i m  idC// ), 2  7.02 (s, 1H, -imid//), 7.11 (d, J=8 Hz, 2H, - A r / / ) , 7.24 (s, 1H, -imid//), 7.35  (t, J=8 Hz, 1H, -Ar//), 7.80 (s, 1H, -imid//). C{ H}  NMR (</ -DMSO): 8 22.5 (-CH ), 29.6 (-CH), 50.7 (-NCH ), 51.3 (-NCH ),  l  l3  6  3  2  2  118.7 (-imidQ, 120.2 (-imidQ, 121.3 (-ArQ, 128.3 (-NCN), 129.4 ( - A r Q , 134.8 (A r Q , 138.4 (-ArQ. Anal. Calcd. for C H N C, 75.23; H , 9.28; N , 15.48. Found: C, 74.97; H , 9.45; N , 1 7  2 5  3  15.33.  Synthesis of 2,6- Pr C H NHCH CH2Cl i  2  6  3  2  2 , 6 - P r C H N H C ( 0 ) C H C l (10 g, 35.1 mmol) and B H - S M e (15.4 mL, 77.1 i  2  6  3  2  3  2  mmol, 5.0 M in E t 0 ) were dissolved in THF (250 ml) in a 500 mL Schlenk flask and 2  refluxed overnight. The THF was removed under reduced pressure and 2 M HC1 (38.6 mL, 2.2 equivalents) was added to the white residue. The solution was made basic with excess NaOH (14.04 g, 8 equivalents) and extracted with C H C 1 (3 x 50 mL). The 2  2  CH C1 was removed and the clear oil was extracted with pentane. The solvent was 2  2  removed to yield a colorless oil that was used without further purification. Yield = 8.19 g, 86 %. *H NMR ( C D C I 3 ) :  8  1.23 (d,  J  = 7 Hz, 12H, -CH(C// ) ), 3.19 (t, 3  2  J  = 8 Hz, 2H, - N C / / ) , 2  3.18 (sept, J = 7 Hz, 2H, -C//(CH ) ), 3.73 (t, J = 8 Hz, 2H, -C// C1), 7.08 (m, 3H, 3  2  2  Ar//). C{'H} NMR (CDCI3): 20.3 (-CH ), 30.6 (-CH), 45.8 (-CH C1), 51.3 (-NCH ), 125.7 (-  13  3  2  2  A r Q , 128.9 (-ArQ, 130.1 (-ArQ, 137.9 (-ArQ.  Synthesis of  Mes  [ N C H N ] (3.5) and cl  Dipp  [NCHN]  cl  (3.6)  The following procedure is representative of the synthesis of 3.5 and 3.6. 2,4,6M e C H N H C H C H C l (6.0 g, 30.4 mmol) and 2,4,6-Me C H NHCH CH (imid) (6.5 g, 3  6  2  2  2  3  6  2  2  2  30.4 mmol) were combined and stirred at 150 °C for 2 hours. The resulting white solid was washed with THF (50 mL) and filtered to give a white crystalline powder. Yield = 11.29 g, 87%. Recrystallization with boiling acetonitrile gave long colorless crystals.  81  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  3.5: 'H NMR (rf -DMSO): 5 2.01 (s, 12H, -o-ArC// ), 2.12 (s, 6H, -p-ArCH ), 6  3  3  = 8 Hz, 4H, - N C / / ) , 3.92 (t, J= 8 Hz, 1H, -N//), 4.40 (t, J= 8 Hz, 4H, - N Ar  2  imid  3.15 (q, J C / / ) , 6.81 2  (s, 4H, -ArH), 7.88 (s, 2H, -imid//), 9.35 (s, 1H, -NC//N). C{'H} NMR (rf -DMSO): 5 17.8 (-CH ), 20.2 (-CH ), 47.2 (-NCH ), 49.2 (-NCH ),  13  6  3  3  2  2  122.6 (-imidQ, 129.0 (-ArQ, 130.2 (-ArQ, 130.7 (-ArQ, 137.2 (-NCHN), 142.4 (-ArQ. Anal. Calc. for C H C 1 N : C, 70.32; H , 8.26; N , 13.12. Found: C, 70.15; H , 8.13; N , 25  35  4  13.02. 3.6: *H NMR (</ -DMSO): 8 1.19 (d, J = 7 Hz, -CH(Cr7 ) ), 2.92 (sept, J = 7 Hz, 6  3  2  Ctf(CH ) ), 3.44 (q, J = 8 Hz, 4H, - N C / / ) , 3.89 (t, J = 8 Hz, 1H, -N//), 4.90 (t, J = 8 3  2  Hz, 4H, - N ,3  Ar  imid  2  C / / ) , 7.01 (m, 6H, -ArH), 7.76 (s, 2H, -imid//), 9.16 (s, 1H, -NC//N). 2  C{'H} NMR (rf -DMSO): 8 20.2 (CH ), 33.5 (-CH), 45.9 (-NCH ), 50.3 (-NCH ), 6  3  2  2  121.5 (-imidQ, 127.6(-ArQ, 129.7 (-ArQ, 131.6 (-ArQ, 139.5 (-NCHN), 143.1 (-ArQ. Anal. Calcd. for C H 7C1N C, 72.84; H , 9.27; N , 10.96. Found: C, 72.78; H , 9.55; N , 31  4  4  10.74.  Synthesis of [NCN]H (3.7) and ,0|  Mes  2  [NCN]H (3.8) 2  The following procedure is representative of the synthesis of 3.7 and 3.8. The following procedure was used in the synthesis of 3.9; however, the product was not isolated. A THF solution (10 mL) of KN(SiMe ) (664 mg, 3.3 mmol) was slowly added 3  2  dropwise to 3.5 (1.24 g, 3.3 mmol) dissolved in 40 mL THF, creating a slightly yellow suspension. The suspension was stirred for A hr and the solvent removed in vacuo. The L  pale yellow residue was extracted with toluene (20 mL) and the solution filtered through celite. Removal of the solvent yielded a white solid which was washed several times with hexane and dried in vacuo. Yield = 1.10 g, 100%. 3.7: 'H NMR (C D ): 8 2.13 (s, 6H, -CH ), 3.40 (t, J = Hz, 4H, - C / / N ) , 4.28 (t, J = Hz, 6  6  3  2  4H, - C / / N ) , 5.74 (br s, 2H, -NH), 6.25 (s, 2H, -imid//), 6.53 (d, J = Hz, 4H, -ArH), 6.85 2  (d, J = Hz, 4H, -ArH).  "CCU} NMR (C D ): 8 22.5 (-CH ), 46.1 (-CH N), 50.9 (-CH N), 114.5 (-ArQ, 118.9 6  6  3  2  2  (-imidQ, 120.6 (-ArQ, 130.7 (-ArQ, 149.8 (-ArQ, 211.4 (-NCN). Anal. Calcd. for C , H N : C, 75.41; H , 7.84; N , 16.75. Found: C, 75.20; H , 7.49; N , 2  2 6  4  16.88.  82  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  3.8: U N M R ( C D ) : 8 2.35 (s, 6H, -/>ArC// ), 2AO (s, 12H, -o-ArC// ), 3.22 (q, J = l  6  6  3  3  8Hz, 4H, - N C / / ) , 3.76 (t, J = 8Hz, 4H, -NCH ), 4.15 (t, J = 8Hz, 1H, -NH), 6.30 (s, 2H, 2  2  imid//), 6.82 (s, 4H, -ArH). 1  3  C{'H}  ( C D ) : 8 20.0 (-o-CH ), 24.5 (-/>CH ), 48.5 (-NCH ), 49.1 (-NCH ),  N M R  6  6  3  3  2  2  121.7 (-imidQ, 126.9 ( - A r Q , 127.5 (-ArQ, 130.1 (-ArQ, 145.0 ( - A r Q , 215.0 (-NCN). Anal. Calc. for C H N : C, 76.88; H , 8.77; N , 14.35. Found: C, 76.54; H , 8.41; N , 2 5  3 4  4  14.28  Synthesis of L i  , 2  o  l  [NCN]  (3.10)  and  L i  M 2  e  s  (3.11),  [ N C N ]  The following procedure is representative of the synthesis of 3.10 and 3.11.  A  toluene solution of 3.7 (530 mg, 1.6 mmol) was cooled to -30°G and 2.0 mL of 1.6M nBuLi (3.2 mmol) was added slowly dropwise. The solution immediately darkened after the first equivalent was added and a white precipitate formed after addition of the second equivalent of base was complete. The white suspension was allowed to warm slowly to room temperature where it is stirred overnight. Filtration yielded a white powder which was washed with several portions of toluene. Yield = 549 mg, 99% yield.  3.10:  ' H N M R  8 2.29 (s, 6H, -Ar.CH ), 3.62(m, 4H, - N C / / ) , 4.13 (m, 4H, -  (C D N): 5  3  5  2  N C / / ) , 6.69 (s, 4H, -Ar//), 7.00 (s, 2H, -imid//). 2  ,  3  C{'H}  8 21.4 (-CH ), 45.6 (-NCH ), 47.2 (-NCH ), 117.9 (-ArQ,  (C5D5N):  N M R  3  2  2  120.5 (-ArQ, 122.9 (-imidQ, 126.9 (-ArQ, 148.6 (-ArQ, 189.9 (-NCN). 7  L i N M R ( C  5  H  5  N ) : 8  2.86.  Anal. Calcd. for C i H L i N : C, 72.83; H , 6.98; N , 16.18; Found: C, 72.79; H , 6.78; N , 2  2 4  2  4  16.01.  3.11:  !  H N M R  (C D N): 5  5  8 2.35 (s, 6H, -/>ArCH ), 2.46 (s, 6H, -o-ArCH ), 4.08 (m, 4H, 3  3  -NC// ), 4.18 (m, 4H, - N C / / ) , 6.81 (s, 4H, -Ar//), 6.91 (s, 2H, -imid//). 2  C{ U}  U  X  2  N M R (C5D5N): 8 20.4 (-CH ), 21.3 (-CH ), 46.8 (-NCH ), 47.8 (-NCH ), 119.5 3  3  2  2  (-ArQ, 119.9 ( - A r Q , 123.6 (-imidQ, 127.9 (-ArQ, 149.5 (-ArQ, 190.2 (-NCN). 7  L i N M R (C5D5N): 8  2.88.  Anal. Calcd. for C H L i N : C, 74.61; H , 8.01; N , 13.92; Found: C, 74.55; H , 7.95; N , 2 5  3 2  2  4  13.86.  83  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  Synthesis of (2,4,6-Me3C6H2NHC H4NHCH )2 (3.15) 6  2  A 100 mL Schlenk was charged with Pd (dba) (151 mg, 0.16 mmol), rac-BINAP 2  3  (103 mg, 0.16 mmol), NaO Bu (1.11 g, 11.6 mmol), 3.14 (1.0 g, 4.1 mmol), mesityl l  bromide (1.81 g, 9.0 mmol) and 50 mL of toluene. The mixture was slowly warmed to 100°C and stirred overnight. The dark brown suspension was filtered through Celite and the solvent removed to yield a dark red residue. Pentane (10 mL) was added to yield a brown powder that was further purified by dissolving the solid in toluene and filtering through a silica plug. Yield = 1.69 g, 86%.  'H NMR (CDC1 ): 5 2.03 (s, 12H, -o-ArC// ), 2.27 (s, 12H, -p-ArCH ), 3  3  3.56 (s, 4H, -  3  N C / / ) , 4.60 (br s, 2H, -N//), 6.22 (d, J - 8 Hz, 2H, -Ar//), 6.62 (t, J = 8 Hz, 2H, -Ar//), 2  6.80-6.86 (m, 4H, -Ar//).  C{'H} NMR  13  (CDCI3):  5 18.9 (-CH ), 20.1 (-CH ), 52.2 (-NCH ), 116.5 (-ArQ, 117.9 3  3  2  (-ArQ, 118.5 ( - A r Q , 120.3 (-ArQ, 125.6 (-ArQ, 127.9 ( - A r Q , 130.4 (-ArQ, 135.2 (ArQ. Satisfactory elemental analysis was not obtained.  Synthesis of Asymmetrical Imidazolinium tetrafluoroborate (3.16) A 25 mL Schlenk flask was charged with 3.15 (980 mg, 2.0 mmol), NH4BF4 (215 mg, 2.0 mmol), and HC(OEt) (0.31 mL, 2.0 mmol) and slowly heated to 120°C. The 3  slurry was stirred at this temperature for 1 hr, then cooled to room temperature. THF was added to give a white suspension, which was filtered and washed with several portions of THF. The white solid was dried in vacuo overnight. Yield = 968 mg, 84 %. *H NMR (rf -DMSO): 5 1.87 (s, 6H, -p-AxCHf), 6  1.89 (s, 6H, -p-AvCH ), 3  2.21 (s, 3H, -o-  A r C / / ) , 2.37 (s, 6H, -o-ArC// ), 3.81 (m, 2H, - N C / / ) , 4.89 (m, 2H, - N C / / ) , 5.04 (m, 3  3  2  2  1H, -NH), 5.71 (m, 1H, -N//), 5.82 (m, 1H, -Ar//), 6.40 (m, 1H, -Ar//), 6.55 (m, 1H, Ar//), 6.61 (m, 1H, -Ar//), 6.87 (s, 2H, -Ar//), 7.20 (m, 2H, -Ar//), 7.39 (m, 1H, -Ar//), 7.66 (m, 1H, -Ar//), 7.76 (m, 1H, -Ar//), 8.26 (m, 1H, -Ar//), 10.04 (s, 1H, -NC//N).  '^{'H} NMR (rfe-DMSO): 5 19.6 (-CH ), 20.4 (-CH ), 20.9 (-CH3), 21.8 (-CH ), 51.3 (3  3  3  NCH2), 55.0 (-NCH2), 113.5 (-ArQ, 115.8 (-ArQ, 117.9 (-ArQ, 118.3 (-ArQ, 118.9 (A r Q , 119.5 (-ArQ, 120.4 (-ArQ, 120.9 (-ArQ, 123.3 ( - A r Q , 124.7 (-ArQ, 125.2 (-  84  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  ArC), 126.3 (-ArQ, 127.5 (-ArQ, 128.5 (-ArQ, 129.3 (-ArQ, 131.6 (-ArQ, 132.7 (A r Q , 133.6 (-ArQ, 135.2 (-ArQ, 137.2 (-ArQ, 143.4 (-NCHN). Satisfactory elemental analysis was not obtained.  Synthesis of (NCN)M(NMe ) [(M=Zr, Ar=tol, R=Et (3.17); M=Zr, Ar=Mes, Ar  2  2  R=Me (3.18); M=Zr, Ar=Dipp, R=Me (3.19); M=Ti, Ar=tol, R=Me (3.20); M=Hf, Ar=Mes, R=Me (3.21)] The following procedure is representative of the synthesis of 3.17-3.21.  In the  case of 3.19, the carbene 3.9 was generated in situ and used as a THF solution. A cooled (-30°C) THF (10 mL) solution of Hf(NMe ) (415 mg, 1.17 mmol) was slowly added 2  4  dropwise to 3.8 dissolved in THF (20 mL).  The mixture was warmed to room  temperature gradually and stirred overnight. After the solvent was removed in vacuo and toluene (15 mL) added, the solution was filtered and the solvent removed to give a pale orange solid, that was recrystallized with Et 0/hexanes at -30°C to give a white powder 2  Yield = 662 mg, 85%. 3.17: 'H NMR (C D ): 5 1.10 (t, J=8 Hz, 12H, - N C H C / / ) , 2.35 (s, 6H, -CH ), 3.40 (m, 6  6  2  3  3  4H, - C / / N ) , 3.44 (q, J = 8 Hz, 8H, - N C / / C H ) , 3.92 (m, 4H, - C / / N ) , 5.80 (s, 2H, 2  2  3  2  imid//), 7.10 (d, J=8 Hz, 4H, -ArH), 7.15 (d, J = 8Hz, 4H, -ArH). C{ H}  13  l  NMR (C D ): 5 17.5 (-CH CH ), 23.0 (-CH ), 50.7 (-CH N), 51.2 (-CH N), 6  6  2  3  3  2  2  53.4 (-ZrNCH ), 119.9 (-ArQ, 120.6 (-imidQ, 127.2 (-ArQ, 130.1 (-ArQ, 157.6 (2  A r Q , 188.8 (-NCN). Anal. Calcd. for C H 4 N Z r : C, 61.33; H, 7.81; N , 14.80. Found: C, 61.11; H , 7.74; N , 29  4  6  14.56. 3.18: H NMR (C D ): 5 2.21 (s, 6H, -/>ArC// ), 2.40 (s, 12H, -o-ArC// ), 2.67 (s, 12H, !  6  6  3  3  -NMe ), 3.34 (m, 4H, -NCH ), 3.61 (m, 4H, - N C / / ) , 6.02 (s, 2H, -imid//), 6.96 (s, 4H, 2  2  2  ArH).  C{'H} NMR (C D ): 5 19.6 (-o-CH ), 23.4 (-p-CR ), 45.6 (-NCH ), 48.8 (-NCH ),  13  6  6  3  3  3  2  49.2 (-NCH ), 122.4 (-imidQ, 130.5 (-ArQ, 132.3 (-ArQ, 132.9 (-ArQ, 140.2 (-ArQ, 2  190.9  (-ZrC  carb  ene).  Anal. Calc. for C H N Z r : C, 61.33; H , 7.81; N , 14.80. Found: C, 61.20; H , 7.58; N , 29  44  6  14.45.  85  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  3.19: ' H N M R ( C D ) : 5 1.20 (d, J = 8 Hz, 12H, -CH(C// ) ), 1.35 (d, J = 8 Hz, 12H, 6  6  3  2  CH(C// ) ), 2.43 (s, 12H, -N(CH ) ), 3.24 (sept, J = 8 Hz, 4H, -C//(CH ) ), 3.86 (m, 4H, 3  2  3  2  3  2  N C / / ) , 4.13 (m, 4H, - N C / / ) , 5.98 (s, 2H, -imid//), 6.98-7.03 (m, 6H, - Ar//). 2  2  ' ^ { ' H } N M R ( C D ) : 8 21.4 (CH ), 31.6 (-CH), 46.7 (-NCH ), 49.6 (-NCH ), 51.5 (6  6  3  3  2  N C H ) , 119.9 (-imidQ, 121.2 (-ArQ, 125.8 (-ArQ, 130.4 ( - A r Q , 140.2 (-ArQ, 192.1 (2  NCN). Anal. Calc. for C35H56N6Zr: C, 64.47; H , 8.66; N , 12.89. Found: C, 64.37; H , 8.83; N , 12.75. 3.20: ' H N M R ( C D ) : 5 2.38 (s, 6H, -C// ), 2.65 (s, 12H, -N(C// ) ), 3.45 (m, 4H, 6  6  3  3  2  C / / N ) , 4.08 (m, 4H, - C / / N ) , 5.78 (s, 2H, -imid//), 7.11 (d, J=8 Hz, 4H, -Ar//), 7.20 (d, J 2  2  = 8Hz, 4H, -Ar//). ' ^ { ' H } N M R ( C D ) : 8 24.3 (-CH ), 49.6 (-CH N), 51.7 (-NCH ), 52.4 (-CH N), 118.4 6  6  3  2  3  2  (-ArQ, 120.3 (-imidQ, 127.2 (-ArQ, 132.3 (-ArQ, 155.7 ( - A r Q , 187.2 (-NCN). Anal. Calc. for C25H36N6Ti: C, 64.10; H , 7.75; N , 17.94. Found: C, 63.98; H , 7.88;N, 17.84. 3.21: *H N M R ( C D ) : 8 2.19 (s, 6H, -/>ArC// ), 2.39 (s, 12H, -o-ArC// ), 2.70 (s, 12H, 6  6  3  3  -NMe ), 3.36 (m, 4H, - N C / / ) , 3.55 (m, 4H, - N C / / ) , 5.95 (s, 2H, -imid//), 6.91 (s, 4H, 2  2  2  ArH).  C{ H}  l3  l  N M R ( C D ) : 8 19.7 (-o-CH ), 24.3 (-/?-CH ), 44.5 (-NCH ), 49.0 (-NCH ), 6  6  3  3  3  2  50.1 (-NCH ), 122.0 (-imidQ, 129.8 (-ArQ, 132.8 (-ArQ, 133.3 ( - A r Q , 142.3 (-ArQ, 2  195.7 ( - H f C  carbene  ).  Anal. Calc. for C H 4 H f N : C, 53.16; H , 6.77; N , 12.83. Found: C, 52.89; H , 6.44; N , 29  4  6  12.68.  Synthesis of  Mes  [ N C N H ] T i ( N M e ) (3.22) 2  3  A cooled (-30°C) THF (10 mL) solution of Ti(NMe ) (200 mg, 0.89 mmol) was 2  4  slowly added dropwise to 3.8 (348 mg, 0.89 mmol) dissolved in THF (20 mL). mixture was warmed to room temperature gradually and stirred overnight.  The  After the  solvent was removed in vacuo and toluene (15 mL) added, the solution was filtered and the solvent removed to give a dark red solid, that was recrystallized with Et 0/hexanes at 2  -30°C to give a red powder. Yield = 662 mg, 85%.  86  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  'H NMR (C D ): 5 2.13 (s, 6H, -o-ArC7/ ), 2.18 (s, 3H, -/>ArC// ), 2.22 (s, 3H, -p6  6  3  3  AvCHj), 2.38 (s, 6H, -o-ArC7/ ), 2.6 (t, J = 8 Hz, 1H, -NH), 3.0 (q, J = 8 Hz, 2H, 3  C / / N H ) , 3.1-3.2 (br s, 18H, - N C / / ) , 3.40 (m, 2H, -NC7/ ), 3.50 (m, 2H, -NC// ), 3.77 (t, 2  3  2  2  J = 8 Hz, -NC7/ ), 6.04 (d, J = 2 Hz, 1H, -imid//), 6.42 (d, J = 2 Hz, 1H, -imid//), 6.78 (s, 2  2H, -Ar//), 7.01 (s, 2H, -Ar//). C{'H} NMR (C D ): 8 19.5 (-CH ), 20.2 (-CH ), 22.6 (-CH ), 22.9 (-CH ), 45.8 (-  ,3  6  6  3  3  3  3  N C H ) , 47.8 (-NCH ), 49.8 (-NCH ), 51.3 (-NCH ), 117.8 ( - A r Q , 118.5 (-ArQ, 119.6 (2  2  2  2  imidQ, 120.6 (-imidQ, 128.9 (-ArQ, 129.8 (-ArQ, 130.5 ( - A r Q , 132.6 (-ArQ, 148.7 (A r Q , 149.9 (-ArQ, 192.6 (-NCN). Satisfactory elemental analysis was not obtained.  Synthesis of [NCN]Ti(NMe ) (3.23) Mes  2  2  To a cooled (-30°C) solution of C l T i ( N M e ) (103 mg, 5.0 mmol) in THF (10 2  2  2  mL) was slowly added a THF solution of 3.11 (200 mg, 5.0 mmol). The solution was left to stand at -30°C for 15 minutes and then slowly warmed to room temperature. The red solution was stirred overnight at which time the solvent was removed to dryness, toluene added, and the solution filtered through Celite. The volume was reduced to several mL's and hexane added to yield a dark red powder. Yield = 1.78 g, 68%. 'H NMR (C D ): 8 2.22 (s, 6H, -p-ArCH ), 6  6  2.40 (s, 6H, -o-ArC// ), 2.78 (br s, 12H, -  3  3  N(C77 ) ), 3.35 (m, 4H, -C77 ), 3.60 (m, 4H, -CH ), 6.05 (s, 2H, -imid//), 6.95 (s, 4H, 3  2  2  2  Ar//). C{'H} NMR (C D ): 8 20.5 (-CH ), 22.4 (-CH ), 50.6 (-NCH ), 52.4 (-NCH ), 54.1 (-  ,3  6  6  3  3  3  2  N C H ) , 117.9 (-imidQ, 120.4 (-ArQ, 128.0(-ArQ, 131.7 (-ArQ, 143.7 (-ArQ, 193.7 (2  NCN). Anal. Calc. for C H 4 N T i : C, 66.40; H , 8.45; N , 16.02. Found: C, 66.52; H , 8.80; N , 2 9  4  6  15.89.  Synthesis of (NCN)MCl [(M=Zr, Ar=tol (3.24), M=Zr, Ar=Mes (3.25), M=Zr, Ar  2  Ar=Dipp (3.26), M=Ti, Ar=tol (3.27), M=Ti, Ar=Mes (3.28), M=Hf, Ar=Mes (3.29)] The following  procedure is representative of the synthesis of 3.24-3.29.  Chlorotrimethylsilane (1.03 mL, 8.14 mmol) was added dropwise to a toluene (20 mL)  87  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  solution of 4 ( 5 3 3 mg, 0.81 mmol) with vigorous stirring. The white suspension was stirred overnight and collected by filtration to give a white powder.  Yield = 4 9 5 mg,  95%.  3.24: EI-MS: 4 9 4 [M ] +  Anal. Calcd. for C2iH 4Cl2N Zr: C, 51.00; H , 4.89; N , 11.33. Found: C, 50.65; H , 4.53; 2  4  N , 11.28. 3.25: EI-MS: 562 [M ] +  Anal. Calc. for C 5 H 3 2 C l N Z r : C, 5 4 . 5 3 ; H , 5.86; N , 10.17. Found: C, 54.36; H , 5.44; N , 2  2  4  10.01. 3.26: EI-MS: 634 [M ] +  Anal. Calcd. for C i H C l N Z r : C, 58.65; H , 6.99; N , 8.83. Found: C, 58.95; H , 7.21; N , 3  44  2  4  8.95.  3.27: EI-MS: 451 [M ] +  Anal. Calcd. for C iH24Cl N Ti: C, 55.90; H , 5.36; N , 12.42. Found: C, 55.78; H , 5.52; 2  2  4  N , 12.23. 3.28: EI-MS: 507 [M ] +  Anal. Calcd. for C H C l N T i : C, 59.19; H , 6.36; N , 11.04. Found: C 59.26; H , 6.45; 2 5  3 2  2  4  N , 10.89. 3.29: EI-MS: 638 [M ] +  Anal. Calc. for C 5H32Cl HfN4: C, 47.07; H , 5.06; N , 8.78. Found: C, 46.85; H , 4.86; N , 2  2  8.53.  Synthesis of [NCN]ZrCl (py) (3.30) ,oI  2  The pyridine adduct was formed by suspending a portion of the solid 3.24 in toluene and adding an excess of pyridine. The solution was filtered, and the solvent was reduced in volume (~ 2 mL). Hexane was then added to precipitate a red-orange solid. Further recrystallization from a saturated solution of benzene afforded red-orange crystals of3.30-l/2C H . 6  ' H  NMR  6  (C D ): 6  6  5 2.18 (s, 6 H , -CH ), 3.60 (m, 3  4H,  - C / / N ) , 4.15 (m, 2  4H,  - C / / N ) , 5.92 2  (s, 2H, -imid//), 6.42 (br s, 2H, -py//), 6.74 (br s, 1H, -py//), 6.90 (d, J = Hz, 4 H , -Ar//), 7.49 (d, J = Hz, 4 H , -ArH), 8.58 (br s, 2H, -py//).  88  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  C{'H} NMR (C D ): 5 23.0 (-CH ), 51.4 (-CH N), 52.9 (-CH N), 119.3 (-ArQ, 121.3  ,3  6  6  3  2  2  (-imidQ, 124.1 (-ArQ, 126.9 (-ArQ, 131.4 (-ArQ, 136.3 (-ArQ, 150.4 (-ArQ, 156.1 (A r Q , 187.9 (-NCN). Anal. Calcd. for C H C l N Z r : C, 56.85; H , 5.26; N , 11.43. Found: C, 56.80; H , 5.33; 29  32  2  5  N , 11.40.  Synthesis of [NCN]ZrR [(Ar = tol, R = CH SiMe (3.31), Me (3.32), CH Ph (3.33); Ar  2  2  3  2  Ar = Mes, R = Me (3.34), CH Ph (3.35)] 2  Method A (SiMe elimination): To a cooled (-30°C) THF solution (10 mL) of 4  3.7 (90 mg, 0.27 mmol) was added dropwise a cooled (-30°C) THF solution (5 mL) of Zr(CH SiMe ) (121 mg, 0.27 mmol). The solution was kept at the reduced temperature 2  3  4  for Vi hour then gradually warmed to room temperature for 15 min. The solvent was removed and the yellow residue was extracted with hexane/toluene (5:1) (3 x 10 mL). The extracts were cooled to -30°C over a period of 1 week giving a large portion of pale yellow crystal. Yield =110 mg, 67%. Method B (Alkylation): A suspension of 3.24 (103 mg, 0.21 mmol) in E t 0 was 2  cooled to -30°C and an E t 0 solution of L i C H S i M e (39 mg, 0.42 mmol) was slowly 2  2  3  added dropwise. The solution was allowed to gradually warm to room temperature where stirring was continued for Vz hour.  The solvent was removed and the yellow residue  extracted with hexane/toluene (5:1) (3 x 10 mL). The extracts were cooled to -30°C over a period of 1 week to give the same pale yellow crystalline material described above. Yield = 50 mg, 40%. 3.31: (Method A) H NMR (C D ): 8 0.11 (s, 18H, -CH SiMe ), 0.95 (s, 4H, !  6  6  2  3  C// SiMe ), 2.23 (s, 6H, -C// ), 3.40 (m, 4H, -C// N), 3.95 (m, 4H, - C / / N ) , 5.79 (s, 2H, 2  3  3  2  2  -imid//), 7.18 (d, J = 8 Hz, 4H, -Ar//), 7.30 (d, J = 8 Hz, 4H, -Ar//). C{ W) NMR (C D ): 6 1.4 (-SiQ, 23.5 (-CH ), 50.9 (-CH N), 54.6 (-CH N), 69.0 4 (-  n  l  6  6  3  2  2  ZrCH ), 121.0 (-ArQ, 121.4 (-imidQ, 129.4 (-ArQ, 132.7 (-ArQ, 155.2 (-ArQ, 186.8 2  (-NCN). Anal. Calcd. For C H N S i Z r : C, 58.24; H , 7.75; N , 9.37. Found: C, 58.05; 29  46  4  2  H, 7.66; N , 9.20.  89  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  3.32: (Method B ) H NMR !  (C D ): 6  6  5 0.62 (s, 6H, -ZrC// ), 2.35 (s, 6H, - C / / ) , 4.01 (m, 3  3  4H, - C / / N ) , 4.33 (m, 4H, - C / / N ) , 5.86 (s, 2H, -imid//), 6.93 (d, J = 8 Hz, 4H, -Ar//), 2  2  7.05 (d, J = 8 Hz, 4H, -Ar//).  C{'H} NMR  13  6 19.9 (-CH ), 39.7 (-ZrCH ), 50.2 (-CH N),  (C D ): 6  3  6  3  2  51.4 (-CH N), 2  118.5 (-ArQ, 120.4 (-imidQ, 127.8 (-ArQ, 130.2 (-ArQ, 148.6 ( - A r Q , 193.5 (-NCN). Anal. Calc. for C H N Z r C, 60.88; H , 6.66; N , 12.35. Found: C, 60.53; H , 6.78; N , 2 3  3 0  4  12.14.  3.33: (Method A) 'H NMR  (C D ): 6  6  5 1.85 (s, 4H,-ZrC// ), 2.35 (s, 12H, -p-AvCHf), 2  3.14 (m, 4H, - N C / / ) , 3.47 (m, 4H, - N C / / ) , 5.89 (s, 2H, -imid//), 6.79 (d, J = 8Hz, 4H, 2  2  o-CH P/7), 6.90 (t, J = 8Hz, 2H, -p-CU Ph), 7.01 (s, 4H, -Ar//), 7.26 (t, J = 8Hz, 4H, -m2  2  CH Ph). 2  C{'H} NMR  13  5 23.4 (-/>CH ), 48.3 (-NCH ), 54.6 (-NCH ), 70.3 (-ZrCH ),  (C D ): 6  3  6  2  2  2  119.8 (-imidQ, 123.1 ( - A r Q , 129.6 (-ArQ, 130.8 (-ArQ, 137.6 ( - A r Q , 145.8 (-ArQ, 150.1 (-ArQ, 195.3 (-ZrCcarbene)- Some aromatic resonances obscured by C(,De solvent. Anal. Calc. for C H N Z r C, 68.11; H , 6.58; N , 9.63. Found: C, 68.22; H , 6.67; N , 3 3  3 8  4  9.52.  3.34: (Method  B )  U NMR  l  (C D ): 6  6  8 0.33 (s, 6H, -ZrC// ), 2.20 (s, 6H, -/?-ArC// ), 2.43 3  3  (s, 12H, -o-ArC// ), 3.37 (m, 4H, - N C / / ) , 3.45 (m, 4H, - N C / / ) , 5.88 (s, 2H, -imid//), 3  2  2  6.98 (s, 4H, -Ar//).  C{'H} NMR  ,3  5 18.6 (-o-CH ), 20.0 (-/>CH ), 48.4 (-ZrCH ), 51.7 (-NCH ),  (C D ): 6  3  6  3  3  2  52.3 (-NCH ), 118.5 (-imidQ, 129.9 (-ArQ, 133.3 (-ArQ, 135.0 ( - A r Q , 148.9 (-ArQ, 2  189.8 (-ZrC -bene)cal  Anal. Calc. for C H N Z r : C, 63.61; H , 7.51; N , 10.99. Found: C, 63.33; H , 7.32; N , 2 7  3 8  4  10.75.  3.35: (Method B ) 'H NMR  (C D ): 6  6  5 1.92 (s, 4H,-ZrC// ), 2.24 (s, 6H, -p-AxCHf), 2.31 2  (s, 12H, -o-ArC// ), 3.03 (m, 4H, - N C / / ) , 3.56 (m, 4H, - N C / / ) , 5.77 (s, 2H, -imid//), 3  2  2  6.84 (d, J=8Hz, 4H, -o-CH Ph), 6.92 (t, J=8Hz, 2H, -p-CH Ph), 6.98 (s, 4H, -Ar//), 7.17 2  2  (t, J=8Hz, 4H, -m-CU Ph). 2  C{'H} NMR  13  (C D ): 6  6  8 20.2 (-0-CH3), 24.3 (-p-CHf), 49.3 (-NCH ), 52.7 (-NCH ), 2  2  65.6 (-ZrCH ), 121.6 (-imidQ, 122.4 (-ArQ, 130.3 (-ArQ, 131.5 ( - A r Q , 136.6 (-ArQ, 2  90  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  148.4 (-ArQ, 156.3 (-ArQ, 190.1 (-ZrC arbene)- Some aromatic resonances obscured by C  C6D6 solvent. Anal. Calc. for C H N Z r : C, 70.75; H , 7.00; N , 8.46. Found: C, 70.43; H , 6.92; N , 39  46  4  8.35.  Synthesis C H  2  P h  of  M  e  s  (3.38), C  ( N C N ) H f ( R ) H  2  C H ( C H  3  )  2  (3.36),  [R=Me  2  C H  2  C H  3  (3.37),  C D  2  C D  3  (</io-3.37),  (3.39)]  The following procedure is representative of the synthesis of 3.36-3.39. 3.29 (400 mg, 0.63 mmol) was dissolved in 5 mL THF and cooled to -30 °C. MeMgBr (0.42 mL, 1.3 mmol, 3 M in Et 0) was added dropwise and the slightly yellow solution was stirred 2  in the dark for 30 minutes. The THF was removed under reduced pressure and to the resulting residue was added a few drops 1,4-dioxane and E t 0 (5 mL). The resulting 2  suspension was filtered through Celite and volatiles were removed to give a white solid, 3.36, which was recrystallized with E t 0 . Yield = 293 mg, 78 %. 2  3.36:  * HN M R  (C D ): 6  6  8  0.12 (s, 6H, -HfC/fc), 2.17 (s, 6H, -p-ArCH ), 2.49 (s, 12H, -o3  A r C / / ) , 3.40 (m, 4H, -NC/fc), 3.49 (m, 4H, -NC/fc), 5.90 (s, 2H, -imid//), 6.99 (s, 4H, 3  Ar//). 1  3  C{'H}  N M R  (C D ): 6  6  19.6 (-CH ), 20.7 (-CH ), 52.2 (-NCH ), 54.1 (-HfCH ), 54.2 (-  8  3  3  2  3  N C H ) , 119.5 (-imidQ, 129.6 (-ArQ, 132.3 (-ArQ, 135.3 (-ArQ, 152.1 (-ArQ, 196.1 (2  HfCcarbene)Anal. Calc. for C H H f N : C, 54.31; H , 6.41; N , 9.38. Found: C, 54.22; H , 6.26; N , 2 7  3 8  4  9.16. 3.37:  * HN M R  (C D ): 6  6  2.24 (s, 6H, -p-ArCH ), 3  8  0.62 (q, J = 8Hz, 4H, -HfC/fc), 1.49 (t, J = 8Hz, 6H, - C H C / / ) , 2  3  2.46 (s, 12H, -o-ArC// ), 3.32 (m, 2H, - N C / / ) , 3.55 (m, 4H, 3  2  N C / / ) , 5.90 (s, 2H, -imid//), 6.70 (s, 4H, -ArH). 2  C{ ll}  l3  l  N M R (C D ): 6  6  8  12.8 (-HfCH CH ), 19.7 (-CH ), 20.9 (-CH ), 51.4 (-NCH ), 2  3  3  3  2  52.5 (-NCH ), 66.1 (-HfCH CH ), 119.9 (-imidQ, 129.6 (-ArQ, 131.8 (-ArQ, 134.9 (2  2  3  A r Q , 152.9 (-ArQ, 196.4 (-HfCcarbene). Anal. Calc. for C H H f N : C, 55.72; H , 6.77; N , 8.96. Found: C, 55.24; H , 6.59; N , 2 9  4 2  4  8.87.  91  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  </io-3.37: ' H and  13  C N M R spectra identical to 11 with the absence of - H f C H C H 2  3  resonances. 3.38:  ' H N M R (C D ): 6  6  5 1.85 (s, 4H,-HfC// ), 2.26 (s, 6H, -p-ArCH ), 2.36 (s, 12H, -o2  3  A r C / / ) , 3.04 (m, 4H, - N C / / ) , 3.46 (m, 4H, - N C / / ) , 5.73 (s, 2H, -imid//), 6.82 (d, J = 3  2  2  8Hz, 4H, -o-CH Ph), 6.90 (t, J = 8Hz, 2H, -p-CU Ph), 7.02 2  (s, 4H, -AiH), 7.18  2  (t, J =  8Hz, 4H, -m-CU Ph). 2  I 3  C{'H} N M R (C D ): 6  6  5 21.2 (-CH ), 22.1 (-CH ), 50.0 (-NCH ), 51.4 (-NCH ), 73.5 (3  3  2  2  HfCH ), 121.3 (-ArQ, 122.9 (-imidQ, 129.6 (-ArQ, 130.9 (-ArQ, 135.5 (-ArQ, 147.9 2  (-ArQ, 155.6 ( - A r Q , 196.5 (-HfCcarbene)- Some aromatic resonances obscured by C D 6  6  resonances. Anal. Calc. for C H H f N : C, 62.51; H , 6.19; N , 7.48. 3 9  4 6  Found: C, 62.42; H , 6.14; N ,  4  7.42. ' H N M R ( C D ) : 5 0.68  3.39:  6  (d, J = 8Hz, 4H, -HfC// ), 1.02  6  2  (d, J = 8Hz,  12H, -  CH(C// ) ), 2.24 (s, 6H, -p-ArCH ), 2.35 (n, J = 8Hz, 2H, - C H C / / ( C H ) ) , 2.46 (s, 12H, 3  2  3  2  3  2  3.23 (m, 2H, - N C / / ) , 3.67 (m, 4H, -NC// ), 5.86 (s, 2H, -imid//), 7.00 (s,  -O-ATCHJ),  2  2  4H, -ArH). N M R (C D ):  C{ H}  l3  l  6  6  8 13.7 (-CH CH(CH ) ), 2  3  2  19.4 (-o-CH ), 20.5 (-p-CU ), 32.3 (3  3  CH CH(CH ) ), 50.5 (-NCH ), 52.1 (-NCH ), 68.4 (-HfCH ), 118.4 (-imidQ, 128.4 (2  3  2  2  2  2  A r Q , 132.1 (-ArQ, 133.9 (-ArQ, 148.4 (-ArQ, 194.9 (-HfC bene). Car  Anal. Calc. for C H o H f N : C, 58.18; H , 7.40; N , 8.22. 33  5  Found: C, 57.91; H , 7.05; N ,  4  8.01.  Decomposition of  M e s  (NCN)Hf(CH CH ) 2  3  to f o r m 3.40  2  a n d rf -3.40. 4  3.37 (110 mg, 0.18 mmol) was dissolved in E t 0 (20 mL) and the pale yellow 2  solution was stirred for 5 days.  The E t 0 was removed under reduced pressure and 2  hexanes added to precipitate a dark orange powder. Yield = 99 mg, 95 %. 5 -0.10 (dq, J = 5, 8Hz, 1H, -HfC// CH ), 0.010 (dq, J = 5, 8Hz, 1H, -  ' H N M R (C D ): 6  6  2  3  H f C / / C H ) , 1.00 (d, J = 12Hz, 1H, -HfC// Ar), 1.01 (t, J = 8Hz, 3H, -HfCH C/Z ), 2.23 2  3  2  (s, 3H, -CH ), 2.25 3  2  (s, 3H, -CH ), 2.37 (s, 3H, -CH ), 2.47 3  3  (s, 3H, -CH ), 2.51 3  3  (d, J =  12Hz, 1H, -HfC// Ar), 2.58 (s, 3H, -C// ), 3.19 (m, 3H, - N C / / ) , 3.22 (m, 3H, -NC// ), 2  3  2  2  3.27-3.31 (m, 3H, - N C / / ) , 3.47 (m, 3H, -NC// ), 3.62 (m, 3H, - N C / / ) , 3.93 (m, 3H, 2  2  92  2  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  N C / / ) , 4.16 (m, 3H, - N C / / ) , 5.89 (d, J=2Hz, 1H, -imid//), 5.92 (d, J=2Hz, 1H, -imid/O, 2  2  6.77 (s, 1H, -Ar//), 6.97 (s, 1H, -Ar//), 7.04 (s, 2H, -Ar//). 1 3  C { ' H } N M R ( C D ) : 8 9.7 (-HfCH CH ), 19.1 (-ArCH ), 19.3 (-ArCH ), 21.1 (6  6  2  3  3  3  ArCH ), 21.3 (-ArCH ), 52.1 (-NCH ), 53.8 (-NCH ), 55.2 (-NCH ), 55.3 (-NCH ), 58.2 3  3  2  2  2  2  (-HfCH CH ), 72.9 (-HfCH Ar), 1.19.5 (-imidQ, 129.3 (-ArQ, 129.9 (-ArQ, 135.0 (2  3  2  A r Q , 138.5 (-ArQ, 138.6 (-ArQ, 142.9 (-ArQ, 145.6 (-ArQ, 197.3  (-HfC rbene). Ca  Some  aromatic resonances obscured by C6D6 solvent. Anal. Calc. for C H H f N : C, 54.49; H , 6.10; N , 9.41. 2 7  3 6  4  Found: C, 54.13; H , 5.86; N ,  9.12. rf -3.40: 4  ' H and  13  C N M R spectra identical to  3.40  with the absence of - H f C H C H 2  3  resonances.  93  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  3.7.  References  (1)  Regitz, M . Angew. Chem., Int. Ed. Engl. 1996, 35, 725.  (2)  Herrmann, W. A . ; Kocher, C. Angew. Chem., Int. Ed. Engl. 1997, 36, 2162.  (3)  Dullius, J. E. L . ; Suarez, P. A . Z.; Einloft, S.; de Souza, R. F.; Dupont, J.; Fischer, J.; De Cian, A . Organometallics 1998, 17, 815.  (4)  Arduengo, A . J., Ill Acc. Chem. Res. 1999, 32, 913.  (5)  Arduengo, A . J., Ill; Krafczyk, R. Chem. Z. 1998, 32, 6.  (6)  Arnold, P. L . ; Mungur, S. A . ; Blake, A . J.; Wilson, C. Angew. Chem. Int. Ed.  2003, 42, 5981. (7)  Arnold, P. L.; Blake, A . J.; Wilson, C. Chem. Eur. J. 2005, 11, 6095.  (8)  Aihara, H.; Matsuo, T.; Kawaguchi, H. Chem. Commun. 2003, 2204.  (9)  Arduengo, A . J., Ill; Dias, H . V . R.; Calabrese, J. C ; Davidson, F. J. Am. Chem. Soc. 1992, 114, 9724.  (10)  Arduengo, A . J., I l l ; Dias, H . V . R.; Harlow, R. L . ; Kline, M . J. Am. Chem. Soc. 1992, 114, 5530.  (11)  Arduengo, A . J., I l l ; Harlow, R. L.; Kline, M . J. Am. Chem. Soc. 1991,113, 361.  (12)  Fryzuk, M . D.; Johnson, S. A . ; Patrick, B. O.; Albinati, A . ; Mason, S. A . ; Koetzle, T. F. J. Am. Chem. Soc. 2001,123, 3960.  (13)  Arduengo, A . J., Ill; Krafczyk, R.; Schmutzler, R.; Craig, H . A . ; Goerlich, J. R.; Marshall, W. J.; Unverzagt, M . Tetrahedron 1999, 55, 14523.  (14)  Malek, A . ; Fresco, J. M . Can. J. Chem. 1973, 51, 1981.  (15)  Chandra, S.; Kumar, R. Transition Met: Chem. 2004, 29, 269.  (16)  Niehues, M . ; Erker, G.; Kehr, G.; Schwab, P.; Froehlich, R.; Blacque, O.; Berke, H. Organometallics 2002, 21, 2905.  (17)  Niehues, M . ; Kehr, G.; Erker, G.; Wibbeling, B.; Frohlich, R.; Blacque, O.; Berke, H . J. Organomet. Chem. 2002, 663, 192.  (18)  Zhang, X . ; Zhu, Q.; Guzei, I. A . ; Jordan, R. F. J. Am. Chem. Soc. 2000,122, 8093.  (19)  Skinner, M . E. G.; L i , Y.; Mountford, P. Inorg. Chem. 2002, 41, 1110.  94  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic Carbene Complexes  (20)  Schrock, R. R.; Seidel, S. W.; Schrodi, Y.; Davis, W. M . Organometallics 1999, 75, 428.  (21)  Scott, M . J.; Lippard, S. J. Inorg. Chim. Acta 1997, 263, 287.  (22)  Petersen, J. R.; Hoover, J. M . ; Kassel, W. S.; Rheingold, A . L.; Johnson, A . R. Inorg. Chim. Acta 2005, 358, 687.  (23)  Straus, D. A.; Kamigaito, M . ; Cole, A . P.; Waymouth, R. M . Inorg. Chim. Acta 2003,349,65.  (24)  Lee, Y.-J.; Lee, J.-D.; Ko, J.; Kim, S.-H.; Kang, S. O. Chem. Commun. 2003, 1364.  (25)  Novak, A.; Blake, A . J.; Wilson, C ; Love, J. B. Chem. Commun. 2002, 2796.  (26)  Harris, S. A.; Ciszewski, J. T.; Odom, A . L. Inorg. Chem. 2001, 40, 1987.  (27)  Boisson, C ; Berthet, J. C ; Ephritikhine, M . ; Lance, M . ; Nierlich, M . J. Organomet. Chem. 1997, 531, 115.  (28)  Mungur, S. A.; Blake, A . J.; Wilson, C ; McMaster, J.; Arnold, P. L. Organometallics, A C S A S A P .  (29)  Arndt, S.; Okuda, J. Chem. Rev. 2002,102, 1953.  (30)  Fagan, P. J.; Manriquez, J. M . ; Marks, T . J.; Day, C. S.; Vollmer, S. H.; Day, V . W. Organometallics 1982,1, 170.  (31)  Okuda, J. Dalton Trans. 2003, 2367.  (32)  Evans, W. J.; Drummond, D. K.; Grate, J. W.; Zhang, H.; Atwood, J. L. J. Am. Chem. Soc. 1987, 109, 3928.  (33)  Scott, M . J.; Lippard, S. J. Organometallics 1997,16, 5857.  (34)  Arnold, P. L.; Liddle, S.  (35)  Warren, T. H . ; Schrock, R. R.; Davis, W. M . Organometallics 1996, 15, 562.  (36)  Alt, H . G.; Denner, C. E.; Milius, W. Inorg. Chim. Acta 2004, 357, 1682.  (37)  Matulenko, M . A.; Hakeem, A . A.; Kolasa, T.; Nakane, M . ; Terranova, M . A . ;  T.  Chem. Commun. 2005, 5638.  Uchic, M . E.; Miller, L. N . ; Chang, R.; Donnelly-Roberts, D. L.; Namovic, M . T.; Moreland, R. B.; Brioni, J. D.; Stewart, A . O. Bioorg. Med. Chem. 2004,12, 3471. (38)  Gowda, B. T.; Svoboda, I.; Fuess, H . Z. Naturforsck, A: Phys. Sci. 2000, 55, 779.  95  References begin on page 94.  Chapter Three: Synthesis of Group 4 Bis(amido)-N-Heterocyclic  (39)  Carbene Complexes  Wilde, R. G.; Billheimer, J. T.; Germain, S. J.; Hausner, E. A . ; Meunier, P. C.; Munzer, D. A . ; Stoltenborg, J. K . ; Gillies, P. J.; Burcham, D. L.; et al. Bioorg. Med. Chem. 1996, 4, 1493.  (40)  McAlexander, L. H . ; L i , L.; Yang, Y.; Pollitte, J. L.; Xue, Z. Inorg. Chem. 1998, 37, 1423.  (41)  Whitesides, G. M . ; Hackett, M . ; Brainard, R. L.; Lavalleye, J. P. P. M . ; Sowinski, A. F.; Izumi, A . N . ; Moore, S. S.; Brown, D. W.; Staudt, E. M . Organometallics 1985,4,1819.  (42)  Bird, R.; Knipe, A . C.; Stirling, C. J. M . J. Chem. Soc, Perkin Trans. 2 1973, 1215.  96  References begin on page 94.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Chapter Four  Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes 4.1. Introduction* To date, research with N H C donors has focused on the application of late transition metal N H C complexes in areas such as homogeneous catalysis. In general, the chemistry of electropositive N H C complexes, which include groups 4, 5, and the s- and fblock metals, has been limited to studying the binding of the N H C donor and the coordination properties of the metal complexes. Surprisingly, little is known about the application and reactivity of these complexes in homogeneous catalysis and small molecule activation. In chapter 3, we demonstrated that by flanking a centrally disposed 1  N H C with two pendant amido donors in a tridentate motif, the carbene donor has been forced to bind to group 4 transition metals by virtue of its position in the chelate array. Given this stability, we were interested in the reactivity and application of these complexes in fundamental processes such as homogeneous catalysis and small molecule activation.  * A portion o f this chapter has been published (Spencer, L . ; Fryzuk, M . D . J. Organomet. Chem. 2005, 690, 5788). 97  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  In this chapter, the applications of group 4 transition metal [NCN] complexes in olefin polymerization and migratory insertion processes will be presented. In addition, the attempted syntheses of coordinated dinitrogen complexes will be outlined. As the topics discussed are unique from each other, separate introductions are included in each section for each reactivity pattern investigated.  4.2.  Hf and Zr Cation Formation and Polymerization Studies  Group 4 transition metal complexes with substituted amide ligands have been 29  extensively examined as olefin polymerization catalysts. " Perhaps the most recognized examples of highly active amide-based olefin polymerization complexes are the constrained geometry catalysts (CGC's) (4.1, M = Ti, Zr, Figure 4.1).  10  This catalyst and  derivatives thereof are active for both ethylene and 1-hexene polymerization. Group 4 complexes stabilized by N H C ligands (4.2-4.3) have also been investigated for the polymerization of a-olefins (Figure 4.1)." These simple N-alkyl substituted N H C supported  complexes exhibit moderate ethylene polymerization activity at room  temperature.  The activity dramatically decreases at elevated temperatures, which is  potentially a result of N H C dissociation from the metal centre. Another example of an NHC-based polymerization catalyst  is the bis(aryloxido)NHC stabilized titanium  complex described in chapter 3.1, which exhibits high ethylene polymerization activity upon M M A O activation.  4.1 Figure 4.1.  12  4.2  4.3  Examples of Group 4 olefin polymerization catalysts.  98  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  In light of the success with the C G C design and spurred by the recent accomplishments of N H C supported complexes, the synthesis of activated zirconium and hafnium  [NCN]  complexes  was  investigated.  The  methyl  cations,  { [NCN]M(CH3)}{B(C F )4}, (M = Zr, 4.4; M = Hf, 4.5) were generated in situ from Mes  6  5  dimethyl precursors 3.33 and 3.35 at -10°C with [Ph C][B(C F )4] (Scheme 4.1). Due to 3  6  5  the thermal sensitivity of the species, the products were identified by *H N M R spectroscopy in solution and not isolated. H N M R spectroscopy of both species shows !  anticipated ligand resonances for C symmetric products in solution with M-Cr7 s  3  resonances at 0.50 ppm for 4.4 and 0.26 ppm for 4.5. Treatment of 3.35 with triflic acid generates the hafnium methyl-triflate complex, Mes  [NCN]Hf(OTf)(CH ) (4.6), which is isolable at room temperature (Scheme 4.1). The 3  *H N M R spectrum of 4.6 shows similar ligand resonances to 4.4 and 4.5, indicative of a C symmetric species in solution with a Hf-C# resonance at 0.19 ppm. These findings s  3  13  are similar to those of previously described hafnium triflate complexes.  M = Zr 4.4 Hf 4.5  Scheme 4.1.  99  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Cationic complexes 4.4 and 4.5 were evaluated as 1-hexene polymerization catalysts. The addition of -500 equivalents of 1-hexene to a chlorobenzene solution of 4.4 resulted in the isolation of a viscous oily polymer.  13  C { ' H } N M R spectroscopy of the  substance reveals the formation of atactic poly-1-hexene in 4% yield.  14  The low yield  observed is quite surprising in light of the many active amido-based non-metallocene group 4 catalysts. " 2  9  It was recently found that 1-hexene polymerization with group 4  metal bearing diamido  Mes  [N(NMe)N] ancillary ligands underwent ortho-methyl C - H  bond activation during polymerization. Investigation of the decomposition products 15  revealed an ortho-methyl C - H bond activated compound similar to 3.39, in addition to other unidentifiable materials. The exposure of 4.4 to ethylene in toluene resulted in a different outcome. A large amount of polyethylene was recovered, which shows that 4.4 is a moderately active catalyst for the polymerization of ethylene (125 g mmol" h" atm" ). It is important to 1  1  1  note that immediately after exposure to ethylene, a noticeable exothermic event was observed. Halting the polymerization experiment at increasingly longer times resulted in a decreased activity. This suggests that the active species, albeit catalytically active, is short-lived in solution.  4.3.  Formation of [NCN] Hafnium tj -Iminoacyls and an  Eneamidolate„  metallacycle  The migratory insertion of carbon monoxide into metal alkyl and hydride bonds represents a fundamental reaction type in organometallic chemistry.  16  Interest in this area  stems from the importance of carbonylation reactions where the migratory insertion of CO is a key step in the catalytic cycle.  CO insertion into transition metal alkyls  17  normally generates r\ or r) -acyl derivatives, with the latter binding mode typically 2  occurring in electron-deficient early d-block, actinide and lanthanide metal centres. Analogous reactivity has been observed in the migratory insertion of isocyanides, 2  16  isoelectronic equivalents of CO, generating n -iminoacyl groups.  100  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Migratory insertion reactions involving transition metal N H C complexes have also been investigated and, in some cases, the destructive modification of the N H C donor has been observed. '  18 19  For example, the facile insertion of an N H C group into a Pd-Me  bond was recently reported (Equation 4.1).  19  DFT calculations on model complexes  suggests all three functionalities of the tridentate ligand coordinate to the palladium centre prior to methyl migration from the metal centre to the N H C moiety.  Ar  Ar  With respect to early transition metal (ETM) complexes and migratory insertion reactions, the participation of the metal-NHC bond during these reactions has yet to be addressed.  Along this line, the migratory insertion of substituted isocyanides into the  halfnium-alkyl bonds of 3.35 was investigated. The hafnium dimethyl derivative reacts immediately in solution with one equivalent of xylyl isocyanide (XyNC) to give the mono-insertion product 4.7 (Scheme 4.2). The *H N M R spectrum is consistent with a C  s  symmetric structure (equivalent N-mesityl groups and backbone linkers); the remaining hafnium-methyl resonance is found at 0.17 ppm. The r| coordination of the iminoacyl 2  group is confirmed by C { ' H } N M R (N=C, 259 ppm) and IR (u = 13  c  spectroscopy and is a typical outcome for this kind of reaction.  16  1575 cm" ) 1  N  In solution, only one of  the two possible orientations of the r| -iminoacyl unit is observed. N O E measurements 2  show a through space enhancement of the or/7zo-methyls of the N-xylyl group upon irradiation of the remaining Hf-Me resonance, which supports the isomer having the N xylyl group pointing towards the Hf-Me.  101  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  r\ XyNC THF N M  e  Hf HC  s  N CH  N  3  3  M  e  s  3  Me  Me  —0"  M e  Me  C  N  3  3.35  M e s =  ^^^^ ^^^^ N-—.Hf—N / H C * / V \ Mes - ^ v Mes CH Me Me  X  y  =  —y)  4.7  Me  THF  RNC  -N .  ,.N-  v  ' ^ ^ ^ ^ ^^^^ ^ N — . H f ^ - N ^ :  Mes ^N ^.i M ^ V N  C  • I  R  H C Xy  MES  CH  3  3  R = Xy R = Pr j  4.8 4.9  Scheme 4.2.  The solid-state molecular structure of 4.7 determined by an X-ray diffraction experiment also verified the nMminoacyl coordination mode. A n ORTEP depiction of 4.7 is shown in Figure 4.2 with relevant bond lengths and angles listed in Table 4.1 and crystallographic details given in appendix A. The imino carbon atom is directly bound to the hafnium centre with the HT1-C36 bond length at 2.251(2) A , which is similar to related iminoacyl-zirconium complexes (2.23-2.25 A ) .  16  The bond angles of the triangle  defined by Hf-C26-N5 are typical of other structurally characterized group 4 n -iminoacyl 2  complexes as is the imino N5-C26 bond length.  16  Surprisingly, the ancillary [NCN]  ligand is distorted towards facial coordination with the N4-HA-N3 angle being 133.65(7)°.  102  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity. Table 4.1.  Selected Bond Distances (A) and Bond Angles (°) for XyNCCH )(CH ), (4.7). 3  [NCN]Hf(r| 2  3  Bond Angles 133.65(7) N3-HT1-N4 N5-C26-HT1 73.05(11) 77.25(7) N4-Hfl-Cl 77.72(7) N3-HH-C1  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N4 Hfl-C26 Hfl-N5 N5-C26  Mes  2.387(2) 2.1352(18) 2.1117(18) 2.251(2) 2.2461(16)  Addition of a second equivalent of xylyl isocyanide to 4 . 7 resulted in an immediate color change from pale yellow to dark purple, with the exclusive formation of the bis(n -iminoacyl) product 4.8 (Scheme 4.2). The presence of an r| -iminoacyl group 2  2  is noted by a U C = N band at 1568 cm" . The room temperature *H N M R spectrum of 4 . 8 in 1  CD2CI2 is consistent with a C symmetric species (four inequivalent ethylene spacer s  103  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  resonances); however, cooling the solution to -40°C is necessary to fully resolve all resonances. At this lower temperature, two unique environments are observed for each r) -iminoacyl group consistent with the solid-state molecular structure of 4.8. A n ORTEP 2  depiction of 4.8 is shown in Figure 4.3. Bond lengths and angles for 4.8 are given in Table 4.2 and crystallographic details are given in appendix A . The characteristic iminoacyl C resonance (~ 260 ppm) was not observed in the C N M R spectrum. This 1 3  1 3  is likely due to fast exchange under the normal acquisition conditions.  depicted with 50% ellipsoids; all hydrogen atoms and mesityl groups have been omitted for clarity.  104  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Table 4.2.  Selected Bond Distances ( A ) and Bond Angles (°) for X y N C C H ) , (4.8). 3  Mes  [NCN]Hf(r) 2  2  Bond Angles 122.6(3) N3-Hfl-N4 34.0(3) C26-Hfl-N5 78.2(3) N4-HT1-C1 76.2(3) N3-Hfl-Cl 32.3(3) N6-Hfl-C36  Bond Lengths Hfl-Cl 2.377(10) 2.154(7) HT1-N3 HT1-N4 2.146(8) 2.249(9) HT1-C26 2.250(8) Hfl-N5 2.305(7) Hfl-N6 2.306(10) Hfl-C36  In the solid state, there are two independent molecules in the unit cell with subtle variations in the n -iminoacyl bond lengths (only one of the molecules is used for 2  structural analysis described below). Although formally seven-coordinate, 4.8 is best described as distorted trigonal bipyramidal about hafnium, with each of the n -iminoacyl groups occupying a single coordination site, one axial and one equatorial. The  Mes  [NCN]  ligand is puckered towards a facial orientation with N4-HA-N3 being 122.6(3)°, presumably to accommodate the additional steric constraints of two xylyl units. The two iminoacyl groups are oriented perpendicular to each other, which is further evidence of the considerable steric interactions in the solid state. In general, thermolysis of groups 4 and 5 bis(r) -iminoacyl) complexes results in the formation of enediamido metallacycles. '  20 21  No reaction was observed by H N M R !  spectroscopy when 4.8 was heated in toluene (110°C for >8h). This is somewhat surprising given that this transformation is reported to be facilitated by lowering the 7i*c=N  orbital via the presence of electron-withdrawing substituents or by having a  relatively electron-rich metal centre.  16  Because NHCs are considered strongly a-  donating, ' this should have facilitated this C-C bond coupling process. 22 23  To probe the effects of sterics on this process, isopropylisocyanide ('PrNC) was added to 4.7 to generate the mixed bis(iminoacyl) species 4.9 (Scheme 4.2). Thermolysis of this material did not result in the formation of an enediamido metallacycle even after extended reaction times at 110°C. Finally, the bis(isopropyl) iminoacyl was prepared by the addition of two equivalents of isopropyl isocyanide to the dimethyl complex 3.35 to generate 4.10 in excellent yield (Equation 4.2). This compound also turned out to be  105  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  stable to thermolysis as evidenced by no change in the ' H N M R spectrum after one day at 110°C. Formation of an enediamido metallacycle is known to be affected by the steric bulk located on the nitrogen atom. '  24 25  Moreover, for enediamide formation to occur,  both n -iminoacyls must rotate into the preferred coplanar configuration, which would appear to be difficult in complexes 4.8-4.10 due to the increased steric bulk around the metal centre. ' ' " 20 21 26  28  The insertion of carbon monoxide into the remaining metal-alkyl bond in 4.7 was investigated with a view that this smaller molecule would insert and facilitate C=C bond formation.  Indeed, a facile reaction is observed when the hafnium methyl-iminoacyl  complex 4.7 is exposed to one atmosphere of CO.  Interestingly, the product was  identified as the eneamidolate complex 4.11 (Equation 4.3). The likely first step is insertion of CO into the remaining Hf-CH.3 bond; however, monitoring this process by N M R spectroscopy did not provide any evidence for the presence of a mixed acyliminoacyl compound implying that the C=C bond formation process is quite facile. To our knowledge, only one other example of eneamidolate synthesis has been reported; however, in contrast to our work, forcing conditions (200-1000 psi of CO) were required.  20  106  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (4.3)  The solid-state molecular structure of 4.11 was determined by an X-ray diffraction experiment and an ORTEP depiction is shown in Figure 4.4. Relevant bond lengths and angles are listed in Table 4.3, and crystallographic details are located in appendix A . The C=C  bond  length  (1.340(9)  A ) compares  metallocyclopentene metallocycles. '  20 29  coordination,  an observation  well  with  previously  described  The eneamidolate ring is distorted from a planar  prominent  in most  enediolate,  eneamidolate and  2  *  *  enediamides systems. This bending has been attributed to a n ,7i bonding interaction between the electron deficient metal centre and the olefinic portion of the metallacyclic 29  backbone, a phenomenon observed in a similar Zr-butadiene system.  A fold angle of  24.0° was found for 4.11, significantly less than the previously reported fold angles (-50°) of other compounds.  20,30  As a result, the Hfl»«C26 and Hfl»»C27 distances (2.728(7)  and 2.660(6) A , respectively) are significantly longer than a previously reported eneamidolate complex (2.549(8) and 2.581(8) A ) .  21  Once again, the  Mes  [ N C N ] ancillary  ligand is distorted towards facial coordination as evidenced by the N4-HT1-N3 bond angle of 124.5(2)°. The molecule possesses C\ symmetry in the solid state as a result of a weak n ,7i 2  interaction from the olefin; however, C symmetry is observed in solution at room s  temperature due to ring flipping of this eneamidolate ring on the N M R time scale. The AG* of 54.1 kJ mol" for the ring flipping process (Equation 4.4) is estimated from the 1  coalescence temperature (268 K ) , and is very similar to the value estimated for a Hfenediamide complex (59.4 kJ mol" ). 1  20  Broad resonances for the 0-C(CH3)= and O-  C(CH )= carbon nuclei are observed in the C{'H} N M R spectrum at room temperature 13  3  at 137.0 ppm and 19.4 ppm, respectively. 107  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Figure 4.4.  ORTEP view of [NCN]Hf(OC(CH )=C(CH )NXy), (4.11) (1/2 E t 0 omitted), depicted with 50% ellipsoids; all hydrogen atoms and mesityl groups have been omitted for clarity.  Table 4.3.  and Bond Selected Bond Distances ( A ) [NCN]Hf(OC(CH )=C(CH )NXy), (4.11).  Mes  3  3  2  Angles  (°)  for  Mes  3  3  Bond Angles  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N4 Hfl-N5 Hfl-C26 Hfl-C27 Hfl-Ol C6-C27 Hfl—C26 Hfl»»C27 4.4.  01-Hfl-N5 N3-Hfl-N4 N3-Hfl-Cl N4-Hfl-Cl  2.348(6) 2.077(5) 2.082(5) 2.061(5) 2.728(7) 2.660(6) 2.032(4) 1.340(9) 2.728(7) 2.660(6)  83.14(19) 124.5(2) 78.1(2) 81.2(2)  Formation of a Hafnium Vinyl-enolate and Enediolate Metallacycle  Due to its ease of preparation and its enhanced thermal stability relative to zirconium dialkyl complexes, the hafnium dimethyl derivative 3.35 was chosen for  108  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  reactivity studies with CO. Exposure of 3.35 to one atmosphere of carbon monoxide for one day results in the formation of  Mes  [NCN]Hf(CH )(0-CH=CH ) (4.13), a hafnium 3  2  vinyl-enolate (Scheme 4.3). Diagnostic resonances appear in the H N M R spectrum at !  3.47 ppm, 3.54 ppm, and 5.75 ppm, with appropriate geminal and vicinal coupling constants. The downfield resonance at 5.75 ppm, assigned to the a-0-CH= proton, splits further when Mes  13  C O is substituted, giving typical  'ji3  C  .i  H  coupling of 145 H z .  31  The  [ N C N ] ligand resonances are diagnostic of a C symmetric compound and also s  consistent with the Hf-CH3 resonance located at 0.37 ppm. The C { ' H } N M R spectrum 13  reveals a Hf-NHC carbene signal at 196.2 ppm, as well as vinyl  1 3  C resonances at 120.2  ppm and 139.0 ppm. From the solution N M R data, a definitive orientation of the ligand remains unknown, and for this reason, a mer geometry is shown, despite the fact that the mono insertion adduct of X y N C (4.7) has a facial coordination of the ancillary ligand.  H 4.13  Scheme 4.3.  Monitoring the reaction of CO with the dimethyl complex showed the formation of the ri -acyl intermediate 2  Mes  [NCN]Hf(n -COCH )(CH ) 4.12, as evidenced by a singlet 2  3  3  at 1.62 ppm for the acetyl methyl protons. This resonance splits into a doublet with the use of C O 1 3  l3  ('ji3 j C  H  = 7 Hz), confirming that simple insertion has occurred. The  C { ' H } N M R spectrum features a resonance at 339.6 ppm, and is typical for the acyl  carbonyl carbon of reported Hf(r] -acyl) complexes. 2  109  16  IR spectroscopy was also useful in  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  the determination of the Hf(r) -acyl) moiety with a t)c=o stretch observed at 1540 cm" , 2  1  characteristic of similar compounds. The rearrangement of the hafnium methyl-acetyl complex 4.12 to the methyl-vinyl enolate derivative 4.13 was unexpected.  The high reactivity of group 4 methyl-acetyl  complexes has been ascribed to the oxy-carbene resonance form of the r\ -acyl moiety. '  This species can undergo intramolecular coupling with the adjacent methyl  31 32  group,  which is followed by hydrogen abstraction by the metal to generate a  33  hydridomethylvinyl-enolate complex (Scheme 4.4).  Cp'  Cp'  2  .Zr.  O CH,  /  Z  r  Cp'  2  \  Cp  2  o  HoCil  :c  H C=C 2  CH,  CH, Scheme 4.4.  In the case of the hafnium methyl-acetyl complex 4.12, the formation of the vinyl enolate suggests that the oxy-carbene resonance form preferentially undergoes a hydrogen-atom shift from the methyl substituent of the carbene carbon to generate the observed vinyl enolate (Scheme 4.5). Presumably, the r) -acetyl unit of 4.12 is oriented in 2  such a way as to disfavor C-C coupling with the Hf-CH3 unit, and instead, hydrogen transfer from the methyl occurs. Whether or not this is a result of a geometric constraint caused by the different ancillary ligands or an electronic effect is unknown. Similar hydrogen and silyl group migrations have been reported for Cp ThR and Cp2*ThR(Cl) 3  derivatives upon reaction with C O .  34  110  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  4.13 Scheme 4.5. Continued exposure of 4.13 to CO results in the formation of an insoluble, white powder.  ES-MS shows a molecular ion peak at 652 m/z indicative of a second CO  insertion; however, the insolubility of this product has hampered further characterization efforts. It has been shown that the nature of carbonylation products is dependent on substituents on the metal.  35  With this in mind, the carbonylation of the hafnium  diisobutyl complex, 3.38, was investigated. Exposure of 3.38 to one atmosphere of CO for an extended period (5 days) results in the precipitation of colorless crystals in reasonable yield. Analysis of these crystals by solid-state X-ray diffraction indicated that this  material  is  the  dihafnium  bis(enediolate)  complex,  ( [NCN]Hf)2(«Mes  OC( Bu)=C( Bu)0) , 4.16 (Equation 4.6). The ORTEP diagram is shown in Figure 4.5, i  i  2  bond lengths and angles are shown in Table 4.4, and crystallographic details are located  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  in appendix A. Examination of the C-C bond length suggests double bond character (avg. 1.342(15) A) and is similar to other early transition metal enediolate complexes. The 36  [NCN] ligand distorts to a facial geometry having an N4-HT1-N3 bond angle of 124.4(3)°. Hf-C alkyl and Hf-N amido bond lengths are similar to previously discussed complexes. The 'lT N M R spectrum is consistent with a C symmetric species in solution with two s  distinct wo-butyl resonances.  In addition, 4.16 exhibits a weak  ppm characteristic of an olefinic C=C bond (  1  1 3  C resonance at 140.0  13  Ji3 j3 C  C  = 20 Hz with CO).  omitted), depicted with 50% ellipsoids; all hydrogen atoms and mesityl groups have been omitted for clarity. Table 4.4.  Selected Bond Distances (A) and Bond Angles (°) for ( [NCN]Hf) GuO C C B u ^ C O B u P ) : , (4.16). Mes  2  Bond Angles 105.4(2) Ol-Hfl-02 N3-HA-N4 124.4(3) 77.8(3) N3-HA-C1 77.1(3) N4-HA-C1 C51-01-Hfl 169.4(6) 163.1(6) C52-01-Hfl  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N4 Hfl-Ol Hfl-02 C51-C61  2.387(9) 2.109(7) 2.097(7) 1.937(5) , 1.912(6) 1.341(12)  112  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  The mechanism of the formation of the dinuclear bis(enediolate) was examined by monitoring the reaction of 3 . 3 8 with CO as a function of time using N M R spectroscopy. The first intermediate formed is the hafnium isobutyl-acyl species, 4.14, clearly distinguished by a C { H } N M R singlet at 338.4 ppm, attributed to a Hf(0=C'Bu) 13  !  resonance. This finding is analogous to other early transition metal n -acyl complexes (Scheme 4.6).  16  The ' H N M R spectrum reveals a C symmetric species in solution with s  two distinct /so-butyl resonances.  A n upfield resonance at 1.68 ppm, assigned to the  methylene protons a to the acyl carbonyl of one z'so-butyl unit, splits into a doublet of doublets when C O was used 1 3  Mes  ( Ji3 _i  = 4.7 Hz). Again, the coordination mode of the  2  C  H  [ N C N ] ligand in 4.14, mer vs fac, is not assignable with the N M R data available.  co  CO ^ CeH 6  N Mes  HfV  N  -N.  'Bu" 'Bu 3.38  \ M  e  s  M  e  -Hf ig '  /  u  s  n  ^ C  N ,  s  °  -Hf  v  Mes 'Bu  N  Mes  \  Mes  4.14 .  ?  y  'Bu  'Bu  4.15  'Bu  /'Bu C=C  / Mes  [NCN]Hf  / \  \ \  /  O \  'Bu  HfTNCN]Mes  O /  c=c 4.16  'Bu  Scheme 4.6.  Continued exposure of 4.14 to C O results in the formation of a new product having C  2 v  symmetry (one set of wo-butyl resonances) in solution and distinct from the  113  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  final dihafnium macrocycle 4.16 (Scheme 4.6). Only one /so-butyl resonance is present in the ' H N M R spectrum at room temperature, suggestive of a CO insertion into the remaining H f - C H  2  alkyl bond of 4.14.  The  13  C { ' H } N M R spectrum of this species  displays a weak resonance at 140.6 ppm which suggests that a new C=C bond is formed. This spectroscopic evidence is consistent with the formation of the mononuclear hafnium-enediolate, 4.15 (Scheme 4.6). The synthesis of this enediolate likely proceeds through a bis(n -acyl) species, the presence of which was not observed by H N M R studies. In solution, the nuclearity of the enediolate 4.15 is assumed to be mononuclear; however, there are early transition metal enediolates reported in both monomeric and dimeric forms, depending on the steric bulk of the alkyl group.  35  For example, when the  alkyl group is bulky (R=CH C(CH ) , CH Si(CH ) ) monomeric species have been 2  3  3  2  3  3  observed, and with smaller groups (R=H, C H , CH Ph), higher nuclearity species have 3  2  been reported. Indeed, there are several reports of monomeric enediolates dimerizing to form dinuclear complexes (Scheme 4.7). '  37 38  In one example, such complexes show  dynamic behavior interconverting oxygen atoms through a low activation-energy process by a ten-membered metallacycle intermediate, similar in structure to the final product  4.16.  37  A reasonable proposal for the formation of 4.16 is shown in Scheme 4.7, and involves dimerization of 4.15 via dative oxygen-hafnium interactions that are converted to covalent bonds. This dimerization is followed by ring-opening to generate the 10membered dihafnium macrocycle. The driving force for the formation of the dinuclear complex 4.16 may be the better oxygen-to-hafnium 7i-donation, an overlap that is more difficult in the mononuclear complex 4.15 with the five-membered enediolate ring. " 39  41  Examination of the solid state structure of 4.16 reveals an average Hf-O-C bond angle of 163.5(3)° and reflects such a 7i-donation.  The reason for the differences in reactivity  between alkyl substituents may be attributed to competitive dimerization and insertion pathways. Such considerations have been attributed to the nucleophilic character of the alkoxy-carbene moiety and have been well-documented in actinide and tantalum metallocene systems. '  34 42  114  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  'Bu  /'Bu  \ /  C=  Bu  2  M e s  [NCN]Hf  / \  M e s  /  C  \  . 0  [NCN]Hf  Hf[NCN]  V O  x  \  'Bu  c^c  o  /  'Bu  'Bu  \  C = C  /  \ Hf[NCN] Mes  /  \  M e s  \  [NCN]Hf  /  O  \  .'Bu  /  Mesi[NCN]Hf,  'Bu  \ x  0  O  c=c  'Bu  'Bu  Bu  M e s  /  Hf[NCN] O  \  c=c  'Bu  M e s  'Bu^  /  ^ ' B u  Scheme 4.7.  4.5.  Formation of Amidate and Amidinate Metallacycles  The transition-metal-assisted  formation of new C-C bonds from insertion  reactions with other simple organic molecules was also investigated.  The insertion of  cumulenes, such as isocyanates and carbodiimides, into zirconium-alkyl bonds has been shown to yield amidate  43  and amidinate "  reaction of terr-butyl isocyanate  43  46  ligands, respectively. With this in mind, the  with the hafnium-dimethyl  complex 3.35 was  investigated (Scheme 4.8). This reaction proceeds immediately at room temperature to yield 4.17 as an off-white powder in 84% yield. The ' H and ' ^ { ' H } N M R spectra are consistent with the symmetrical bidentate coordination of an amidate ligand. notably, a  1 3  Most  C resonance at 180.4 ppm is indicative of an - N C ( M e ) 0 moiety, which is  similar to other reported metal amidate compounds.  115  43  Interestingly, the addition of  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  excess isocyanate did not produce a bis(amidate) product, which could result from increased steric interactions at the metal centre.  r\  N,  ,N  'BUNCO  PhMe N Mes  Hf |_| Q  3  N c\-\  3  H C, .N-  ^  3  e  Mes  s  3.35  Hf  «Bu-V/°  N  v  Mes  HC 4.17 3  'PrN=C=N'Pr PhMe  f = \  N  Hfr  Mes^'Pr'"N  N  N  \^ s CH  ?>\  HC  '  3  ^ Mes  P r  4.18  Scheme 4.8.  A single crystal X-ray diffraction experiment confirmed the identity of the product as 4.17. A n ORTEP depiction of 4.17 is shown in Figure 4.6 with relevant bond lengths and angles listed in Table 4.5 and crystallographic details located in appendix A . The geometry about the hafnium metal centre is a distorted trigonal bipyramid with the amidate group occupying one of the coordination sites. The metallacycle core as defined by N5-Hfl-01-C26 is essentially planar (torsion angle of N-Hf-O-C = 8.9°). The N5-C26 and 01-C26 bond lengths (1.299(3) A and 2.1351(17) A , respectively) are similar to previously reported group 4 amidate compounds as is the amidate bite angle defined by 01-Hfl-N5 bond angle (58.02(8)°)  4 3  .  116  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Figure 4.6.  Table 4.5.  ORTEP view of [NCN]Hf(Me)(ri - BuNC(Me)0) (4.17) depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  3  Selected Bond Distances (A) and Bond Angles (°) for [NCN]Hf(Me)(n - BuNC(Me)0), (4.17).  Mes  3  t  Bond Angles N3-HA-N4 N3-Hfl-Cl N4-HH-C1 HA-N5-C26 HA-01-C26 01-C26-N5 Ol-Hfl-NS C26-N5-Hfl-01  Bond Lengths Hfl-Cl Hfl-N3  Hfl-N4 Hfl-N5 Hfl-Ol Hfl-C26 Hfl-C32  C26-N5 C26-01  t  2.385(3) 2.116(2) 2.124(2) 2.374(2) 2.1351(17) 2.646(3) 2.270(3) 1.299(3) 1.305(3)  145.47(8) 78.59(9) 78.35(8) 87.02(8) 97.65(8) 115.04(8) 58.02(8) 8.9  Carbodiimides have also been shown to insert into titanium- and zirconium-alkyl bonds to form amidinate complexes.  43  Indeed, the addition of one equivalent of  'PrN=C=N'Pr to a toluene solution of 3.35 results in the formation of 4.18 as the exclusive product (Scheme 4.8).  The *H N M R spectrum reveals that the desired  117  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  amidinate was produced with no evidence of multiple insertions of the carbodiimide molecule. In solution, a single hafnium-methyl resonance was observed at -0.06 ppm in addition to a methyl resonance at 1.74 ppm. Two inequivalent isopropyl moieties are also observed, implying the orientation of the amidinate ligand shown in Scheme 4.8. The 13  C{'H} N M R spectrum is also informative with a C resonance at 179.4 ppm, indicative 1 3  of a -NC(Me)N group. The formation of 4.18 was confirmed by an X-ray diffraction experiment performed on crystals grown from a concentrated E t 2 0 solution. A n ORTEP depiction of 4.18 is shown in Figure 4.7 with bond lengths and angles given in Table 4.6 and crystallographic details located in appendix A . Although formally six-coordinate, the geometry at the hafnium centre is best described as a distorted trigonal bipyramid, with the amidinate moiety occupying one coordination site. The N3-Hfl-N4 and N 3 - H f l - C l bond angles in 4.18 are similar to the amidate complex 4.17. The amidinate bite angle defined by the N5-Hfl-N6 bond angle is 58.45(7)°, similar to other reported metalamidinate complexes. ' '  The metal carbene bond length is 2.418(3) A , typical of  44 47 48  other [NCN] H f complexes. The R C ( N R ' ) 2 H f core forms a nearly planar metallacycle as defined by the torsion angle formed by C27-N5-Hfl-N6.  The C - N bond distances are  approximately equal and are intermediate between C=N double bond distances in carbodiimides (1.16-1.22 A )  4 9  and C(sp )-N single bond distances (1.47 A ) . 2  118  5 0  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Figure 4.7.  Table 4.6.  ORTEP view of [NCN]Hf(Me)(ri - PrNC(Me)N Pr) (4.18) depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  3  i  Selected Bond Distances ( A ) and Bond Angles (°) for [NCN]Hf(Me)(n - PrNC(Me)N Pr), (4.18).  Mes  3  i  i  Bond Angles N3-Hfl-N4 N3-Hfl-Cl N4-HT1-C1 Hfl-N5-C27 HT1-N6-C27 N6-C27-N5 N5-HA-N6 C7-N5-HT1-N6  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N4 Hfl-N5 HT1-N6 Hfl-C26 Hfl-C(7 C27-N5 C27-N6  i  2.418(3) 2.130(2) 2.120(2) 2.235(2) 2.292(2) 2.282(2) 2.714(2) 1.345(2) 1.321(2)  119  147.38(7) 78.91(6) 77.88(7) 92.80(7) 96.06(8) 112.05(8) 58.45(7) 4.9  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  4.6.  Attempted Synthesis of Group 4 [NCN] Dinitrogen Complexes  Research in the Fryzuk group has centered on the use of [PNP],  [P2N2]  and [NPN]  ligands for the preparation of early transition metal dinitrogen complexes. In particular, the reduction of metal chlorides with strong reducing agents in the presence of dinitrogen 5157  generally affords dinitrogen complexes with different N 2 binding modes. "  For  example, the reduction of [P2N2]ZrCb with KCg in the presence of dinitrogen yields the side-on dinitrogen complex ([P N ]Zr)(//-ri :ri -N2) in good yields (Scheme 4.9). 2  2  2  54  2  Although this reduction method is successful for many amidophosphine stabilized E T M complexes, reduction of the cyclohexyl-substituted analog  C y  [P2N2]ZrCl2  dinitrogen complex, instead producing a paramagnetic Zr(III) complex.  fails to yield a 58  Evidently, a  slight modification in the electronic nature of the ligand can influence the products obtained from the reduction process.  Paramagnetic product  Zr(lll)  Scheme 4.9.  The first molecular dinitrogen complex stabilized by an N H C ligand was recently reported. - The reduction of the iron complex 4.19 with an excess of Na/Hg amalgam in 59  THF under dinitrogen gives the bis-dinitrogen complex 4.20 (Equation 4.4). Like many  120  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  L T M dinitrogen complexes, the nitrogen ligands are weakly activated by the iron centre and display N - N bond lengths (avg. 1.114 A) that are similar to free N (1.0975 A). 2  N—Ar  N—Ar  Na/Hg THF, N -2 NaBr  t  (4.4)  2  N—Ar Ar = 2,6-'Pr C H 2  6  N—Ar  3  4.20  4.19  The reduction of metal-NHC complexes does not necessarily result in the formation of dinitrogen complexes. '  60 61  Treatment of the samarium derivative of 4.21  with 2.2 equivalents of KCg in the presence of D M E results in the isolation of 4.22, a bridging ether cleavage product (Scheme 4.10). The formation of 4.22 was postulated to proceed via a reduced Sm(II) intermediate, which could activate the D M E solvent. The reduction of an yttrium derivative of 4.21 reveals that the N H C is also capable of participating in this reduction chemistry.  The olefinic carbon backbone of the five-  membered N H C ring undergoes reduction during the reaction of KCgHio with the yttrium derivative 4.21, which facilitates deprotonation of the N H C ring to generate 4.23.  These  results suggest that both the metal centre and the N H C unit are capable of engaging in reduction chemistry.  121  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  4.23  Scheme 4.10.  The addition of 2.2 equivalents of potassium graphite to 3 . 2 5 in a solution of THF under 4 atmospheres of nitrogen results in the immediate formation of a yellow solution. A small amount of a yellow crystalline solid was obtained upon removal of the solvent, addition of E t 2 0 , and filtration through Celite (Equation 4.5). Surprisingly, the *H N M R spectrum is consistent with a C symmetric species in solution with the appropriate ligand s  resonances and unexpected alkyl resonances between 1.0 and 1.5 ppm. Additionally, a triplet is observed at 3.5 ppm indicative of a - O C / /  2  moiety.  The C { ' H } N M R 13  spectrum confirms a metal-carbene interaction in addition to a downfield  -OCH2  1 3  C  resonance. The presence of these functionalities in the N M R spectra suggests that THF is incorporated in the final product.  122  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  r\  r\  cn Mes'  N  Zr  2.2  KC:  THF 4 atm N - KCI N  (4.5) 2  Mes  Mes  4.24  3.25  Single crystals of 4.24 were grown from a concentrated E t 2 0 solution and the molecular solid state structure was determined by X-ray crystallography.  A n ORTEP  depiction is shown in Figure 4.8 with bond lengths and angles given in Table 4.7 and crystallographic details located in appendix A . Remarkably, the solid state structure shows the presence of an rc-butoxide group, in addition to the typical arrangement of the [NCN] ligand. The ligand assumes a meridional orientation with respect to a distorted trigonal bipyramidal zirconium metal centre. The Z r l - O l bond distance of 1.912(3) A is similar to other reported Zr-alkoxide complexes, '  62 63  as are the Zr-N amide and Zr-C  N H C bond distances.  123  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Figure 4.8.  Table 4.7.  ORTEP view of [ N C N ] Z r ( C l ) ( O C H 2 C H C H 2 C H 3 ) (4.24) depicted with 50% ellipsoids; all hydrogen atoms have been omitted for clarity. Mes  2  Selected Bond Distances (A) and Bond Angles (°) for [NCN]Zr(Cl)(OCH CH CH2CH3), (4.24).  Mes  2  2  Bond Angles N3-Zrl-N4 126.35(11) 78.70(11) N3-Zrl-Cl 78.84(10) N4-Zrl-Cl 167.44(12) Ol-Zrl-Cl 87.85(8) Cll-Zrl-Cl  Bond Lengths Zrl-Cl Zrl-N3 Zrl-N4 Zrl-Ol Zrl-Cll  2.379(3) 2.101(3) 2.103(3) 1.912(2) 2.4649(14)  This phenomenon of reductive ring-opening of THF has precedent in several reduced early transition metal complexes. " 64  66  For example, a titanium(III) hydride dimer  [Cp2TiH]2 was reported to add THF to form solvated monomers that add the 0 - C a bond  of THF across the Ti-H bond in a concerted step.  64  In light of these findings and the C - 0  bond activation reported in the NHC-derived complex 4.24, it is plausible that reduction of 3.25 generates a monochloro Zr(III) intermediate, which could promote scission of the  124  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  C - 0 bond in THF. It is important to note that no conclusive evidence of this intermediate was observed as attempts to trap or observe a Zr(III) intermediate were not performed. Given that the reduction of 3.25 in the presence of THF yielded a species that reacts with the solvent, the reduction in toluene was examined.  Unfortunately, no  reaction between 3.25 and KCg was observed, potentially a result of the insolubility of 3.25 in toluene.  In an attempt to increase the solubility of the metal dichlorides in  toluene, the diisopropylphenyl-substituted 3.26  was used in the same reduction  conditions, however, no reaction was observed.  Other reducing reagents such as M g ,  Na/Hg amalgam, and Na have been investigated in similar conditions described above, however, no tractable materials were recovered.  4.7.  Synthesis of Hydrazido(l-) Hafnium [NCN] Complexes The coordination of hydrazine and substituted  hydrazines has generated  considerable interest, in particular for modeling transition metal intermediates in the biological fixation of dinitrogen. " 67  69  In light of our inability to isolate a dinitrogen  complex using the [NCN] ancillary ligand, the coordination of substituted hydrazines was investigated.  It was hoped that such studies would form N - N bonded complexes that  resemble intermediates in the metal-mediated reduction of dinitrogen to ammonia. Hydrazido ligands have been reported to coordinate to a metal centre in a variety of binding modes. This coordination is classified according to the charge carried by the hydrazido donor.  70,71  Widespread examples of this ligand include hydrazido(l-)  (NRNR ), hydrazido(2-) (NNR ) (where R signifies an organic group or H), and 2  hydrazido(4-) complexes.  2  Examples of the known coordination modes are given in  Figure 4.9.  125  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  R  R. R  FT  R  N'  N  N N \ / M  M  M r) -hydrazido(2-)  r\ -hydrazido(l-)  n -hydrazido(l-) 1  R  R  R  N  N' .N. M  p : r|',r| -hydrazido(2-) 1  Figure 4.9.  M=N  .N  M 2  .R N'  "M  M'  (j, : r] ,r| -hydrazido(4-)  [i : ri ,r| -hydrazido(2-) 2  N=M  2  2  1  1  1  Coordination modes of hydrazido ligands.  Despite many advances in the area of hydrazido transition metal chemistry, there are relatively few reports of early transition metal complexes incorporating this ligand. For example, mononuclear titanium cyclopentadienyl and porphyrin-supported complexes have been reported with n -hydrazido(l-) ligands.  72-74  A slight modification of the  supporting ligand can result in a dinuclear complex, as has been observed with a N,Ndi(pyrrolyl-a-methyl)-A^-methylamine (dpma) titanium complexes (Figure 4.10).  71  The  synthesis of hydrazido(2-) ligands also has precedent in E T M chemistry with reports of both  terminal  derivatives  mononuclear  complexes  71  and  binuclear  bridging  hydrazido(2-)  75  126  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Me  Me N  Me Me  \  T/ (mer-dpma)Ti^  l  N H  d p m  \ ^(/ac-dpma)  N Me  Me Me  NMe  ,ac-  /  (mer-dpmaJTi^  N Me  \  N  .  2  a)<  P  h  "  N  X  .  T  i  > -  N  ;  P  h  'Bu  Figure 4.10.  Examples of hydrazido(l-) and hydrazido(2-) titanium complexes.  The addition of 1 equivalent of 1,1-Me2NNH2 to 3.35 at -30°C resulted in the formation of 4.25, which was identified by N M R spectroscopy (Equation 4.6). The *H N M R spectrum reveals the presence of one amino - N H moiety as a singlet at 4.13 ppm and a - N M e 2 resonance at 2.0 ppm. Based on this data, the exact coordination mode of the hydrazido(l-) moiety cannot be determined, although given the coordination mode of the amidate ligands in 4.17 and 4.18, an n -orientation of the hydrazido(l-) group might be expected. This r\ coordination mode has precedent in hydrazido (1-) early transition 2  metal complexes (Figure 4.10).  71  ,N Me NNH PhMe -CH 2  N Mes'  Hf  N  (4.6)  2  4  / V C. H 3 \ Mes H3C  N Mes'  3.35  /  :Hf H cf 3  -N  N -NH Me' 'Me 'Mi  Mes  4.25  127  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  The expected ^-coordination mode is observed in the solid state structure of 4.25, which was determined by an X-ray diffraction experiment on crystals grown from a saturated solution of E t 2 0 .  A n ORTEP depiction of 4.25 is shown in Figure 4.11.  Relevant bond lengths and angles are listed in Table 4.8, and crystallographic details are located in appendix A . The molecular dimensions of the hydrazido(l-) complex are similar to reported Ti hydrazido(l-) complexes. '  The Hf-N bond length for the anionic  71 75  nitrogen containing the hydrogen is shorter than the nitrogen containing the two methyl substituents. The N3-N4 bond length is 1.437(5) A , reminiscent of the bond length found in hydrazine itself {ca. 1.47 A ) ,  Figure 4.11.  7 6  and consequently can be considered a single N - N bond.  ORTEP view of [NCN]Hf(Me)(n -NHNMe ) (4.25) depicted with 50% ellipsoids; with the exception of HI00, all hydrogen atoms have been omitted for clarity. Mes  2  2  128  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Table 4.8.  Selected Bond Distances (A) and Bond Angles (°) for [NCN]Hf(Me)(n -NHNMe ), (4.25).  Mes  2  2  Bond Angles 153.11(14) N3-HA-N4 78.06(7) N3-Hfl-Cl 83.3(2) HA-N5-N6 59.5(2) HH-N6-N5 r 37.2(2) N5-HA-N6  Bond Lengths Hfl-Cl Hfl-N3 Hfl-N5 Hfl-N6 Hfl-CT4 N5-N6  2.423(4) 2.123(3) 2.042(4) 2.355(3) 2.232(4) 1.437(5)  The addition of a second equivalent of 1,1 - M e 2 N N H 2 to 4.25 at -30°C produced 4.26, a bis(hydrazido)(l-) complex (Equation 4.7).  The ' H N M R spectrum reveals  equivalent - N ( C / / 3 ) 2 , aryl, and imidazole resonances, suggestive of a species with C 2  V  symmetry in solution. Although the solid state molecular structure of 4.26 remains unknown, two possible structural isomers could exist in solution which are consistent with the symmetry observed in the *H N M R spectrum. The two possibilities are: 1) the NMe2  moieties of the n - N H N M e 2 ligands are trans to each other (structure 4.26a,  Equation 4.7); or 2) the - N M e 2 moieties of the n - N H N M e 2 ligands are cis to each other 2  (structure 4.26b, Equation 4.7). Unfortunately, NOE measurements did not shed insight into the configuration of the hydrazido(l-) groups, but based on possible steric interactions  between  -NMe2  groups,  and  the  reported  structures  of  other  bis(hydrazido)(l-) complexes, the structure is most likely 4.26a. 71  129  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (4.7)  N N Me Me 2  2  4.26b  4.8.  Conclusions  In chapter 3, it was demonstrated that having the N H C situated between two anionic amide donors prevented the dissociation of a carbene moiety from an early transition metal.  What was not known was how stable early transition metal N H C  interactions would be during processes such as olefin polymerization and migratory insertion.  Driven by the precedent for activated NHC-derived group 4 catalysts to  polymerize a-olefins, the potential of several [NCN] group 4 metal alkyl compounds was investigated. Activation of the zirconium-dimethyl derivative with [Ph3C][B(C6Fs)4] in the presence of ethylene yielded a moderately active polymerization catalyst.  In the  presence of 1-hexene, the activated zirconium- and hafnium-dimethyl catalysts yielded a marginal amount of polymer. Investigation into the migratory insertion of isocyanides and CO into the hafnium-sp -carbon bond of several hafnium-alkyl derivatives revealed 3  the N H C moiety remains coordinated to the metal centre and does not participate in a manner that would alter the N H C donor.  130  Multiple insertions of substrates was References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  accomplished; in some examples further C-C bond coupling was observed to generate new eneamidolate and enediolate metallacycles.  Attempts to synthesize zirconium  [NCN] dinitrogen complexes by previously successful reduction methods  were  unsuccessful. In one case, an ether cleavage product was recovered (4.22), which is a result of solvent C - 0 bond activation. In the next chapter, the coordination of the [NCN] ligand to tantalum will be examined in an attempt to promote the reduction of dinitrogen.  131  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  4.9.  Experimental  4.9.1. General Considerations  Unless otherwise stated, general procedures were performed as described in Section 2.5.1.  4.9.2. Materials and Reagents  A l l materials were purchased from an appropriate supplier and purified by published methods prior to use. KCg was synthesized by the method described in the literature.  77  4.9.3. Synthesis and Characterization of Complexes 4.4 - 4.18, 4.24 - 4.26  In situ generation of [  Mes  [NCN]M(CH )][B(C F )4] (M=Zr (4.4), H f (4.5)). 3  6  5  The following procedure is representative of the synthesis of 4.4 and 4.5. To a cooled solution of 3.33 (35 mg, 0.069 mmol) in CD C1 (0.5 mL) was added a cooled 2  2  CD C1 (0.5 mL) solution of [Ph C][B(C F )4] (64 mg, 0.069 mmol). The pale orange 2  2  3  6  5  solution was immediately transferred to an N M R tube and then frozen in liquid N . The 2  N M R spectrum was taken immediately after warming the solution to -10°C. 4.4: ' H N M R (CD C1 ): 8 0.50 (s, 3H, -ZrC// ), 2.10 (br s, 12H, o-ArC// ), 2.15 (s, 6H, 2  2  3  3  />ArC// ), 3.45 (m, 2H, - N C / / ) , 3.94 (m, 2H, - N C / / ) , 4.14 (m, 2H, -NCH ), 4.29 (m, 3  2  2  2  2H, -NCH ), 6.85 (br s, 4H, -ArH), 7.04 (s, 2H, -imid//). 2  4.5: ' H N M R (CD C1 ): 8 0.26 (s, 3H, -HfC// ), 2.15 (br s, 12H, o-ArC// ), 2.20 (s, 6H, 2  2  3  3  />ArC// ), 3.70 (m, 2H, - N C / / ) , 4.05 (m, 2H, - N C / / ) , 4.28 (m, 2H, -NCH ), 4.60 (m, 3  2  2  2  2H, -NCH ), 6.99 (br s, 4H, -ArH), 7.15 (s, 2H, -imid//). 2  Synthesis of  Mes  [NCN]Hf(OTf)(CH ) 3  (4.6)  To a cooled ethereal solution (5 mL) of 3.35 (200 mg, 0.33 mmol) was added an ethereal solution (2 mL) of C F S 0 H (48 mg, 0.32 mmol). The solution was gradually 3  3  allowed to warm to room temperature and stirred overnight. The solvent was removed  132  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  and the residue recrystallized from Et20/hexane at -30°C to give a colorless solid. Yield = 205 mg, 85%. ' H N M R (CD C1 ): 5 0.19 (s, 3H, -UfCH ), 2.19 (br s, 12H, o-ArC// ), 2.21 (s, 6H, p2  2  3  3  A r C / / ) , 3.34 (m, 2H, - N C / / ) , 4.00 (m, 2H, -NCH ), 4.13 (m, 2H, - N C / / ) , 4.55 (m, 2H, 3  2  2  2  -NCH ), 6.87 (br s, 4H, -ArH), 7.09 (s, 2H, -imidtf). 2  Anal. Calcd. for C H F H f N 0 S : C, 44.35; H , 4.83; N , 7.66. 2 7  3 5  3  4  Found: C, 43.85; H ,  3  4.61; N , 7.09.  Synthesis of  Mes  [ N C N ] H f ( i i - X y N C C H ) ( C H ) (4.7) 2  3  3  To a cooled toluene (5 mL) solution of 3.35 (200 mg, 0.33 mmol) was added a cooled toluene (2 mL) solution of xylyl isocyanide (44 mg, 0.33 mmol). The pale yellow solution was allowed to gradually warm to room temperature and stirred overnight. The solvent was removed and suspended in cold (-30°C) hexanes. The solid was filtered and washed with cold hexanes to give a white powder. The solid was further recrystallized with E t 0 at -30°C. Yield = 183 mg, 74%. 2  ' H N M R (C D ): 5 0.17 (s, 3H, -HfC// ), 1.61 (s, 6H, -xylylC// ), 1.63 (s, 3H, -CCH ), 6  6  3  2.21 (s, 6H, -p-Ar -CH ), Mes  3  3  2.39 (s, 6H, -o-Ar -CH ), Mes  3  2.48 (s, 6H, - o - A r s CH ), 3.08  3  Me  3  (m, 2H, -NC/fc), 3.18 (m, 2H, -NCH ), 3.81 (m, 2H, -NCH ), 4.07 (m, 2H, -NCH ), 2  2  2  6.06  (s, 2H, -imid/f), 6.82-6.92 (m, 7H, -ArH). 13  C{'H} N M R (C D ): 8 18.2 (-ArCH ), 19.7 (-ArCH ), 19.8 (-ArCH ), 20.5 (-ArCH ), 6  6  3  3  3  3  22.4 (-ArCH ), 34.2 (-HfCH ), 52.2 (-NCH ), 56.9 (-NCH ), 118.7 (-imidQ, 124.3 (3  3  2  2  A r Q , 128.8 (-ArQ, 129.2 (-ArQ, 129.6 (-ArQ, 131.1 (-ArQ, 134.4 (-ArQ, 134.6 (A r Q , 147.2 (-ArQ, 154.8 (-ArQ, 197.5  (-HfC bene), car  259.0  (-HfC  imin0  acyi).  IR (nujol): u(C=N) 1575 cm" . 1  Anal. Calc. for C H 7 N H f : C, 59.37; H , 6.50; N , 9.62. Found: C, 59.23; H , 6.33; N , 36  4  5  9.46.  Synthesis of  Mes  [ N C N ] H f ( t i - R N C C H ) (R = Xy (4.8); R = Pr (4.10)) 2  j  3  2  The following procedure is representative of the synthesis of 4.8 and 4.10. To a toluene (2 mL) solution of 4.7 (200 mg, 0.33 mmol) was added a toluene (2 mL) solution  133  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  of xylyl isocyanide (92 mg, 0.70 mmol). The pale yellow solution gradually turned dark purple (or orange in the case of 4.8) and was stirred overnight, whereupon the solvent was removed quickly and E t 0 (2 mL) added to precipitate a white solid.  Cooling of the  2  solution, followed by filtration yielded colorless microcrystals. Yield = 260 mg, 92%. 4.8: *H NMR (CD C1 ): 8 1.45 (br s, 18H, -CCH 2  2  and - A r C 7 / ) , 1.85 (br s, 12H, -o-  3  Xy  3  Ar sCf7 ), 2.14 (br s, 6H, -/?-Ar C// ), 4.2 (br s, 8H, - N C / / ) , 6.60 (br s, 4H, -Ar Me  3  Mes  3  2  Mes  #),  6.80-6.85 (br s, 6H, - A r / / ) . 6.90 (s, 2H, -imid//). ' H N M R (CD C1 , 233 K): 8 1.21 (s, Xy  2  2  3H, - C C / / ) , 1.27 (s, 6H, - A r C / / ) , 1.57 (s, 6H, - A r C / / ) , 1.78 (s, 6H, -o-Ar sC// ), 3  X y  3  X y  I. 85 (s, 6H, -o-Ar sC// ), 2.10 (s, 6H, -p-Ar CH ), Me  3  Mes  3  Me  2.24 (s, 3H, -CCH ), 2.80 (m, 2H, -  3  3  N C / / ) , 3.98 (m, 4H, - N C / / ) , 4.27 (m, 1H, - N C / / ) , 6.56 (s, 2H, -Ar H), 2  Ar  Mes  2  2  6.64 (s, 2H, -  Mes  # ) , 6.81 (m, 1H, - A r / / ) , 6.85 (m, 2H, - A r / / ) , 6.90 (s, 2H, -imid/f). Xy  C{ U}  i3  3  l  Xy  NMR (C D ): 8 18.5 (-ArCH ), 20.4 (-ArCH ), 20.8 (-ArCH ), 23.6 (-ArCH ), 6  6  3  3  3  3  52.7 (-NCH ), 57.9 (-NCH ), 118.5 (-imidQ, 124.7 (-ArQ, 125.6 ( - A r Q , 129.1 (-ArQ, 2  2  129.9 (-ArQ, 130.3 (-ArQ, 135.1 (-ArQ, 156.5 (-ArQ, 196.5 (-HfC  carben  e).  IR(nujol): u(C=N) 1568 cm" . 1  Anal. Calc. for C 5H56HfN : C, 62.89; H , 6.57; N , 9.78. Found: 4  6  4.9: 'H NMR (C D ): 8 0.88 (d, J=7Hz, 12H, -CH(C// ) ), 1.32 (s, 6H, n - PrNCC// ), 2  6  6  3  -p-Av -CH3),  2.25 (s, 12H, - o - A r - C / / 3 ) , 2.31 (s, 6H,  MES  Mes  i  2  3  3.28 (m, 2H, - N A T C / / ) , 3.47 2  (sept, J=7Hz, 2H, -C//(CH ) ), 3.55 (m, 2H, - N C / / ) , 3.67 (m, 2H, - N C / / ) , 4.01 (m, 2H, 3  2  2  2  - N C / / ) , 6.07 (s, 2H, -imid//), 6.93-7.07 (m, 13H, -Ar//). 2  13  C{'H} NMR (C D ): 8 20.4 (-ArCH ), 20.9 (-ArCH ), 21.1 (-CCH ) 23.2, 48.8 (6  6  3  3  3  NCH), 53.3 (-NCH ), 56.4 (-NCH ), 119.4 (-imidQ, 128.7 ( - A r Q , 129.8 (-ArQ, 135.3 (2  2  A r Q , 157.6 (-ArQ, 194.5 (-HfC bene) 266.2 (-HfC acyi). car  irnn0  IR(nujol): u(C=N) 1562 cm" . 1  Anal. Calc. for C ^ F ^ H f N e : C, 57.17; H , 7.13; N , 11.43. Found: C, 56.89; H , 7.00; N , II. 26.  Synthesis of  Mes  [NCN]Hf(n -XyNCCH )(ii - PrNCCH3) (4.9). 2  2  i  3  To a toluene (2 mL) solution of 4.7 (100 mg, 0.14 mmol) was added a toluene (2 mL) solution of 'PrNC (10 mg, mmol). No observable color change was noted.  134  The  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  solution was stirred for 1 hour, whereupon the solvent was removed quickly and E t 0 (2 2  mL) added to precipitate a white solid, which was washed with hexanes and dried in vacuo. Yield = 96 mg, 86%. L  H N M R ( C D ) : 5 0.97 (d, J=7Hz, 6H, -CH(C// ) ), 1.23 (s, 3H, r^-'PrNCC/^), 1.91 (s, 6  6  3  6H, -xylylC// ), 2.26 (s, 6H, -p-Ar -CH ), 3  Ar  Mes  2  2.38 (s, 6H, -o-Ar -CH ),  3  Mes  2.39 (s, 6H, -o-  3  - C / / ) , 2.47 (s, 3H, - n - X y N C C / / ) , 3.10 (m, 2H, -NC// ), 3.43 (m, 2H, -NC// ), 2  Mes  3  3  2  2  3.56 (sept, J=7Hz, 1H, -C//(CH ) ), 3.69 (m, 2H, -NC// ), 3.88 (m, 2H, -NC// ), 6.01 (s, 3  2H, -imid//), 6.89 (s, 2H, - A r ,3  Mes  2  2  / / ) , 6.95 (s, 2H, - A r  Mes  2  / / ) , 6.97-7.04 (m, 3H, -Ar ,/7). xyly  C { ' H } N M R ( C D ) : 8 18.5 (-CCH ), 18.7 (-CCH ), 20.3 (-CH(CH ) ), 20.7 (-ArCH ), 6  6  3  3  3  2  3  20.9 (-ArCH ), 26.0 (-ArCH ), 50.3 (-NCH), 52.6 (-NCH ), 56.5 (-NCH ), 118.7 (3  3  2  2  imidQ, 124.3 ( - A r Q , 128.9 (-ArQ, 129.4 (-ArQ, 130.2 ( - A r Q , 134.7 (-ArQ, 135.8 (A r Q , 148.9 ( - A r Q , 157.4 (-ArQ, 195.1 (-HfC ben ), 262.4 (-HfC car  e  iminoacyl  ),  264.1 (-  HfCjminoacyl)IR (nujol): u(C=N) 1558, 1570 cm" . 1  Anal. Calc. for C ^ F ^ H f N e : C, 60.25; H, 6.83; N, 10.54. Found: C, 60.01; H, 6.82; N , 10.36.  Synthesis of  [ N C N ] H f ( O C ( C H ) = C ( C H ) N X y ) (4.11).  Mes  3  3  A toluene (10 mL) solution of 4.7 (102 mg, 0.14 mmol) was freeze-pumpedthawed with 1 atm CO several times and left to stand for 1 day. The solvent was removed in vacuo and the yellow powder was washed with hexane (5 mL). The yellow solid was recrystallized from E t 0 at -30°C to give crystals suitable for X-ray diffraction. Yield = 2  88 mg, 83%. ' H N M R ( C D , 298K): 8 1.37 (s, 3H, -NCC// ), 1.59 (s, 3H, -OCC// ), 2.21 (s, 6H, 6  6  3  3  C//3), 2.37 (s, 6H, -C//3), 3.01 (m, 4H, -NC// ), 3.51 (m, 2H, -NjC// ), 3.77 (m, 2H, 2  2  NC// ), 5.81 (s, 2H, -imid//), 6.90-6.96 (m, 5H, -ArH), 7.07-7.09 (m, 2H, -ArH). 2  ' H N M R ( C D C D , 223 K ) : 8 1.31 (s, 3H, -NCC// ), 1.60 (s, 3H, -OCC// ), 1.98 (s, 3  6  5  3  3  6H, -ArC//3), 2.24 (s, 6H, -ArC//3), 2.38 (s, 6H, -ArC//3), 2.69 (s, 6H, -ArC//3), 2.94 (m, 4H, -NC// ), 3.47 (m, 2H, -NC// ), 3.73 (m, 2H, -NC// ), 5.74 (s, 2H, -imid//), 6.81 2  (s, 2H, -Ar H), Mes  2  2  6.99 (m, 3H, -Ar H), 7.08 (s, 2H, xy  135  -Ar H). Mes  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  C{ H} NMR (C D , 298K): 5 15.2 (-NCCH ), 17.4 (-ArCH ), 19.0 (-OCCH ), 19.4 (-  i3  l  6  6  3  3  3  ArCH ), 20.9 (-ArCH ), 52.9 (-NCH ), 57.3 (-NCH ), 116.2 (-CN), 118.7 (-imidQ, 123.1 3  3  2  2  (-ArQ, 129.6 (-ArQ, 131.5 (-ArQ, 133.0 (-ArQ, 136.0 (-ArQ, 137.0 (-CO), 147.9 (A r Q , 149.6 (-ArQ, 196.7  (-HfC  carben  e)..  Anal. Calc. for C ^ y H f N s O : C, 58.76; H, 6.26; N , 9.26. Found: C, 58.29; H, 6.05; N , 9.33.  Synthesis of (NCN)Hf(n. -C(0)CH )(CH ) (4.12), C-4.12 Mes  2  13  3  3  The product was identified in situ by N M R and IR spectroscopy. A CeD6 solution (1 mL) of 3.35 was freeze-pumped-thawed three times with CO, and the solution left at 1 atmosphere. The solution was left to stand for 6 hours and the solvent removed in vacuo to yield a pale yellow solid. The product was contaminated with - 5 % 4.13. 'H NMR (C D ): 5 0.56 (s, 3H, -HfC// ), 1.62 (s, 3H, -HfC(0)C7/ ), 2.11 (s, 6H, -p6  6  3  3  ArC// ), 2.34 (s, 6H, -o-ArC// ), 2.44 (s, 6H, -o-ArC// ), 2.92 (m, 2H, -CH ), 3.20 (m, 3  3  2H, -CH ),  3.65 (m, 2H, -CH ),  2  AIH),  6.86 (s, 2H,  C{ H}  l3  l  2  NMR  3  3.96 (m, 2H, -CH ), 2  2  6.01 (s, 2H, -imid//), 6.76 (s, 2H, -  -ArH).  (C D ): 8 19.7 (-ArCH ), 19.8 (-ArCH ), 20.8 (-ArCH ), 31.1 6  6  3  3  3  (-  HfC(0)CH ), 34.7 (-HfCH ), 53.7 (-NCH ), 55.9 (-NCH ), 119.1 (-imidQ, 128.8 (-ArQ, 3  2  2  2  129.5 (-ArQ, 130.0 (-ArQ, 132.1 (-ArQ, 134.9 (-ArQ, 135.5 (-ArQ, 151.5 (-ArQ, 153.0 (-ArQ, 195.6  (-HfC  carben  e),  339.6 (-HfC ). acyl  IR(nujol): u(C=0) 1540 cm" . 1  C-4.12: ' H and  13  1 3  C N M R spectra identical to 19 except 1.62 (d, J=7Hz, 3H, -  HfC(0)C// ). 3  Synthesis of (NCN)Hf(OCH=CH )(CH ) (4.13) and C-4.13 Mes  13  2  3  A benzene solution (10 mL) of 3.35 (250 mg, 0.42 mmol) was freeze-pumpedthawed three times with CO, and the solution left to stir under 1 atmosphere for three days. The solvent was removed residue recrystallized with Et 0/hexanes at -30°C. Yield 2  = 162mg, 62%.  136  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  'H NMR (C D ): 8 0.37 (s, 3H, -HfC// ), 2.21 (s, 6H, -p-ArCH ), 6  6  3  2.34 (s, 6H, -o-  2  A r C / / ) , 2.62 (s, 6H, -o-ArC// ), 2.92 (m, 2H, - N C / / ) , 3.15 (m, 2H, - N C / / ) , 3.47 (d, J = 3  3  2  2  MHz, -CH), 3.54 (d, J = 6 Hz, -CH), 3.74 (m, 2H, -NCH ),  3.96 (m, 2H, - N C / / ) , 5.75  2  2  (dd, J = 6, 14 Hz, 1H, -CH), 5.94 (s, 2H, -imid//), 6.95 (s, 2H, -Ar//), 7.01 (s, 2H, -Ar//). '^{'H} NMR (C D ): 8 19.5 (-o-CH ), 20.9 (-/>CH ), 38.4' (-HfCH ), 52.1 (-NCH ), 6  6  3  3  3  2  55.1 (-NCH ), 117.4 (-imidC), 120.2 (-HfOCH=CH ), 129.4 (-ArQ, 130.4 (-ArQ, 133.7 2  2  (-ArQ, 139.0 (-HfOCH=CH ), 145.3 (-ArQ, 196.2 (-HfC 2  carbe  ne).  Anal. Calcd. for C H 8 H f N 0 : C, 53.80; H , 6.13; N , 8.96. Found: C, 53.53; H , 5.89; N , 28  3  4  8.61. C-4.13: ' H N M R resonances are identical except 8 5.75 (ddd, J= 6,14,145 Hz, 2H, -  13  Hf0 C/Z=CH ). 13  2  In situ generation of ^ [ N C N J H f ^ - C O C B u N B u ) (4.14) and C-4.14. 13  A C6D6 (1 mL) solution of 3.38 was freeze-pumped-thawed three times with CO. The reaction was followed by *H N M R spectroscopy and upon complete conversion to the monoacyl complex, a C N M R spectroscopy experiment was performed. 1 3  'H NMR (C D ): 8 0.66 (d, J = 7Hz, 6H, -CH(C// ) ), 1.06 (d, J = 7Hz, 2H, -HfC// ), 6  6  3  2  2  1.40 (d, J = 7Hz, 6H, -C(0)CH(C// ) ), 1.68 (d, J = 7Hz, 2H, -HfC(0)C// ), 1.80 (sept, J 3  2  2  = 7Hz, 1H, -C//(CH ) ), 2.18 (-ArC// ), 2.34(-ArC// ), 2.38 (-ArC// ), 2.75 (sept, J = 3  2  3  3  3  7Hz, 1H, -C(0)C//(CH ) ), 3.07 (m, 2H, -NC//), 3.28 (m, 2H, -NC//), 3.51 (m, 2H, 3  2  NC//), 4.00 (m, 2H, -NC//), 6.01 (s, 2H, -imid//), 6.78 (s, 2H, -ArH), 6.85 (s, 2H, -ArH). C{ H} l  l3  NMR (C D ): 8 19.8 (-ArCH ), 20.0 (-ArCH ), 21.2 (-ArCH ), 32.3 (6  6  3  3  3  HfC(0)CH ), 36.4 (-HfCH ), 54.2 (-NCH ), 55.6 (-NCH ), 118.4 (-imidQ, 128.4 (-ArQ, 2  2  2  2  128.6 (-ArQ, 129.2 (-ArQ, 130.4 (-ArQ, 131.2 (-ArQ, 132.4 (-ArQ, 149.8 (-ArQ, 153.2 (-ArQ, 196.1 ( - H f C  carbene  ) , 338.4 (-HfC ,).  C-21: *H N M R resonances are  13  acy  identical except 8 1.68  (dd,  J=4,7Hz, 2H, -  Hf C(0)C// ). 13  2  137  References begin on page 143.  Chapter Four: Reactivity  and Applications  of Group 4 [NCN] Transition  Metal  Complexes  In situ generation of [NCN]Hf(OC( Bu)=C( Bu)0) (4.15) and C-4.15. Mes  i  i  13  The same procedure was followed as described in the synthesis of 4.14; however the reaction was further monitored by H N M R spectroscopy after conversion to the [  monoacyl complex. Within 1 day, the presence of 4.15 was noted. 'H NMR (C D ): 8 1.06 (d, J = 8Hz, 12H,-CH(C// ) ), 1-99 (n, J = 8Hz, 2H, 6  6  3  2  C H C / / ( C H ) ) , 2.02 (d, J = 8Hz, 4H, -OCC// ), 2.22 (s, 6H, -p-AxCH ), 2.40 (s, 12H, -o2  3  2  2  3  A r C / / ) , 3.41(m, 4H, - N C / / ) , 3.61 (m, 4H, -NC// ), 5.89 (s, 2H, -imid//), 6.92 (s, 4H, 3  2  2  ArH).  NMR (C D ): 8 15.5 (-CH(CH ) ), 19.0 (-o-CH ), 21.2 (-/>CH ), 33.8 (-  C{ H} l  l3  6  6  3  2  3  3  CH(CH ) ), 38.3 (-CCH ), 49.4 (-NCH ), 52.1 (-NjCH ), 120.4 (-imidQ, 129.2 (-ArQ, 3  2  2  2  2  132.1 (-ArQ, 134.3 (-ArQ, 140.6 (-C=Q, 153.5 (-ArQ, 198.5 (-HfC  carben  e).  C-4.15: C N M R resonances are identical except 8 140.6 (d, J=30Hz, -C=Q.  13  1 3  Synthesis of [ [NCN]Hf(OC( Bu)=C( Bu)0)] (4.16) and C-4.16. Mes  i  i  13  2  A benzene solution (20 mL) of 3.38 (115 mg, 0.17 mmol) was freeze-pumpedthawed three times with CO, and the solution left to stand under 1 atmosphere for five days. Colorless crystalline material began to precipitate after three days. The solution was filtered and the crystalline material was washed with pentane. Yield - 82 mg, 66%. 'H NMR (C D ): 8 0.79 (d, J = 8Hz, 6H,-CH(C// ) ), 0.87 (d, J = 8Hz, 6H,-CH(C// ) ), 6  6  3  2  3  2  1.09 (m, 2H, - C C / / C H ) , 1.51 (m, 2H, - C C / / C H ) , 2.21 (s, 6H, - A r C / / ) , 2.33 (s, 6H, 2  2  3  A r C / / ) , 2.74 (s, 6H, - A r C / / ) , 3.40 (m, 4H, - N C / / ) , 3.55 (m, 2H, - N C / / ) , 4.16 (m, 2H, 3  3  2  2  -NC// ), 6.01 (s, 2H, -imid//), 6.96 (s, 2H, -ArH), 7.05 (s, 2H, -ArH) (multiplet from 2  C H C / / ( C H ) obscured by aryl resonances). 2  3  2  '^{'H} NMR (C D ): 8 14.6 (-CH(CH ) ), 14.8 (-CH(CH ) ), 19.6 (-ArCH ), 19.7 (6  6  3  2  3  2  3  ArCH ), 20.4 (-ArCH ), 34.3 (-CH(CH ) ), 34.6 (-CH(CH ) ), 39.4 (-CCH ), 39.6 (3  3  3  2  3  2  2  CCH ), 51.3 (-NCH ), 54.4 (-NCH ), 119.8 (-imidQ, 130.4 ( - A r Q , 131.6 (-ArQ, 131.8 2  2  2  (-ArQ, 133.4 (-ArQ, 134.1 (-ArQ, 140.0 (-C=Q, 149.4 (-ArQ, 153.2 (-ArQ, 195.4 (HfCcarbene)C-4.16: C N M R resonances are identical except 8 140.0 (d, J=30Hz, -C=Q.  ,3  1 3  138  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  Anal. Calc. for C 7 o H o H f N 0 4 : C, 57.02; H , 6.84; N , 7.60. Found: 56.72; H , 6.59; N , 10  2  8  7.43.  Synthesis  of  Mes  [NCN]Hf(Me)(ri -N( Bu)C(Me)0) 3  (4.17),  t  Mes  [NCN]Hf(Me)(r] 3  N( Pr)C(Me)N( Pr)) (4.18) i  i  The following procedure is representative of the synthesis of 4.17 and 4.18. In a 50 mL Erlenemeyer flask, 3.35 (100 mg, 0.17 mmol) was dissolved in 10 mL toluene and cooled to -30°C. At this temperature, a toluene (3 mL) solution of TSuNCO (17 mg, 0.17 mmol) was added dropwise and the colorless solution was slowly warmed to room temperature. Upon warming, the solution turned a pale yellow color and was stirred overnight. The solution was filtered through Celite and solvent was reduced in volume. Addition of hexane and cooling to -30°C resulted in the formation of colorless crystals which were recovered by filtration. Yield = 99 mg, 84%. 4.17: 'H NMR (C D ): 5 0.26 (s, 3H, -HfC// ), 1-05 (s, 9H, -C(C// ) ), 1.30 (s, 3H, 6  6  3  3  3  C C / / ) , 2.21 (s, 6H, -/>ArC// ), 2.35 (s, 6H, -o-ArCHf), 2.52 (s, 6H, -o-ArC// ), 3.42 (m, 3  3  3  2H, - N C / / ) , 3.45 (m, 2H, - N C / / ) , 3.59 (m, 2H, - N C / / ) , 3.64 (m, 2H, - N C / / ) , 6.07 (s, 2  2  2  2  2H, -imid//), 6.91 (s, 4H, -Ar//) I3  C{ H} NMR (C D ): 5 17.7 (-CH ), 20.3 (-CH ), 21.7 (-CH ), 23.2 (-CH ), 40.1 (!  6  6  3  3  3  3  C(CH ) ), 48.3 (-NCH ), 52.9 (-NCH ), H8.6 (-ArQ, 119.0 (-imidQ, 128.2 (-ArQ, 3  3  2  2  131.4 (-ArQ, 148.9 (-ArQ, 180.4 (-NCO), 193.8 (-NCN). Anal Calcd. for C ^ y H f N s O : C, 55.20; H , 6.80; N , 10.06. Found: C, 55.35; H , 6.64; N , 10.30. 4.18: *H NMR (C D ): 5 -0.06 (s, 3H, -HfC// ), 0.88 (d, J = 9 Hz, 6H, -CH(C//3) ), 0.90 6  6  3  2  (d, J = 9 Hz, 6H, -CH(C// ) ), 1.74 (s, 3H, - C C / / ) , 2.26 (s, 6H, -/>ArC// ), 2.46 (s, 6H, 3  2  3  3  o-AxCHf), 2.49 (s, 6H, -o-ArC// ), 3.32 (m, 2H, - N C / / ) , 3.41 (m, 2H, - N C / / ) , 3.50 3  2  2  (sept, J = 9 Hz, 1H, -C//(CH ) ), 3.68, (m, 2H, - N C / / ) , 3.78 (sept, J = 9 Hz, 1H, 3  2  2  C//(CH ) ), 4.34 (m, 2H, - N C / / ) , 6.06 (s, 2H, -imid//), 6.97 (s, 2H, -Ar//), 7.01 (s, 2H, 3  2  2  Ar//).  139  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  C{'H} NMR (C D ): 8 19.6 (-CH ), 20.4 (-CH ), 21.9 (-CH ), 30.2 (-CH ), 30.4 (-  13  6  6  3  3  3  3  CH ), 38.6 (-CH), 38.9 (-CH), 49.7 (-NCH ), 54.8 (-NCH ), 117.9 (-ArQ, 120.4 (3  2  2  miidQ, 127.9 (-ArQ, 132.6 (-ArQ, 150.2 (-ArQ, 179.5 (-NCN), 193.8 (-NCN). Anal Calcd. for C H H f N : C, 56.46; H , 7.25; N , 11.62. Found: C, 56.21; H , 7.35; N , 3 4  5 2  6  11.42.  Synthesis of [NCN]ZrCl(OCH CH CH CH ) (4.24) Mes  2  2  2  3  To a 250 mL thick-walled bomb charged with 3.25 (500 mg, 0.91 mmol) and K C  8  (270 mg, 2.0 mmol) was vacuum transferred 40 mL THF at -196°C. The frozen solution was freeze-pump-thawed three times with N and sealed at -196°C. The brown slurry 2  was slowly warmed to room temperature to yield a dark black suspension. After stirring for three days, the pressure in the bomb was reduced to one atmosphere and filtered through Celite. The solvent was removed and the yellow residue was extracted with E t 0 . The solvent was concentrated and left to stand at -30°C upon which time yellow 2  block crystals formed. Yield = 187 mg, 35%. 'H NMR (C D ): 8 0.9-1.1 (m, 7H, - C / / C / / C / / ) , 2.06 (s, 12H, -o-ArC// ), 2.24 (s, 6H, 6  6  2  2  3  3  -p-AxCH ), 3.42 (m, 2H, -NC//H), 3.50 (t, J = 8 Hz, 2H, -OCH \ 3.78 (m, 2H, -NC//H), 3  2  3.89 (m, 2H, -NC//H), 4.03 (m, 2H, -NC//H), 5.82 (s, 2H, -imid//), 6.89 (s, 2H, -Ar//), 6.94 (s, 2H, -Ar//). '^{'H} NMR (C D ): 8 16.9 (-CH ), 20.2 (-CH ), 20.9 (-CH ), 21.2 (-CH ), 22.4 (6  6  3  3  3  3  CH ), 48.9 (-NCH ), 51.3 (-NCH ), 60.4 (-OCH ), 118.5 (-ArQ, 120.3 (-imidQ, 128.6(3  2  2  2  A r Q , 130.5 (-ArQ, 149.2 (-ArQ, 192.5 '(-NCN). Anal Calcd. for C H i C l N O Z r : C, 59.20; H , 7.02; N , 9.52. Found: C, 59.35; H , 7.33; 29  4  4  N,9.67.  Synthesis of [NCN]Hf(Me)(NHNMe ) (4.25), [NCN]Hf(NHNMe ) (4.26) Mes  Mes  2  2  2  The following procedure is representative of the synthesis of 4.25 and 4.26.  In a  50 mL Erlenmeyer flask, 3.35 (200 mg, 0.33 mmol) was dissolved in 10 mL of toluene and cooled to -30°C. A toluene solution of M e N N H (20 mg, 0.33 mmol) was carefully 2  2  added dropwise at this temperature and the colorless solution was slowly warmed.to room  140  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  temperature.  After stirring overnight, the solution was filtered through Celite, and the  solvent removed in vacuo. E12O was added and the solution was carefully concentrated and cooled to -30°C to yield large block colorless crystals. Yield =131 mg, 62%. 4.25:  ' H  NMR ( C  6  D ): 6  5 0.35 (s, 3H, -HfC// ), 2.00 (s, 6H, -N(C# ) ), 2.32 (s, 6H, -o3  3  2  AxCHf), 2.44 (s, 6H, -o-ArC// ), 2.63 (s, 6H, -p-ArCH ), 3.44 (m, 2H, - N C / / ) , 3.62-3.70 3  2  2  (m, 6H, -NCH ), 4.13 (s, 1H, -NH), 6.08 (s, 2H, -imid//), 7.05 (s, 2H, -ArH), 7.09 (s, 2H, 2  -Ar//). 1 3  C{'H}  NMR ( C  HfCH ), 53.1 3  D ):  5 22.4 (-CH ), 23.1 (-CH ), 35.2 (-NCH ), 49.6 (-NCH ), 50.2 (-  (-NCH2),  118.6 (-ArQ, 119.2 (-imidQ, 128.4 (-ArQ, 130.1 (-ArQ, 143.2  6  3  6  3  3  2  (-ArQ, 191.4 (-NCN). Anal Calcd. for C28H HfN : C, 52.45; H , 6.60; N , 13.11. Found: C, 52.58; H , 6.51; N , 42  6  13.29. 4.26:  ' H  NMR  (C D ): 6  6  2.12 (s, 12H, -N(C// ) , 2.31 (s, 6H, -p-ArCH ), 2.50 (s, 12H, -o3  2  3  A r C / / ) , 3.60 (m, 4H, - N C / / ) , 3.78 (m, 4H, - N C / / ) , 6.04 (s, 2H, -imid//), 7.02 (s, 4H, 3  2  2  ArH). , 3  C{ H} l  NMR ( C  6  8 20.3 (-CH ), 21.5 (-CH ), 39.5 (-NCH ), 48.6 (-NCH ), 52.3 (-  D ):  3  6  3  3  2  N C H ) , 53.8 (-HfCH ), 118.0 (-ArQ, 118.5 (-imidQ, 127.9 (-ArQ, 133.2 (-ArQ, 145.9 2  3  (-ArQ, 192.5 (-NCN). Anal Calcd. for C 9H4 HfN : C, 50.83; H , 6.77; N , 16.35. Found: C, 50.77; H , 6.93; N , 2  6  8  16.18.  4.8.4. Polymerization protocols  a) Ethylene polymerization: A 100 mL Schlenk flask was charged with 50 mL toluene inside a glove box and attached to a vacuum line.  The toluene was degassed with  ethylene for 30 minutes at room temperature, whereby a toluene (5mL) solution of [Ph C][B(CeF5)4] was syringed into the flask. The orange solution was stirred for 5 3  minutes under ethylene. A toluene (5 mL) solution of the catalyst was quickly added and the opaque solution stirred for 15 minutes. The experiment was stopped by venting the ethylene and quenching the reaction with 10% methanolic HC1.  141  The resulting  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  polyethylene was filtered and washed with 10% methanolic HCI and methanol and airdried overnight.  b) 1-hexene polymerization: 4.4 and 4.5 were generated in chlorobenzene and 1-hexene was added immediately (-500 equivalents) by syringe. The solution was stirred for 1 hour and quenched with 10% methanolic HCI. The solvents were removed, the residue dissolved in pentane, and filtered through silica gel. The solvents were removed in vacuo to yield a minor amount of a viscous gel.  142  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  4.10.  References  (1)  Arnold, P. L . ; Mungur, S. A . ; Blake, A . J.; Wilson, C. Angew. Chem. Int. Ed.  2003, 42, 5981. (2)  Scollard, J. D.; McConville, D. H.; Vittal, J. J. Organometallics 1997, 16, 4415.  (3)  Keaton, R. J.; Jayaratne, K . C ; Fettinger, J. C ; Sita, L. R. J. Am. Chem. Soc. 2000,122, 12909.  (4)  Tshuva, E. Y . ; Groysman, S.; Goldberg, I.; K o l , M . ; Goldschmidt, Z. Organometallics 2002, 21, 662.  (5)  Tian, J.; Hustad, P. D.; Coates, G. W. J. Am. Chem. Soc. 2001,123, 5134.  (6)  Jeon, Y . - M ; Park, S. J.; Heo, J.; Kim, K . Organometallics 1998, 17, 3161.  (7)  Killian, C. M . ; Tempel, D. J.; Johnson, L. K . ; Brookhart, M . J. Am. Chem. Soc. 1996, 118, 11664.  (8)  Mashima, K . ; Fujikawa, S.; Tanaka, Y . ; Urata, H . ; Oshiki, T.; Tanaka, E.; Nakamura, A . Organometallics 1995, 14, 2633.  (9)  Mitani, M . ; Mohri, J.; Yoshida, Y . ; Saito, J.; Ishii, S.; Tsuru, K . ; Matsui, S.; Furuyama, R.; Nakano, T.; Tanaka, H . ; Kojoh, S.-i.; Matsugi, T.; Kashiwa, N . ; Fujita, T. J. Am. Chem. Soc. 2002,124, 3327.  (10)  Stevens, J. C.; Timmers, F. J.; Wilson, D. R.; Schmidt, G. F.; Nickias, P. N . ; Rosen, R. K . ; Knight, G. W.; Lai, S. Y.; (Dow Chemical Co., USA). Application: EP, 1991, p 58 pp.  (11)  Niehues, M . ; Kehr, G.; Erker, G.; Wibbeling, B.; Frohlich, R.; Blacque, O.; Berke, H. J. Organomet. Chem. 2002, 663, 192.  (12)  Aihara, H.; Matsuo, T.; Kawaguchi, H . Chem. Commun. 2003, 2204.  (13)  Skoog, S. J.; Mateo, C ; Lavoie, G. G.; Hollander, F. J.; Bergman, R. G. Organometallics 2000, 19, 1406.  (14)  Asakura, T.; Demura, M . ; Nishiyama, Y. Macromolecules 1991, 24, 2334.  (15)  Warren, T. H.; Schrock, R. R.; Davis, W. M . Organometallics 1996, 15, 562.  (16)  Durfee, L. D.; Rothwell, I. P. Chem. Rev. 1988, 88, 1059.  143  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (17)  Ford, P. C ; Editor ACS Symposium Series, Vol. 152: Catalytic Activation of Carbon Monoxide, 1981.  (18)  Grundemann, S.; Kovacevic, A.; Albrecht, M . ; Faller Jack, W.; Crabtree Robert, H. J. Am. Chem. Soc. 2002, 124, 10473.  (19)  Danopoulos, A . A . ; Tsoureas, N . ; Green, J. C.; Hursthouse, M . B. Chem. Commun. 2003, 756.  (20)  Chamberlain, L. R.; Durfee, L. D.; Fanwick, P. E.; Kobriger, L. M . ; Latesky, S. L.; McMullen, A . K.; Steffey, B. D.; Rothwell, I. P.; Foltin, K.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 6068.  (21)  Berg, F. J.; Petersen, J. L . Tetrahedron 1992, 48, 4749.  (22)  Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1290.  (23)  Bourissou, D.; Guerret, O.; Gabbaie, F. P.; Bertrand, G. Chem. Rev. 2000, 100, 39.  (24)  Chamberlain, L. R.; Durfee, L. D.; Fanwick, P. E.; Kobriger, L . ; Latesky, S. L.; McMullen, A . K.; Rothwell, I. P.; Folting, K.; Huffman, J. C ; et al. J. Am. Chem. Soc. 1987,109, 390.  (25)  Lappert, M . F.; Ngoc Tuyet Luong, T.; Milne, C. R. C. J. Organomet. Chem. 1979,174, C35.  (26)  Durfee, L. D.; McMullen, A . K . ; Rothwell, I. P. J. Am. Chem. Soc. 1988, 110, 1463.  (27)  Latesky, S. L.; McMullen, A . K.; Niccolai, G. P.; Rothwell, I. P.; Huffman, J. C. Organometallics 1985, 4, 1896.  (28)  Chamberlain, L. R.; Rothwell, I. P.; Huffman, J. C. J. Chem. Soc, Chem. Commun. 1986, 1203.  (29)  Erker, G.; Engel, K.; Krueger, C ; Mueller, G. Organometallics 1984, 3, 128.  (30)  Bristow, G. S.; Lappert, M . F.; Martin, T. R.; Atwood, J. L.; Hunter, W. F. J. Chem. Soc, Dalton Trans. 1984, 399.  (31)  Manriquez, J. M . ; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1978,100, 2716.  (32)  Wolczanski, P. T.; Bercaw, J. E. Acc Chem. Res. 1980, 73, 121.  144  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (33)  Choukroun, R.; Douziech, B.; Soleil, F. J. Chem. Soc., Chem. Commun. 1995,  2017. (34)  .;  Sonnenberger, D. C ; Mintz, E. A . ; Marks, T. J. J. Am. Chem. Soc. 1984, 106, 3484.  (35)  Marks, T. J. Science 1982, 217, 989.  (36)  Manriquez, J. M . ; Fagan, P. J.; Marks, T. J.; Day, C. S.; Day, V. W. J. Am. Chem. Soc. 1978, 100, 7112.  (37)  Erker, G.; Noe, R. J. Chem. Soc, Dalton Trans. 1991, 685.  (38)  S. Gambarotta, C. F., A. Chiesi-Villa, C. Guastini J. Am. Chem. Soc. 1983, 1690.  (39)  Erker, G.; Petrenz, R. J. Chem. Soc, Chem. Commun. 1989, 345.  (40)  Erker, G.; Sosna, F.; Zwettler, R.; Krueger, C. Organometallics 1989, 5, 450.  (41)  Erker, G.; Engel, K . ; Atwood, J. L.; Hunter, W. E. Angew. Chem., Int. Ed. 1983, 95, 506.  (42)  Meyer, T. Y . ; Garner, L. R.; Baenziger, N . C.; Messerle, L . Inorg. Chem. 1990, 29, 4045.  (43)  Gambarotta, S.; Strologo, S.; Floriani, C.; Chiesi-Villa, A . ; Guastini, C. Inorg. Chem. 1985, 24, 654.  (44)  Koterwas, L. A.; Fettinger, J. C ; Sita, L. R. Organometallics 1999, 75, 4183.  (45)  Sita, L. R.; Babcock, J. R. Organometallics 1998,17, 5228.  (46)  Jayaratne, K. C ; Sita, L. R. J. Am. Chem. Soc. 2000, 722, 958.  (47)  Littke, A.; Sleiman, N . ; Bensimon, C ; Richeson, D. S.; Yap, G. P. A.; Brown, S. J. Organometallics 1998, 7 7, 446.  (48)  Coles, M . P.; Swenson, D. C ; Jordan, R. F.; Young, V . G., Jr. Organometallics 1997,16, 5183.  (49)  Obermeyer, A . ; Kienzle, A.; Weidlein, J.; Riedel, R.; Simon, A . Z. Anorg. Allg. Chem. 1994, 620, 1357.  (50)  Sutton, L . E.; Editor Tables of Interatomic Distances and Configuration in Molecules and Ions: Supplement 1956-1959 (Chemical Society (London) Special Publication No. 18), 1965.  145  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (51)  Fryzuk, M . D.; Johnson, S. A.; Patrick, B. 0.; Albinati, A.; Mason, S. A.; Koetzle, T. F. J. Am. Chem. Soc. 2001,123, 3960.  (52)  Morello, L.; Y u , P.; Carmichael, C. D.; Patrick, B. O.; Fryzuk, M . D. J. Am. Chem. Soc. 2005,127, 12796.  (53)  Fryzuk, M . D.; Yu, P.; Patrick, B. O. Can. J. Chem. 2001, 79, 1194.  (54)  Basch, H.; Musaev, D. G.; Morokuma, K.; Fryzuk, M . D.; Love, J. B.; Seidel, W. W.; Albinati, A . ; Koetzle, T. F.; Klooster, W. T.; Mason, S. A . ; Eckert, J. J. Am. Chem. Soc. 1999,121, 523.  (55)  Cohen, J. D.; Fryzuk, M . D.; Loehr, T. M . ; Mylvaganam, M . ; Rettig, S. J. Inorg. Chem. 1998, 37, 112.  (56)  Cohen, J. D.; Mylvaganam, M . ; Fryzuk, M . D.; Loehr, T. M . J. Am. Chem. Soc. 1994,116, 9529.  (57)  Fryzuk, M . D.; Haddad, T. S.; Mylvaganam, M . ; McConville, D. H . ; Rettig, S. J. J. Am. Chem. Soc. 1993, 115, 2782.  (58)  Fryzuk, M . D.; Jin, W. Unpublished Results 1998.  (59)  Danopoulos, A . A.; Wright, J. A.; Motherwell, W. B. Chem. Commun. 2005, 784.  (60)  Arnold, P. L.; Liddle, S. T. Organometallics 2006, 25, 1485.  (61)  Arnold, P. L.; Liddle, S. T. Chem. Commun. 2005, 5638.  (62)  Fandos, R.; Hernandez, C ; Otero, A . ; Rodriguez, A . ; Ruiz, M . J.; Terreros, P. J. Organomet. Chem. 2000, 606, 156.  (63)  Chang, S.-J.; Liu, H.-J.; Chen, C.-T.; Shih, W.-E.; Lin, C . - C ; Gau, H.-M. J. Organomet. Chem. 1996, 523, 47.  (64)  Sobota, P.; Janas, Z. J. Organomet. Chem. 1983, 243, 35.  (65)  Covert, K . J.; Mayol, A.-R.; Wolczanski, P. T. Inorg. Chim. Acta 1997, 263, 263.  (66)  Miller, R. L.; Toreki, R.; LaPointe, R. E.; Wolczanski, P. T.; Van Duyne, G. D.; Roe, D. C. J. Am. Chem. Soc. 1993,115, 5570.  (67)  Burgess, B. K . Chem. Rev. 1990, 90, 1377.  (68)  Malinak, S. M . ; Coucouvanis, D. Prog. Inorg. Chem. 2001, 49, 599.  (69)  Einsle, O.; Tezcan, F. A.; Andrade, S. L. A.; Schmid, B.; Yoshida, M . ; Howard, J. B.; Rees, D. C. Science 2002, 297, 1696.  146  References begin on page 143.  Chapter Four: Reactivity and Applications of Group 4 [NCN] Transition Metal Complexes  (70)  Nugent, W. A . ; Haymore, B. L. Coord. Chem. Rev. 1980, 37, 123.  (71)  Li, Y.; Shi, Y.; Odom, A. L. J. Am. Chem. Soc. 2004,126, 1794.  (72)  Wiberg, N . ; Haering, H . W.; Huttner, G.; Friedrich, P. Chem. Ber. 1978, 777, 2708.  (73)  Blake, A . J.; Mclnnes, J. M . ; Mountford, P.; Nikonov, G. I.; Swallow, D.; Watkin, D. J. J. Chem. Soc, Dalton Trans. 1999, 379.  (74)  Thorman, J. L.; Woo, L. K . Inorg. Chem. 2000, 39, 1301.  (75)  Hughes, D. L.; Latham, I. A.; Leigh, G. J. J. Chem. Soc, Dalton Trans. 1986, 393.  (76)  Yamaguchi, A . ; Ichishima, I.; Shimanouchi, T.; Mizushima, S. J. Chem. Phys.  1959, 37, 843. (77)  Podall, H . E.; Foster, W. E.; Giraitis, A . P. J. Org. Chem. 1958, 23, 82.  147  References begin on page 143.  Chapter Five: Synthesis and DFT Studies of Tantalum [NCN] Transition Metal Complexes  Chapter Five  Synthesis and DFT Studies of Tantalum [NCN] Transition Metal Complexes 5.7.  Introduction*  Given the absence of N H C dissociation in group 4 [NCN] complexes discussed in chapter 4, we were interested in the synthesis of other early transition metal [NCN] complexes. As was previously discussed in chapter 2, a tantalum [NPN] complex has been isolated displaying a unique side-on end-on coordination mode for dinitrogen. The synthesis of this complex is quite remarkable as this occurs in the absence of strong reducing agents such as KCg or Na/Hg amalgam. In chapter 4, the synthesis of group 4 [NCN] dinitrogen complexes was attempted; however, no dinitrogen containing products were recovered. While the reasons for this are unclear, the potential for other [NCN] transition metal complexes to promote dinitrogen activation is of interest.  Tantalum  [NCN] complexes are of particular appeal, in light of the successful synthesis of the tantalum [NPN] dinitrogen complex 2.5.  * A version of this chapter has been accepted for publication (J. Am. Chem. Soc). 148  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  To the best of our knowledge, only one previous report describes the chemistry of tantalum-NHC complexes.  1  The addition of a simple alkyl-substituted N H C to  TaCi4(py)2 results in the displacement of both pyridine ligands to give TaCl4(NHC)2 (Scheme 5.1). Although these results appear promising, no solid state molecular structures, reactivity, or applications of the complexes were mentioned.  + TaCI (py) 4  2  2py  S c h e m e 5.1.  Pincer {NCN}-based ligands that have an anionic aryl group flanked by two amino donors have also been a subject of investigation in organotantalum chemistry (Scheme 5.2). " 2  8  In particular, a monoanionic {NCN} ligand has been found to be an  excellent spectator ligand that stabilizes and controls tantalum centered reactions. For example, the central metal-aryl unit of the {NCN} ligand was found to be chemically inert during a variety of alkylidene-based transformations reactions that resulted in the formation of reactive tantalum alkene adducts.  149  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Scheme  5.2.  This chapter details the synthesis of tantalum-amide,  -halide, and -alkyl  compounds bearing an [NCN] ancillary ligand. In addition, our unsuccessful attempts to prepare a coordinated dinitrogen stabilized by this ligand are also included. In the case of tantalum alkyl compounds, an unexpected C - H activation process occurs, which was investigated by DFT calculations and N M R experiments using deuterium labeled compounds.  5.2.  Synthesis of Amine-Amide fNCNH] Tantalum Derivatives  In light of the success using aminolysis reactions described in chapter 3, a similar approach was examined as a convenient entry into tantalum [NCN] derivatives. Disappointingly, there was no reaction between  Mes  [ N C N ] H (3.8) and Ta(NMe )5, even 2  2  at elevated temperatures. Decreasing the steric bulk on the amide donors did promote a reaction. The addition of  tol  [ N C N ] H (3.7) to Ta(NMe )s in toluene yielded a product 2  2  150  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  that displayed a set of H and C resonances in the N M R spectra indicative of C !  1 3  symmetric species (5.1). This is in contrast to the expected C tol  2 v  s  symmetry anticipated for  [NCN]Ta(NMe )3. N M R spectroscopy shows four multiplets for the ethylene spacers, 2  two doublets for the imidazole groups, two distinct sets of doublets typical of parasubstituted aryl rings, two aryl-methyl signals, and a broad resonance attributable to the N M e groups. Furthermore, a triplet at 3.32 ppm is observed which can be ascribed to an 2  amino - N H group. The C { ' H } N M R spectrum features a weak downfield resonance at 13  198.5 ppm, typical of a metal-carbene carbon atom.  From these results, it appears  coordination of the [NCN] ligand to tantalum is incomplete, one amine donor is still present, giving the molecule an overall C symmetry in solution (Equation 5.1). s  Ta(NMe ) , PhMe, ?  5  -HNMe ^NH  /  tol  (5.1)  2  HN'  \  tol  tol =  -Me  Orange crystals of 5.1 were grown from a saturated solution of toluene and were studied by X-ray crystallography. A n ORTEP depiction of the solid state molecular structure 5.1 is shown in Figure 5.1, with selected bond angles and lengths given in Table 5.1 and crystallographic details located in appendix A . The ligand assumes an amideamine donor configuration with respect to a distorted octahedral metal centre. The Taalkyl carbene bond length is 2.407(4) A and represents, to the best of our knowledge, the first crystallographically characterized Ta-C N H C bond. The Ta-N amido bond lengths are similar to other reported compounds. " 9  13  Although introduction of the [NCN] ligand  is incomplete, we were encouraged by the formation of a new Ta-C N H C bond. Thus far, all attempts to promote the coordination of the other pendant amine donor have been unsuccessful.  151  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Figure 5.1.  ORTEP view of [NCNH]Ta(NMe ) (5.1) ( C H C H omitted) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 5.1.  Selected bond distances (A) and angles (°) for [NCNH]Ta(NMe ) , 5.1.  tol  2  4  3  6  5  tol  2  Bond Angles N8-Tal-N3 90.58(12) N6-Tal-N3 178.48(11) N3-Tal-Cl 80.14(11)  Bond Lengths Tal-Cl Tal-N3 Tal-N8  4  2.407(4) 2.181(3) 2.050(3)  In chapter 3, alkyl elimination reactions between 3.7 and Zr(CH R) (R = SiMe3, 2  Ph) provided the desired five-coordinate dialkyl similar approach was examined with  Mes  tol  [NCN]Zr(CH R) 2  2  4  complexes.  A  [ N C N ] H (3.8) and Ta(CH Ph) . The reaction 2  2  5  proceeds immediately in toluene to give dark brown 5.2, which displays a ' H N M R spectrum with inequivalent imidazole and aryl resonances (Equation 5.2). A benzylidene resonance is observed at 4.81 ppm and correlates with a 13  ppm in the a tetraalkyl  C resonance located at 236.3  1  C{ H} N M R spectrum. Presumably, alkylidene formation proceeds through Mes  (NCNH)Ta(CH Ph) intermediate, which is not observed in solution. This 2  4  species undergoes a-hydrogen abstraction to generate the benzylidene product, a phenomenon that has been observed in other tantalum alkyl complexes. 152  14  Interestingly,  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  there is no change in the  1 3  C carbene resonance (or that in 5.1) in the presence of pyridine  over a long period of time, a surprising result despite the carbene dissociation reported in similar bidentate amido-carbene early transition metal complexes.  Ta(CH Ph) PhMe 2  'NH / Mes  HN' \ Mes  -  2  P  h  M  5  V  15  J ^"2"' s  (  5.2)  e  An ORTEP depiction of the solid state molecular structure for 5.2 is shown in Figure 5.2 as determined by an X-ray diffraction experiment. Relevant bond lengths and angles are listed in Table 5.2, and crystallographic details are located in Appendix A. A benzylidene moiety is clearly observed  in addition to an amide-amine  ligand  configuration on a distorted square pyramidal metal centre. The alkylidene moiety is clearly defined by a large Ta-C-C bond angle of 164.5(4)° and a short Ta-C alkyl bond (1.940(4) A ) , with the latter being significantly shorter than that of the other two Ta-C alkyl bonds (-2.26 A ) .  The Ta=C bond compares well with previously described Ta-  alkylidene complexes.  The Ta-C carbene and Ta-N amido bond lengths are similar to  16  5.1. Attempts to promote coordination of the pendant amine arm by thermolysis have proven futile leading only to decomposition.  153  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Figure 5.2.  Table 5.2.  ORTEP view of [NCNH]Ta(CHPh)(CH Ph) (5.2), depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity with the exception of HI 01. Mes  2  Selected bond distances (A) [NCNH]Ta(CHPh)(CH Ph) (5.2).  2  and  angles  (°)  for  Mes  2  2  Bond Angles N3-Tal-Cl 80.90(9) C41-C28-Tal 164.5(2) C29-C26-Tal 126.44(18)  Bond Lengths Tal-C28 Tal-N3 Tal-C26 Tal-C27 Tal-Cl  5.3  1.940(3) 2.011(2) 2.243(3) 2.259(3) 2.290(3)  Successful Synthesis of TafNCNJ Amide Complexes  Given the difficulty of coordinating both amide donors to a Ta(V) centre by aminolysis and alkane elimination reactions, an alternative method was sought as a means to generate the desired tridentate coordination mode for this ligand system. Metathesis reactions with Li [NPN] have successfully been used by many groups 2  154  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  including our own in the synthesis of tantalum [NPN] metal complexes. reaction of 3.10 and Cl Ta(NMe ) proceeds at -30°C to produce 2  (5.3) in good yield.  2  tol  3  17  The metathesis  [NCN]Ta(NMe ) 2  3  The *H N M R spectrum features two multiplets for the ethylene  spacers and one set of resonances for the imidazole, aryl, and /?ara-methyl aryl groups. There are two sets of resonances for the N-methyl protons of the N M e groups in a ratio 2  of 2:1 at 3.22 and 3.68 ppm. A weak  1 3  C resonance in the C { ' H } N M R spectrum is 13  also observed at 186.7 ppm, indicative of a metal-carbene carbon atom (Equation 5.3).  -N CI Ta(NMe ) 2  ,„»^ '".„, L |  tol  3.10  2  N-  (5.3)  3>  -30°C, THF -2 LiCI  .  tol  t 0  ''  M e  2 Le  tol  N /  2  5.3  Crystals suitable for an X-ray diffraction experiment were grown from toluene and an ORTEP depiction of the solid state molecular structure of 5.3 is shown in Figure 5.3. Relevant bond lengths and angles are listed in Table 5.3, and crystallographic details are located in appendix A . Clearly the ligand exists in a dianionic state with both pendant amide donors coordinating to a single tantalum centre. The ligand adopts a meridional orientation with respect to a distorted octahedral metal centre as evidenced by the cis oriented amido donors (N2-Tal-N3 = 89.25(4)° and N2-Tal-N4 = 98.46(4)°). The Ta-C carbene and Ta-N amido bond lengths are similar to previously discussed complexes.  155  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Figure 5.3.  ORTEP view of [NCN]Ta(NMe )3 (5.3), depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 5.3.  Selected bond distances ( A ) and angles (°) for [NCN]Ta(NMe )3 (5.3).  tol  2  tol  2  Bond Angles N3-Tal-N2 89.25(13) N3-Tal-Cl 82.93(10) N2-Tal-Cl 81.54(9) N4-Tal-Cl 180.000(2)  Bond Lengths Tal-N3 Tal-N4 Tal-N2 Tal-Cl  2.055(3) 2.078(4) 2.132(3) 2.365(6)  Modification of the tantalum starting material serves as a useful entry into mixed amide-chloride metal complexes. The reaction of 3.10 and Cl3Ta(NMe ) (THF) yields 2  2  the expected product [NCN]TaCl(NMe ) (5.4) (Scheme 5.3). The H N M R spectrum tol  !  2  2  reveals a C symmetric species in solution with four sets of multiplets for the ethylene s  spacers and most noticeably three singlets integrating to six protons each. This evidence suggests a cis arrangement of N M e groups on the tantalum centre. Although no crystals 2  of the product could be recovered, N M R evidence is quite compelling given that trans deposited N M e groups would yield a species with C 2  2 v  symmetry in solution. A similar  reaction with 3.10 and TaCl (NEt )(Et 0) also yields the expected [NCN]TaCl (NEt ) tol  4  product.  2  2  2  2  The ' H N M R spectrum reveals the presence of two structural isomers in 156  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  solution. The minor species possesses C symmetry, a result that would be expected with s  cis deposited chloride groups on the tantalum centre (5.5). C  2 v  The major species possesses  symmetry, indicative of trans oriented chloride groups on the metal centre (5.6).  5.5 S c h e m e 5.3.  5.6  The reactivity of these amide-substituted TafNCN] complexes was investigated, in particular the synthesis of [NCNJTaCh. and alkyl derivatives. These complexes could be used in reductive processes to activate N . Unfortunately, attempts to convert the 2  amide groups of 5.3-5.6 to chloride ligands with TMSC1, BCI3, or NEt3-HCl yields a mixture of intractable materials. Similar results were found when alkylation of 5.3-5.6 was attempted with A l M e , MeLi, MeMgBr, or ( BuCH ) Zn. The reduction of 5.3-5.6 l  2  6  2  2  with strong reducing reagents under N was also investigated; however, no dinitrogen 2  containing products were identified.  5.4.  Isolation of Cyclometallated [NCCNJTa Dialkyl Derivatives  One of the precursors for the synthesis of the [NPN] tantalum dinitrogen complex 2.5 is an [NPN]-substituted tantalum trialkyl derivative.  Given the success of  coordinating the [NCN] ligand to tantalum by metathesis reactions with mixed alkyl-  157  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  chloro precursors of Ta(V), C^TaR^ (R = Ctb'Bu, Me, CH2PI1), was examined. The reaction of 3.11 with Cb-Taf^CHVBu^ is representative of these metathesis reactions and proceeds immediately at -30°C in THF to give a brown solution. The ' H N M R spectrum of the product reveals a complicated set of resonances indicative of a low-symmetry species.  The ethylene arms of the ligand backbone are observed as sets of complex,  coupled resonances.  The asymmetry of the product is further  exemplified by  inequivalent imidazole-hydrogen resonances at 5.82 and 5,88 ppm. Two different tantalum alkyl ' H resonances are also observed, which is unexpected for the anticipated ^[NCNJTaCCHz'BuJs product. The C{'H} N M R spectrum shows two distinct Ta-C 13  alkyl resonances around 70 ppm, and one weak resonance at 85 ppm suggestive of another Ta-C moiety (Equation 5.4).  (5.4)  R = CH Bu l  2  CH  3  CH Ph 2  5.7  5.8 5.9  The solid state molecular structure of 5.7 was determined from an X-ray diffraction experiment and an ORTEP depiction is shown in Figure 5.4. Selected bond angles and lengths are given in Table 5.4 and crystallographic details are located in appendix A .  Surprisingly, one of the six-membered metallacycles has undergone  cyclometallation to form new five- and three-membered rings. In lieu of the amide C - H bond activation, only two neopentyl groups are observed rather than the expected trialkyl substitution. The C-H bond activated ligand (denoted [NCCN]) adopts a distorted facial orientation about a distorted trigonal bipyramidal metal centre. The bond angles defined by Tal-C7-N4 are typical of another structurally characterized metallaaziridine tantalum  158  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  complex.  18  A l l Ta-C alkyl bonds are similar in length (-2.24 A ) , and are representative  of other reported Ta-C alkyl bond lengths. ' '  16 17 19  Figure 5.4.  ORTEP view of [NCCN]Ta(CH Bu) (5.7), depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 5.4.  Selected bond distances ( A ) and angles (°) for  Mes  t  2  2  Mes  [NCCN]Ta(CH Bu) t  2  2  (5.7). Bond Angles 153.91(6) N4-Tal-N3 89.46(6) N4-Tal-Cl 79.59(6) N3-Tal-Cl 39.37(6) N4-Tal-C7 61.34(9) N4-C7-Tal 79.29(10) C7-N4-Tal  Bond Lengths Tal-N4 1.9877(15) 2.0738(17) Tal-N3 2.1833(17) Tal-C31 2.2247(17) Tal-Cl Tal-C7 2.2257(19) 2.255(2) Tal-C26  159  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  5.5.  Mechanistic Insight Into the Formation of 5.7-5.9  Intramolecular C - H bond activation of ligands in Ta complexes is relatively common, '  particularly with amido-based systems. '  20 21  18 19,22  "  25  Among these reports, the  formation of metallaaziridine rings by exocyclic ' ' C-H bond activation is known; the 18 24 25  only example of endocyclic C-H bond activation involves a tripodal tris(aryloxy)amine 19  system that activates next the amine donor.  In most examples, metallaaziridine ring  formation appears to follow a a-bond metathesis mechanism involving direct elimination of an alkane, although in some cases the mechanism was not fully investigated. 24  19  Two plausible mechanisms were explored for the formation of 5.7-5.9. Assuming that metathesis reactions between L i [ N C N ] and Cl TaR Ar  2  Ar  2  3  provide the trialkyl  [NCN]TaR derivatives, the ligand backbone P-H abstraction process may occur by 3  either a one-step a-bond metathesis pathway (Path 1, Figure 5.5) or a two-step pathway that involves a-H abstraction to produce a [NCN]Ta(=CHR')R alkylidene intermediate (Path 2, Figure 5.5). This alkylidene intermediate could then mediate C - H bond activation of the ligand backbone. Given the literature precedence for both mechanisms, density functional calculations and isotopic labeling experiments were used to elucidate a mechanism for the formation of 5.7-5.9.  160  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  r=\  TaCI R 2  Ar  x  NLi  3  - 2 LiCI  LiN  Ar  7\r  Path 1 i) a-bond metathesis  c  r=\  Ar = 2,4,6-Me C H R = benzyl, neopentyl 3  6  2  R' Path 2 ii) a-H abstraction followed by iii) alkylidene mediated C-H activation Figure 5.5. 5.6.  Potential pathways for ligand P-H abstraction.  Determination of Mechanism by DFT Calculations DFT calculations were performed using the model complex shown in Figure 5.6  and the B3LYP/BS1 level of theory. A l l the DFT calculations were performed by Dr. Chad Beddie at the Texas A & M University under the supervision of Professor Michael Hall.  The proposed mechanisms were investigated by calculating the structures and  energies of intermediates and transition state structures along both pathways (Figure 5.5). The results of these calculations are discussed in detail in appendix B .  161  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  r=\ N  r=\  N  H  Experimental M e s  Figure 5.6.  H  Computational  Ligand  [NCN]  H  Ligand  [NCN]  Computational model of the trimethyl tantalum starting complex.  The computational results suggest the lowest energy pathway involves a tantalum alkylidene intermediate, which can then mediate C-H bond activation with a neighboring backbone linker C - H group to form a new metallaaziridine.  The energies of the  intermediates and transition states for both path 1 and 2 are shown in Figures 5.7 and 5.9, respectively.  The structures of the energy minimized transition states are given in  Figures 5.8 (Path 1) and 5.10 (Path 2).  162  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  TS-A-B (49.6)  These isomers vary in the conformation of the 6 member rings  Gas-phase relative free energies at the B3LYP/BS1 level of theory based on the energy of separated 1 set to 0.0 kcal/mol are provided in parentheses in kcal/mol. Electronic energies, corrected zero-point energies, enthalpies, and free energies are provided in Table 1. a  Figure 5.8.  JIMP  Pictures of the one-step a-bond metathesis pathway.  163  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  TS-A-E (36.4)  A  F-J  D  These isomers vary in the conformation of the 6 member rings  Gas-phase relative free energies at the B3LYP/BS1 level of theory based on the energy of separated 1 set to 0.0 kcal/mol are provided in parentheses in kcal/mol. Electronic energies, corrected zero-point energies, enthalpies, and free energies are provided in Tabiei. Figure 5.9. Relative energies of the intermediates and transition states in a potential two-step a-H abstraction/alkylidene mediated C-H activation mechanism. a  164  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal  TS-J-D  J  Figure 5.10.  5.7.  Complexes  D  J I M P Pictures of alkylidene mediated C - H activation of the ligand backbone. 26  Verification of the Mechanism proposed by DFT Calculations  Based on the computational support for the intermediacy of a tantalum alkylidene in the endocyclic C - H activation process, the synthesis of an [NCN] tantalum alkylidene complex was attempted. Beginning with Cl3Ta=CH Bu(THF)2, the reaction with 3 . 1 1 t  proceeds to give 5 . 1 0 in good yield (Scheme 5.4).  Both the H and ]  l3  C{'H} N M R  spectra display resonances similar to the previous cyclometallated complexes 5.7-5.9. Examination of the H N M R spectrum during the reaction reveals the presence of 2 , 2 !  dimethylpropane formation and no observable intermediate.  165  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  5.10 S c h e m e 5.4.  An X-ray diffraction experiment was performed on crystals grown from  Et20  with an ORTEP depiction of 5.10 given in Figure 5.11. Relevant bond lengths and angles are listed in Table 5.5, and crystallographic details are located in appendix A . The solid state molecular structure reveals an endocyclic C-H bond activated complex with similar structural characteristics to 5.7.  Clearly, there is no neopentylidene present as the Ta-C  alkyl bonds from both complexes are of similar length. The Tal-C5 alkyl bond length of 2.216(4) A is similar to length to 5.7, as are the bond angles defined by the N3-C5-Tal metallaaziridine ring.  166  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Figure 5.11.  ORTEP view of [NCCN]Ta(Cl)(CH Bu) (5.10), depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 5.5.  Selected bond distances ( A ) and angles (°) for (5.10).  Mes  t  2  [NCCN]Ta(Cl)(CH Bu) t  2  Bond Angles N3-Tal-N4 115.35(15) 39.64(16) N3-Tal-C5 84.96(15) N3-Tal-Cl 77.84(15) N4-Tal-Cl 79.6(2) C5-N3-Tal 60.8(2) N3-C5-Tal  Bond Lengths Tal-N3 Tal-N4 Tal-C5 Tal-C26 Tal-Cl Tal-Cl 1  Mes  1.967(4) 2.010(3) 2.216(4) 2.224(4) 2.241(4) 2.3996(11)  Although these experimental results cannot confirm the presence of an alkylidene intermediate in the decomposition of [NCN]Ta(alkyl)3 complexes, they infer that an alkylidene species can undergo rapid amido C - H bond activation. Further evidence for the mechanism postulated by DFT calculations was observed in N M R experiments using deuterium labeled complexes. Utilizing Cl Ta(CD Ph)3 as a starting material, we can 2  2  examine the proton distribution in the final C - H bond activated product was examined 167  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  (Scheme 5.5).  If the mechanism proceeds as suggested by calculations, the tantalum  alkylidene intermediate would abstract a proton from the ethylene spacer to yield a TaC//(D)Ph moiety (Path 1, Scheme 5.5).  If a concerted a-bond metathesis was the  operant mechanism, this reaction would yield two - C D 2 P h groups and no benzylic proton resonances would be observed (^4-5.9, Path 2, Scheme 5.5). The reaction of 3.11 with Cl Ta(CD Ph) yields <i -5.9. The ' H N M R spectrum clearly shows a 1:1:1 triplet at 2.70 2  2  3  3  ppm, evidence for the -TaC//(D)Ph moiety in d -5.9. 3  This result suggests DFT  calculations are correct and implies that the decomposition of [NCN]Ta(alkyl)  3  complexes proceeds through an alkylidene intermediate which rapidly undergoes C-H bond activation with an amido donor.  Scheme 5.5.  5.8.  Conclusions  In this chapter, the potential of the [NCN] ligand architecture to stabilize tantalum amide, halide, and alkyl complexes has been presented.  168  Aminolysis and alkyl  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  elimination reactions, which were previously successful in the synthesis of group 4 [NCN] complexes, provided a route to incorporate one flanking amido arm. Thus far, attempts to promote coordination of the second pendant amine arm have been unsuccessful. Coordination of both pendant amide donors was achieved by metathesis reactions between Lia^fNCN] and substituted tantalum chlorides. In the case of trialkyl tantalum  derivatives, amide  C - H bond activation occurs to generate a new  cyclometallated metallaaziridine. DFT calculations on model complexes suggested that the mechanism for this phenomenon  proceeds  through  a tantalum alkylidene  intermediate, which can then mediate C - H bond activation with a neighboring amido group to form a new metallaaziridine. In light of these findings, we examined the synthesis of tantalum alkylidene complexes stabilized by an [NCN] ancillary ligand and found that similar amide C-H bond activation occurs. While this result cannot confirm the mechanism postulated by DFT calculations, deuterium labeling experiments have shown that a tantalum alkylidene intermediate is involved during this process.  169  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  5.9.  Experimental Section  5.9.1. General Considerations Unless otherwise stated, general procedures were performed as described in Section 2.5.1. DFT calculations were performed at the Department of Chemistry at the University of Texas A & M by Dr. Chad Beddie.  5.9.2. Materials and Reagents Ta(NMe2)5 were purchased from Strem Chemicals and used as received. A l l other 27  chemicals were purchased Cl Ta(NMe ) , 2  2  Cl Ta(NMe ) (THF),  13  3  3  Cl Ta(CH Ph) , 2  2  from Aldrich and used as received.  3()  3  2  2  Cl Ta(CD Ph) ,  30  2  2  3  Cl Ta(NEt )(Et 0),  28  4  Cl Ta(CH Bu) , t  2  2  2  Ta(CH Ph)5, 2  Cl TaMe ,  28  2  2  Cl Ta=CH Bu(THF)  31  t  3  3  29  3  were all  32 2  synthesized by literature methods.  5.9.3. Synthesis and Characterization of Complexes 5.1 - 5.10 Synthesis of [NCNH]Ta(NMe ) (5.1) tol  2  4  To a stirred toluene solution (5 mL) of Ta(NMe )5 (216 mg, 0.54 mmol) in a 50 2  mL Erlenmeyer flask was added a toluene solution (5 mL) of 3.7 (181 mg, 0.54 mmol). The orange solution was stirred overnight and filtered thru Celite.  The solvent was  removed until the volume was ~2 mL, and then cooled to -30°C to yield orange blocks. Yield - 246 mg, 66%. 'H NMR (C D ): 2.22 (s, 3H, -ArC// ), 2.44 (s, 3H, -ArC// ), 3.06 (br s, 12H, -NC// ), 6  6  3  3  3  3.16 (m, 2H, - N C / / ) , 3.27 (m, 2H, -NC// ), 3.32 (br m, 1H, -N//), 3.52 (br s, 6H, 2  2  N C / / ) , 3.75 (br s, 6H, - N C / / ) , 4.03 (m, 2H, -NC// ), 4.19 (m, 2H, - N C / / ) , 5.98 (br s, 3  2  2  2  1H, -imid//), 6.29 (br s, 1H, -imid//), 6.38 (d, J=7 Hz, 2H, -Ar//), 6.91 (d, J=7 Hz, 2H, Ar//), 7.01 (d, J=7 Hz, 2H, -Ar//), 7.24 (d, J=7 Hz, 2H, -Ar//). C{'H} NMR (C D ): 18.1 (-CH ), 20.2 (-CH ), 45.5 (br, -NCH ) 46.9 (-NCH ), 47.0 (-  13  6  6  3  3  3  2  N C H ) , 47.5 (-NCH ), 48.9 (-NCH ), 118.6 (-ArQ, 119.3 (-ArQ, 120.5 (-imidQ, 122.6 2  2  2  170  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  (-imidQ, 124.8 (-ArQ, 124.9 (-ArQ, 128.7 (-ArQ, 129.2 (-ArQ, 140.5 (-ArQ, 141.6 (A r Q , 198.5 (-NCN). Anal. Calcd. for C 9 H N T a : C, 50.43; H , 7.15; N , 16.22; Found: C, 50.11; H , 7.00; N , 2  4 9  8  15.95.  Synthesis of [NCNH]Ta=CHPh(CH Ph) (5.2) Mes  2  2  To a stirred toluene solution (5 mL) of Ta(CH Ph) (328 mg, 0.51 mmol) was 2  5  added a toluene solution (5 mL) of 3.8 (200 mg, 0.51 mmol) in a 50 mL Erlenmeyer flask.  The dark brown solution was stirred overnight and filtered thru Celite. The  solvent was removed to yield a brown residue, which was triturated with hexanes (10 mL) to yield a brown powder.  Yield = 327 mg, 76%.  X-ray quality crystals were  obtained from a cooled (-30°C) toluene solution. !  H NMR ( C D ) : 2.02 (s, 3H, -/?-ArCH ), 2.08 (s, 6H, -o-ArCH ), 2.20 (s, 6H, -o6  6  3  3  ArCH ), 2.31 (s, 3H, -p-ArCR ), 2.42 (m, 4H,-TaC// ), 2.43-3.10 (m, 7H, - N i / and 3  3  2  NC//2J and 3.58 (dt, J = 6Hz, 1H, -NC//), 4.40 (dt, J = 6Hz, 1H, -NC//), 4.81 (s, 1H, C//Ph), 5.81 (d, J=2 Hz, 1H, -imid//), 6.23 (d, J=2 Hz, 1H, -imid//), 6.60-6.85 (m, H , ArH), 7.42 (d, J=8 Hz, 4H, -ArH).  C{ H}  l3  l  NMR ( C D ) : 17.9 (-CH ), 18.2 (-CH ), 20.7 (-CH ), 21.0 (-CH ), 48.7 (6  6  3  3  3  3  N C H ) , 48.8 (-NCH ), 51.6 (-NCH ), 54.5 (-NCH ), 69.9 (-TaCH ), 85.0 (-TaCH ), 119.6 2  2  2  2  2  2  (-ArQ, 120.3 ( - A r Q , 121.2 (-imidQ, 123.7 (-imidQ, 125.6 ( - A r Q , 129.3 (-ArQ, 129.8 (-ArQ, 129.9 (-ArQ, 130.6 (-ArQ, 131.0 (-ArQ, 132.0 (-ArQ, 136.1 (-ArQ, 137.6 (A r Q , 137.8 ( - A r Q , 138.2 (-ArQ, 142.7 (-ArQ, 147.8 (-ArQ, 148.7 (-ArQ, 155.3 (A r Q , 205.0 (-NCN), 236.3 (-TaCH). Anal. Calcd. for C 6 H N T a : C, 65.55; H , 6.34; N , 6.65; Found: C, 65.26; H , 6.22; N , 4  5 3  4  6.59.  Synthesis tol  of  tol  [NCN]Ta(NMe ) 2  (5.3),  3  tol  [NCN]Ta(NMe ) Cl 2  2  (5.4),  [NCN]Ta(NEt )Cl (5.5-5.6) . 2  2  The following procedure is representative of the synthesis of 5.3-5.6. To a cooled (-30°C) THF solution (5 mL) of Cl Ta(NMe ) (288 mg, 0.75 mmol) was added a chilled 2  2  3  (-30°C) THF solution (5 mL) of 3.10 (408 mg, 0.75 mmol) in a 50 mL Erlenmeyer flask.  171  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  The solution slowly darkened to brown upon warming to room temperature. The solution was stirred overnight whereupon the solvent was removed and toluene added. The solution was filtered thru Celite and the solvent removed to yield an orange/brown residue.  Trituration of the residue with hexane yielded an orange solid which was  recrystallized from toluene. Yield = 383 mg, 79%. 5.3:  'H N M R (C D ): 2.45 (s, 6H, -ArCH ), 3.22 (s, 12H, - N C / / ) , 3.53 (m, 4H, 6  6  3  3  N C / / ) , 3.68 (s, 6H, -NCr7 ), 4.15 (m, 4H, - N C / / ) , 6.00 (s, 2H, -imid//), 7.11 (d, J = 2  3  2  8Hz, 4H, -ArH), 7.27 (d, J = 8Hz, 4H,  C{ H}  l3  -ArH).  N M R (C D ): 18.7 (-CH ), 45.4 (-NCH ), 47.0 (-NCH ), 48.0 (-NCH ), 50.7 (-  l  6  6  3  3  3  2  N C H ) , 117.3 (-ArQ, 118.3 (-ArQ, 124.4 (-imidQ, 126.6 (-ArQ, 152.6 (-ArQ, 186.7 (2  NCN). Anal. Calcd. for C H N T a : C, 50.23; H, 6.56; N , 15.19; Found: C, 50.10; H , 6.35; N , 27  42  7  15.05. 5 . 4 : 'H N M R (C D ): 2.26 (s, 6H, - A r C / / ) , 3.26 (s, 6H, - N C / / ) , 3.36 (m, 2H, -NC//H), 6  6  3  3  3.60 (m, 2H, -NC//H), 3.80 (s, 6H, - N C / / ) , 3.88 (m, 2H, -NC//H), 4.35 (m, 2H, 3  NC//H), 5.96 (s, 2H, -imid//), 7.10 (d, J = 8 Hz, 4H, -ArH), 7.36 7.10 (d, J = 8 Hz, 4H, ArH).  C{'H} N M R (C D ): 19.5 (-CH ), 45.6 (-NCH ), 46.5 (-NCH ), 47.5 (-NCH ), 48.9 (-  13  6  6  3  3  3  2  N C H ) , 116.8 (-ArQ, 119.1 (-ArQ, 123.9 (-imidQ, 127.5 (-ArQ, 149.9 (-ArQ, 187.1 (2  NCN). Anal. Calcd. for C H C l N T a : C, 47.14; H, 5.70; N , 13.19; Found: C, 47.09; H, 5.52; N , 25  36  6  12.95. M i n o r isomer  *H N M R (C D ): 0.60 (t, J = 9 Hz, 6H, - N ( C H C / / ) ) , 2.28 (s, 6H,  (5.5):  6  6  2  3  2  -ArC// ), 3.25 (m, 2H, -NC//H), 3.52 (m, 2H, -NC//H), 3.56 (q, J = 9 Hz, 4H, 3  N ( C / / C H ) ) , 3.98 (m, 2H, -NC//H), 4.70 (m, 2H, -NC//H), 6.10 (s, 2H, -imid//), 7.17 2  3  2  (d, J = 8 Hz, 4H, -ArH), 7.61 (d, J = 8 Hz, 4H,  -ArH).  C{ U} N M R (C D ): 15.0 (-NCH CH ), 22.5 (-CH ), 45.4 (-NCH CH ), 48.0 (-NCH ),  l3  l  6  6  2  3  3  2  3  2  50.7 (-NCH ), 119.5 (-ArQ, 120.5 (-ArQ, 125.6 (-imidQ, 131.5 (-ArQ, 151.6 (-ArQ, 2  189.5 (-NCN).  172  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN]  Transition Metal  Complexes  Major isomer (5.6): 'H NMR (C D ): 0.81 (t, J = 9 Hz, 6H, -N(CH C// ) ), 2.21 (s, 6H, 6  6  2  3  2  -ArCH ), 3.30 (m, 4H, - N C / / ) , 3.74 (q, J = 9 Hz, 4H, - N ( C / / C H ) ) , 4.52 (m, 4H, 3  2  2  3  2  N C / / ) , 5.78 (s, 2H, -imid//), 7.02 (d, J = 8 Hz, 4H, -Ar//), 7.49 (d, J = 8 Hz, 4H, -ArH). 2  C{'H} NMR (C D ): 15.2 (-NCH CH ), 23.4 (-CH ), 45.9 ( - N C H C H ) , 48.6 (-NCH ),  13  6  6  2  3  3  2  3  2  51.6 (-NCH ), 117.6 ( - A r Q , 120.9 (-ArQ, 126.8 (-imidQ, 132.6 ( - A r Q , 153.9 (-ArQ, 2  185.6 (-NCN). Anal. Calcd. for C 5 H C l N T a : C, 45.74; H , 5.22; N , 10.67; Found: C, 45.45; H , 5.01; 2  3 4  2  5  N , 10.52. Ratio of minor isomer 5.5: major isomer 5.6 =1:1.3.  Synthesis Mes  of  (5.7)  ^[NCCNJTafCH^Buk  [NCCN]Ta(CH Ph) (5.9) 2  2  Mes  Mes  [NCCN]TaMe  2  (5.8)  [NCCN]Ta(CD Ph) (d -5.9) 2  2  3  The following procedure is representative of the synthesis of 5.7-5.9. To a cooled (-30°C) THF solution (5 mL) of Cl Ta(CH 'Bu) (360 mg, 0.77 mmol) in a 50 mL 2  2  3  Erlenmeyer flask was added a chilled (-30°C) THF solution (5 mL) of 3.11 (270 mg, 0.77 mmol). The dark brown solution was slowly warmed to room temperature. The solution was stirred overnight whereupon the solvent was removed and toluene added.  The  solution was filtered thru Celite and the solvent removed to yield a dark orange solid. Yield = 356 mg, 68%. Yellow crystals were obtained from recrystallization in hexane. 5.7: *H NMR (C D ): 0.80 (d, J = 8 Hz, 1H, -TaC/ffl), 0.92 (s, 9H, -C(C// ) ), 1.10 (d, J 6  6  3  3  = 8 Hz, 1H, -TaC//H), 1.18 (d, J = 8 Hz, 1H, -TaC//H), 1.29 (d, J = 8 Hz, 1H, -TaCMf), 1.30 (s, 9H, -C(C/7 ) ), 2.18 (s, 3H, - A r C / / ) , 2.25 (s, 3H, - A r C / / ) , 2.28 (s, 3H, - A r C / / ) , 3  3  3  3  3  2.67 (m, 1H, -NC//H), 2.86(s, 3H, - A r C / / ) , 3.60 (m, 1H, -NC//H), 3.67 (m, 1H, 3  N C / / H ) , 3.84 (m, 2H, -NC//H), 4.34 (m, 1H, -NC//H), 4.48 (m, 1H, -NC//H), 5.82 (d, J = 2Hz, 1H, -imid//), 5.88 (d, J = 2Hz, 1H, -imid//) 6.80 (br s, 2H, -ArH), 7.05 (s, 1H, ArH), 7.14 (s, 1H, -ArH).  C{ H}  l3  l  NMR (C D ): 18.8 (-CH ), 19.2 (-CH ), 20.5 (-CH ), 21.9 (-CH ), 22.9 (-CH ), 6  6  3  3  3  3  3  35.1 (-C(CH )), 36.0 (-C(CH )), 51.2 (-NCH ), 55.9 (-NCH ), 56.3 (-NCH ), 68.1 (-TaQ, 3  3  2  2  2  72.1 (-TaQ, 85.6 (-TaQ, 117.5 (-ArQ, 119.5 (-ArQ, 120.5 (-imidQ, 121.6 (-imidQ, 129.6 (-ArQ, 130.9 ( - A r Q , 132.1 (-ArQ, 133.9 (-ArQ, 148.6 ( - A r Q , 149.9 (-ArQ, 197.5 (-NCN).  173  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  Anal. Calcd. for C H N T a : C, 59.14; H,' 7.52; N , 7.88; Found: C, 58.95; H , 7.26; N , 33  47  4  7.59. 5.8: 'H NMR (C D ): 0.46 (s, 3H, -TaCZZ ), 0.62 (s, 3H, -TaCZZ ), 1.89 (s, 3H, -ArCZZ ), 6  6  3  3  3  2.21 (s, 3H, -AvCH ), 2.27 (s, 3H, -ArCZZ ), 2.70 (s, 3H, -ArCZZ ), 2.72 (m, 1H, -NCZZH), 3  3  3  3.31 (m, 1H, -NC/ZH), 3.49 (m, 1H, -NCZZH), 3.71 (m, 1H, -NCZZH), 3.86 (m, 1H, NCZZH), 4.19 (m, 1H, -NCZZH), 4.37 (m, 1H, -NCZZH), 5.91 (d, J=2 Hz, 1H, -imid//), 5.94 (d, J=2 Hz, 1H, -imid//), 6.84 (br s, 2H, -ArH), 7.02 (s, 1H, -ArH), 7.09 (s, 1H, ArH). A satisfactory C N M R spectrum and elemental analysis could not be obtained due to the 13  sensitivity of the product. 5.9: 'H NMR (C D ): 1.67 (d, J = 7 Hz, -TaC/ZH), 2.27 (s, 3H, -ArC// ), 2.29 (s, 3H, 6  6  3  A r C / / ) , 2.32 (s, 3H, -ArC// ), 2.45 (d, J = 7 Hz, -TaC//H), 2.61 (d, J = 7 Hz, -TaCZZH), 3  3  2.76 (s, 3H, -ArC// ), 2.82 (d, J = 7 Hz, -TaCZZH), 3.28 (m, 1H, -TaC//H), 3.45 (m, 1H, 3  TaC//H), 3.55 (m, 1H, -TaC//H), 3.88 (m, 1H, -TaCZZH), 4.12 (m, 1H, -TaC//H), 4.55 (m, 1H, -TaCZZH), 5.90 (d, J=2 Hz, 1H, -imid//), 5.92 (d, J=2 Hz, 1H, -imid//), 6.64-6.71 (m, 3H, -ArH), 6.81-6.93 (m, 6H, -ArH), 6.99-7'.17 (m, 7H, -ArH). 13  C{ H} NMR (C D ): 17.6 (-CH ), 18.9 (-CH ), 19.6 (-CH ), 20.5 (-CH ), 50.1 (J  6  6  3  3  3  3  N C H ) , 54.6 (-NCH ), 55.4 (-NCH ), 79.2 (-TaQ, 81.6 (-TaQ, 90.1 (-TaQ, 119.2 (2  2  2  ArC), 120.2 (-imidQ, 121.9 (-ArQ, 122.3 (-imidQ, 124.6 (-ArQ, 124.9 (-ArQ, 129.6 (A r Q , 130.6 (-ArQ, 131.5 (-ArQ, 135.6 (-ArQ, 145.6 (-ArQ, 148.6 (-ArQ, 149.6 (A r Q , 151.2 (-ArQ, 196.2 (-NCN). Some aryl resonances obscured by solvent signals. Anal. Calcd. for C H i N T a : C, 62.39; H , 6.04; N , 7.46; Found: C, 61.98; H, 5.89; N , 43  4  4  7.19. ^3-5.9: 'H NMR (C D ): N M R is identical to 5.9 with the absence of the peaks at ppm 6  6  and ppm and the presence 8 2.70 (t, J=l 1 Hz, 1H, -TaC/ZD).  Synthesis of  Mes  [NCCN]Ta(CH Bu)Cl (5.10) t  2  To a cooled (-30°C) THF solution (5 mL) of Cl Ta=CH( Bu)(THF) t  3  2  (311 mg,  0.62 mmol) in a 50 mL Erlenmeyer flask was added a chilled (-30°C) THF solution (5 mL) of 3.11 (249 mg, 0.62 mmol). The dark brown solution was slowly warmed to room temperature. The solution was stirred overnight whereupon the solvent was removed and  174  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  toluene added. The solution was filtered thru Celite and the solvent removed to yield a dark orange solid.  Yield = 344 mg, 84%. Yellow crystals were obtained from  recrystallization in hexane. ' H N M R (C D ): 1.26 (s, 9H, -C(CH ) ), 1.93 (d, J = 12 Hz, 1H, -TaC//H), 2.10 (s, 3H, 6  6  3  3  A r C / / ) , 2.12 (s, 3H, -ArC// ), 2.21 (d, J = 12 Hz, 1H, -TaC//H), 2.24 (s, 3H, -ArC// ), 3  3  3  2.73 (s, 3H, -ArC// ), 2.91 (m, 1H, -NC//H), 3.13 (m, 1H, -NC//H), 3.60 (m, 1H, 3  NC7/H), 3.83 (m, 2H, -NC//H), 3.96 (m, 1H, - N C / / H ), 4.42 (m, 1H, -NC//H), 5.82 (br s, 1H, -imid//), 5.85 (br s, 1H, -imid//), 6.60 (s, 1H, -ArH), 6.87 (s, 2H, -ArH), 7.01 (s, 1H, -ArH). ,3  C { ' H } N M R (C D ): 19.1 (-CH ), 20.1 (-CH ), 21.1 (-CH ), 21.9 (-CH ), 36.1 (6  6  3  3  3  3  C(CH )), 52.0 (-NCH ), 54.6 (-NCH ), 57.2 (-NCH ), 75.2 (-TaQ, 83.3 (-TaQ, 116.9 (3  2  2  2  A r Q , 121.5 (-imidQ, 122.8 (-imidQ, 132.0 (-ArQ, 134.2 (-ArQ, 136.2 (-ArQ, 138.6 (A r Q , 150.6 (-ArQ, 150.8 (-ArQ, 196.3 (-NCN). Anal. Calcd. for C H C l N T a : C, 53.37; H , 6.27; CI, 5.25; N , 8.30; Found: 53.05; H , 29  39  4  6.02; N , 8.22.  5.9.4. Theoretical Calculations 33  A l l calculations were performed using the Gaussian 03 suite of programs. Optimized gas-phase geometries were obtained using the Becke3 exchange functional,  34  in combination the Lee, Yang, and Parr correlation functional, i.e. the B 3 L Y P method, 35  as implemented in Gaussian 03. The basis set (BS1) used for geometry optimizations and energy calculations was implemented as follows: for tantalum, the valence double-^ L A N L 2 D Z " basis set was supplemented with a set of 6p functions for transition metals 36  38  developed by Couty and H a l l , while for all hydrogen, carbon, and nitrogen atoms, the 639  31G(d',p') basis sets " were used. A l l structures were calculated in singlet spin states 40  45  using the restricted B 3 L Y P method. Calculating the harmonic vibrational frequencies and noting the number of imaginary frequencies confirmed the nature of all intermediates (NImag = 0) and transition state structures (NImag = 1). A l l gas-phase relative free energies are reported in kcal mol" , with the energy of [NCN]TaMe 1  H  ( [NCN] = H  3  ( H N C H C H ) N C H ) set to 0.0 kcal mol" . Relative electronic energies, zero-point 1  2  2  2  2  3  2  175  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  corrected energies, and enthalpies are provided in the supplemental information. For the computational investigation, [NCN] was used in place of the experimental ligand (pH  Me-CH4NCH2CH2)2N2CH2 ( [NCN]) in order to reduce the computational demands, Tol  6  3  while still providing two amide donors and one ./V-heterocyclic carbene donor to the tantalum centre.  176  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  5.10.  (1)  References  Herrmann, W. A . O., Karl; Elison, Martina; Kuehn, Fritz E.; Roesky, Peter W. J. Organomet. Chem. 1994, 480, C7.  (2)  Rietveld, M . H . P.; Klumpers, E. G.; Jastrzebski, J. T. B. H . ; Grove, D. M . ; Veldman, N . ; Spek, A . L.; van Koten, G. Organometallics 1997,16, 4260.  (3)  Rietveld, M . H . P.; Lohner, P.; Nijkamp, M . G.; Grove, D. M . ; Veldman, N . ; Spek, A . L.; Pfeffer, M . ; Van Koten, G. Chem. Eur. J. 1997, 3, 817.  (4)  Abbenhuis, H . C. L.; Rietveld, M . H . P.; Haarman, H . F.; Hogerheide, M . P.; Spek, A . L.; van Koten, G. Organometallics 1994,13, 3259.  (5)  Abbenhuis, H . C. L.; Feiken, N . ; Haarman, H . F.; Grove, D. M . ; Horn, E.; Spek, A. L.; Pfeffer, M . ; van Koten, G. Organometallics 1993, 12, 2227.  (6)  Abbenhuis, H . C. L.; Feiken, N . ; Grove, D. M . ; Jastrzebski, J. T. B. H . ; Kooijman, H.; Van der Sluis, P.; Smeets, W. J. J.; Spek, A . L.; Van Koten, G. J. Am. Chem. Soc. 1992,114, 9773.  (7)  Abbenhuis, H . C. L.; Feiken, N . ; Haarman, H . F.; Grove, D. M . ; Horn, E.; Kooijman, H.; Spek, A . L.; Van Koten, G. Angew. Chem., Int. Ed. 1991,103, 1046.  (8)  Abbenhuis, H . C. L.; Grove, D. M . ; Van der Sluis, P.; Spek, A . L.; Van Koten, G. Reel. Trav. Chim. Pays-Bas 1990,109, 446.  (9)  Tanski, J. M . ; Parkin, G. Inorg. Chem. 2003, 42, 264.  (10)  Tin, M . K . T.; Yap, G. P. A.; Richeson, D. S. Inorg. Chem. 1998, 37, 6728.  (11)  Tin, M . K . T.; Yap, G. P. A . ; Richeson, D. S. Inorg. Chem. 1999, 38, 998.  (12)  Guzei, I. A . ; Yap, G. P. A . ; Winter, C. H . Inorg. Chem. 1997, 36, 1738.  (13)  Chisholm, M . H . ; Huffman, J. C.; Tan, L.-S. Inorg. Chem. 1981, 20, 1859.  (14)  Schrock, R. R. Chem. Rev. 2002,102, 145.  (15)  Arnold, P. L.; Mungur, S. A.; Blake, A . J.; Wilson, C. Angew. Chem. Int. Ed. 2003,42,5981.  (16)  Messerle, L. W.; Jennische, P.; Schrock, R. R.; Stucky, G. J. Am. Chem. Soc. 1980,102, 6744.  177  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition Metal Complexes  (17)  Fryzuk, M . D.; Johnson, S. A.; Patrick, B. O.; Albinati, A . ; Mason, S. A.; Koetzle, T. F. J. Am. Chem. Soc. 2001,123, 3960.  (18)  Bazinet, P.; Yap, G. P. A.; Richeson, D. S. Organometallics 2001, 20, 4129.  (19)  Groysman, S.; Goldberg, I.; Kol, M . ; Genizi, E.; Goldschmidt, Z. Organometallics 2004, 23, 1880.  (20)  Chamberlain, L . R.; Kerschner, J. L.; Rothwell, A . P.; Rothwell, I. P.; Huffman, J. C. J. Am. Chem. Soc. 1987, 109, 6471.  (21)  Chamberlain, L. R.; Rothwell, I. P.; Huffman, J. C. J. Am. Chem. Soc. 1986,108, 1502.  (22)  Freundlich, J. S.; Schrock, R. R.; Davis, W. M . Organometallics 1996,15, 2777.  (23)  Freundlich, J. S.; Schrock, R. R.; Davis, W. M . J. Am. Chem. Soc. 1996, 118, 3643.  (24)  Abbenhuis, H . C. L.; Van Belzen, R.; Grove, D. M . ; Klomp, A . J. A.; Van Mier, G. P. M . ; Spek, A . L.; Van Koten, G. Organometallics 1993,12, 210.  (25)  de Castro, I.; Galakhov, M . V.; Gomez, M . ; Gomez-Sal, P.; Royo, P. Organometallics 1996, 75, 1362.  (26)  Manson, J.; Webster, C. E.; Hall, M . B. InJIMP Development Version  O.l.vlll  (built for Windows PC and Redhat Linux 7.3) Department of Chemistry, Texas A & M University, College Station, T X 77842, 2006. (27)  Groysman, S.; Goldberg, I.; Kol, M . ; Goldschmidt, Z. Organometallics 2003, 22, 3793.  (28)  Chao, Y . W.; Poison, S.; Wigley, D. E. Polyhedron 1990, 9, 2709.  (29)  Schrock, R. R.; Sharp, P. R. J. Am. Chem. Soc. 1978,100, 2389.  (30)  Schrock, R. R. J. Organomet. Chem. 1976,122, 209.  (31)  L i , L.; Diminnie, J. B.; Liu, X . ; Pollitte, J. L.; Xue, Z. Organometallics 1996, 75, 3520.  (32)  Boncella, J. M . ; Cajigal, M . L.; Abboud, K . A . Organometallics 1996, 75, 1905.  (33)  Frisch, M . J.; Trucks, G. W.; Schlegel, H . B.; Scuseria, G. E.; Robb, M . A . ; Cheeseman, J. R.; Montgomery, J. A . J.; Vreven, T.; Kudin, K . N . ; Burant, J. C ; Millam, J. M . ; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M . ; Scalmani, G.; Rega, N . ; Petersson, G. A.; Nakatsuji, H.; Hada, M . ; Ehara, M . ;  178  References begin on page 177.  Chapter Five: Synthesis and DFT Studies on Tantalum [NCN] Transition  Metal  Complexes  Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M . ; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M . ; L i , X . ; Knox, J. E.; Hratchian, H . P.; Cross, J. B.; Adamo, C ; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A . J.; Cammi, R.; Pomelli, C ; Ochterski, J. W.; Ayala, P. Y . ; Morokuma, K.; Voth, G. A . ; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V . G.; Dapprich, S.; Daniels, A. D.; Strain, M . C ; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M . A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M . ; Gill, P. M . W.; Johnson, B.; Chen, W.; Wong, M . W.; Gonzalez, C ; Pople, J. A . Gaussian 03, Revision B.4; Gaussian, Inc.: Pittsburgh, PA, 2003. (34)  Becke, A. D. J. Chem. Phys. 1993, 98, 5648.  (35)  Lee, C ; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter 1988, 37, 785.  (36)  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270.  (37)  Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284.  (38)  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299.  (39)  Couty, M . ; Hall, M . B. J. Comput. Chem. 1996, 17, 1359.  (40)  Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1971, 54, 724.  (41)  Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.  (42)  Hariharan, P. C ; Pople, J. A . Theor. Chim. Acta 1973, 28, 213.  (43)  Petersson, G. A.; Al-Laham, M . A. J. Chem. Phys. 1991, 94, 6081.  (44)  Petersson, G. A.; Bennett, A.; Tensfeldt, T. G.; Al-Laham, M . A.; Shirley, W. A . ; Mantzaris, J. J. Chem. Phys. 1988, 89, 2193.  (45)  Foresman, J. B.; Frisch, A . E. Exploring Chemistry with Electronic Structure Methods, 2nd Ed. (Gaussian, Inc, Pittsburgh, PA), p. 110. The 6-31G(d',p') basis set has the d polarization functions for C, N, O, and F taken from the 6-31 lG(d) basis set, instead of the original arbitrarily assigned value of 0.8 used in the 631G(d) basis set.  179  References begin on page 177.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Chapter Six  Thesis Extensions: Chiral Group 4 [NCN] Complexes 6.1.  Introduction  Several of the preceding chapters have explored the synthesis of a diamido-Nheterocyclic carbene ligand set and the coordination to group 4 and 5 transition metals. A logical extension of this research is to introduce chirality into the [NCN] architecture to produce chiral transition metal complexes that could facilitate enantioselective catalysis. The development of efficient and practical chiral ligands and derived catalysts is believed to be "one of the most critical research objectives in modern organic synthesis".  1  Because of the incredible success enjoyed by the application of chiral phosphine ligands in asymmetric catalysis, '  2 3  interest in introducing chirality into NHCs, so-called  phosphine analogs, has dramatically increased. To date, several distinct classes of chiral N H C ligands have emerged, which can be characterized by the position of the chiral unit in relation to the N H C donor.  Furthermore, each of these classes can be broadly  subdivided into (i) monodentate and (ii) bidentate N H C ligands, the former being further divided into substitution of chiral groups on either the carbon backbone or the nitrogen atoms of the N H C ring, and the latter into chirality on either the spacer group or substituent on the donor atom.  180  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  In the case of monodentate ligands, chiral information can be provided by the incorporation of chiral units at different positions of the five-membered heterocyclic ring. " 4  14  For example, introduction of chiral substituents on the nitrogen atoms as shown  in the use of chiral imidazolinium precursors 6.1 and 6.2 was examined in the palladiumcatalyzed asymmetric oxindole reaction (Scheme  6.1).  1 3  Moderate enantioselectivities  were obtained using 6.1 and 6.2 as ligand precursors in the cyclization of a-napthyl-amethyl amides.  Substitution on the carbon backbone of the five-membered N H C ring has also been exploited. " 15  22  Chiral ruthenium complexes 6 . 3 and 6.4 were examined in the  desymmetrization of triolefins and found to give the ring-closed metathesis products with high enantioselectivities (Scheme 6.2).  19  In this example, steric repulsion between the  chiral backbone phenyl groups and the ortho-aryl substituents stabilizes a mutual  anti  configuration that permits efficient transmission of chiral information at the active site of the catalyst.  181  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Scheme 6.2. Chiral multidentate N H C ligands have also been exploited in asymmetric catalysis. In contrast to monodentate ligands, this class has the benefit that chiral substituents can be introduced at unique positions on the chelating ligand. For example, the introduction of chiral spacer units between the N H C and a pendant donor atom has been reported. " 23  27  A ruthenium complex employing an anionic bidentate ligand with a  chiral 1,1-binaphthyl spacer (6.5) has been investigated in the asymmetric ring opening cross-metathesis ( A R O M - C M ) of olefins (Scheme 6.3).  26  Examination of this catalyst in  the A R O M - C M of tricyclic norbornenes with a terminal monoalkene revealed excellent stereoselective control on the product formed.  182  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  6.5 Scheme 6 . 3 .  Transition metal complexes incorporating chiral oxazoline-NHC ligands have also emerged as promising asymmetric catalyst precursors. " 28  33  The design of this ligand was  inspired by chiral bidentate phosphine-oxazoline complexes, which are highly selective in the enantioselective hydrogenation of alkenes.  34  In both the phosphine and N H C  examples, the chiral information is provided by a stereodirecting substituent located adjacent to the N-donor on the oxazoline heterocyclic ring. This substituent is positioned in close proximity to the metal centre and can control the space available for substrate coordination. For example, the rhodium complex 6 . 6 has been shown to be a highly selective catalyst for the asymmetric hydrosilylation of ketones (Scheme 6.4).  O  1.0% 6.6  30  OH  6.6 Scheme 6.4.  183  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  The use of chiral N H C derivatives in asymmetric catalysis continues to expand. However, research in this area has been focused on late transition-metal-mediated catalysis.  In this chapter, the synthesis of chiral group 4 transition metal [NCN]  complexes will be investigated. Several complexes will be examined for their potential to promote asymmetric hydroamination catalysis.  6.2.  Synthesis of Group 4 [NCN] Complexes  The construction of a chiral [NCN] ligand introduces the possibility to incorporate chiral substituents at discrete positions in the [NCN] framework. Chiral groups could be substituted at: 1) the amide-N-donor; 2) along the ethylene spacer; or 3) at the 4- and 5positions on the N H C ring. The latter two possibilities introduce stereocentres remote from the metal centre, options that may not effectively transfer stereochemical information during • the catalytic process.  Given this possibility, a ligand design  incorporating chiral amine groups was investigated, which would introduce chiral information in close proximity to the metal centre. In chapter 3, aryl amido substituted imidazolium precursors were synthesized utilizing a substituted chloroethylamine precursor. Given this result, a similar approach was investigated for the preparation of a chiral [NCN] ligand. A well-known procedure for the synthesis of these derivatives is the reaction of a substituted aminoethanol derivative  with  S0C1 . 2  35  (li?,2' S,47?)-2-(l,7,7-Trimethylbicyclo[2.2.1]-hept-21  ylideneamino)ethanol 6 . 7 offers the desired chiral amine component and has been previously prepared.  36  Treatment of optically pure 6 . 7 with S O C l in CHCI3 yields 6.8 in 2  near quantitative yield as an air-stable white solid (Equation 6.1). The ' H N M R spectrum of 6.8 is shown in Figure 6.1 and features three distinct methyl resonances, several complicated cyclohexyl methylene resonances, and methylene resonances attributable to a - N C / / C r Y C l moiety. Two broad diastereotopic - N / / resonances are also observed at 2  2  8.31 and 9.45 ppm.  184  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  (ppm)  Figure 6.1.  *H N M R spectrum of (li?,2'5,4i?)-2-(l,7,7-trimethylbicyclo[2.2.1]hept-2ylamino)ethyl ammonium chloride (6.8) in CDCI3. (* denotes V2 equivalent of C H C ( 0 ) C H ) . 3  3  X-ray quality crystals of 6.8 were grown from a saturated solution of methanol and the molecular solid state structure was determined by an X-ray diffraction study. Selected bond lengths and angles are given in Table 6.1 and crystallographic details are presented in Appendix A . The orientation of the stereocentre on the cyclohexyl ring  185  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  shows there has been no change in configuration as a result of the reaction of 6.7 with SOCb.  Furthermore, the presence of a chloride counterion infers that an ammonium  moiety is present. Unfortunately, the data collected from X-ray diffraction is quite poor and the results presented here are used to establish the connectivity and orientation of the atoms in the molecule.  Figure 6.2.  ORTEP view of (-)-(li?,2'5,4i?)-2-(l,7,7-trimethylbicyclo[2.2.1]hept-2ylamino)ethyl ammonium chloride (6.8) depicted with 50% thermal ellipsoids; all hydrogen atoms have been omitted for clarity.  Table 6.1.  Selected Bond Distances (A) and Bond Angles (°) for (-)-(li?,2'5,4i?)-2(1,7,7-trimethylbicyclo[2.2.1 ]hept-2-ylamino)ethyl ammonium chloride, (6.8). Bond Angles C11-C1-C2 107.6(10) C3-N1-C2 110.1(10)  Bond Lengths N1-C2 N1-C3 Cll-Cl  1.453(13) 1.571(13) 1.771(19)  Conversion of the ammonium salt 6.8 to the corresponding amine was achieved by the reaction of 6.8 with an excess of K2CO3 (Equation 6.2). This reaction provides the free amine 6.9 in quantitative yield as a colorless oil. The *H N M R spectrum of 6.9, shown in Figure 6.3, reveals the absence of the ammonium resonances at 8.31 and 9.45  186  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  ppm that were observed in 6.8, in addition to ethylene spacer units at 2.88 and 3.63 ppm. The -NH resonance was not located in the *H N M R spectrum.  K C0 2  3 >  (6.2)  Et 0 ?  6.9  6.8  6.9  -NHCtf, -CH C\ 2  7.5  7.0  6.5  6.0  5.5  5.0  4.5  4.0  3.5  3.0  25  2.0  1.5  1.0  OS  (ppm)  Figure 6.3.  ' H N M R spectrum of (li?,2'5,4/?)-2-(l,7,7-trimethylbicyclo[2.2.1]hept-2ylamino)ethyl chloride (6.9) in CDCI3. (* denotes E t 2 0 impurity).  The first approach to the synthesis of a chiral [NCN] imidazolium species was the reaction of two equivalents of 6.9 with imidazole in the presence of NEt (Equation 6.3). 3  This reaction produced a  CH2CI2  insoluble solid in low yield that was identified as 6.10  by *H and C { ' H } N M R spectroscopy. l3  The formation of 6.10 was confirmed by the  187  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  presence of an iminium resonance at 9.05 ppm, along with anticipated ethylene spacer, imidazole and cyclohexylamine resonances.  The resonances in the ' H N M R spectrum  are broad, possibly a result of a fluxional process in the molecule or fast exchange with ^ - C D O D (Figure 6.4). 4  3  (ppm)  Figure 6.4.  ' H N M R spectrum of THF impurity).  scam  [ N C H N ] H - C l (6.10) in d - C D O D (* denotes 2  4  3  Intrigued by the low yield of 6.10 in this reaction, the C H 2 C I 2 soluble fraction was examined to ascertain the formation of other products. The *H N M R spectrum of the crude product suggested the synthesis of the neutral chiral 2-aminoethyl imidazole compound 6.11 (Equation 6.3), with imidazole resonances at 7.00, 7.08, and 7.69 ppm. Although the synthesis or purification of this compound was not optimized, the crude CH2Ci2-soluble fraction could be used as a precursor for the synthesis of 6.10. Treatment of the crude chiral 2-aminoethyl imidazole 6.11 with the chiral 2-chloroethylamine 6.9 at 160°C provided the imidazolium chloride 6.10 in excellent yields.  188  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  6.11  Deprotonation of 6.10 with one equivalent of KN(SiMe3)2 at -30°C resulted in the isolation of a highly soluble yellow oil. The disappearance of the iminium resonance at 9.05 ppm in the *H N M R spectrum supports the presence of an N H C , however, other unidentifiable resonances were present. Over an extended period of time (ca. 2 days), the resonances attributed to the N H C disappear, which suggests decomposition of the N H C ligand. As a result, the synthesis of the N H C ligand was performed in situ and used immediately in further reactions. Given the success with aminolysis reactions in the synthesis of group 4 [NCN] complexes described in chapter 3, a similar approach was investigated for the synthesis of chiral group 4 [NCN] complexes. The reaction of 6.10 with T i ( N M e 2 ) 4 in the presence of one equivalent of KN(SiMe3)2 at -30°C yielded 6.12 as a highly soluble orange solid (Equation 6.4).  The ' H N M R spectrum of 6.12 is shown in Figure 6.5 and shows 13  equivalent ethylene spacer, imidazole, and N{CH )2 groups. 3  The  1  C{ H} N M R  spectrum features a weak resonance at 190.5 ppm indicative of a Ti-C rbene bond. Single ca  crystals suitable for an X-ray structure determination have yet to be obtained due to the high solubility of 6.12 in organic solvents.  189  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Figure 6.5.  *H N M R spectrum of  scam  [ N C N ] T i ( N M e ) (6.12) in C D . 2  2  6  6  Alkyl elimination reactions were also successful for the synthesis of chiral group 4 [NCN] complexes. The addition of a solution of 6.10 to Zr(CH Ph) in the presence of 2  4  one equivalent of KN(SiMe ) at -30°C yielded 6.12 as a highly soluble yellow solid 3  2  (Equation 6.5). The ' H N M R spectrum of 6.12 shows a C symmetric species in solution 2  with equivalent ethylene spacer and imidazole resonances.  The Z r C / /  2  groups are  observed as a diastereomeric set of doublets and are obscured by the resonances of an 13  1  ethylene spacer group. A Z r C H resonance is also observed at 77.2 ppm in the C { ' H } IJ  2  N M R spectrum. Unfortunately, crystals of 6.13 suitable for X-ray diffraction have yet to be obtained. 190  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  KN(SiMe ) Zr(CH Ph) 3  2  Me  HN Me  M  e  f=\  N  2  h 1  (6.5)  THF -30°C - KCI Me -HN(SiMe ) 3  2  6.13  6.10  6.3.  ss  1 11  4  Asymmetric Intramolecular Hydroamination Studies The catalytic formation of organic nitrogen containing molecules is of great  academic and industrial interest.  One method that has shown success is the  hydroamination reaction, in which an amine is added to an olefin in either an intermolecular or intramolecular fashion.  37,38  Transition metal complexes have been  extensively examined as catalysts for this process with examples reported for many transition metals.  39,40  One common goal for the design of these catalysts has been to gain  control over the diastereoselectivity and regiochemistry of the hydroamination product. The enantioselective addition of amines to olefins is a logical extension of this chemistry and remains a challenging task. With respect to early transition metals and lanthanides, several examples that display moderate to high enantioselectivities are known. Chiral yttrium binaphtholate complexes and cationic zirconium aminophenolate complexes are known to accomplish this with high enantioselectivity values.  4 1 , 4 2  Chiral  lanthanide complexes with salicylaldimine and binaphthyl diamine ligands have also 43  44  been reported to catalyze intramolecular hydroamination with moderate enantiomeric excess values. Preliminary experiments in our laboratory with the titanium and zirconium species, 6.12 and 6.13, focused on the intramolecular hydroamination of 2,2-diphenyl-4pentenylamine (Equation 6.6). The catalytic reaction was initially performed at 110°C in dg-toluene with a 10 mol % precatalyst loading. ' H N M R spectroscopy was used to monitor the disappearance of the olefinic signals in the amine substrate and the presence of diagnostic signals for the pyrrolidine product.  191  A heated (is-toluene solution of References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  diphenyl-4-pentenylamine and the titanium precursor 6.12 was monitored by ' H N M R spectroscopy and revealed no conversion to the corresponding heterocycle after 24 hours.  H  6.14  [ c a t ] = 6.12 6.13  0 % yield 0% ee > 9 9 % yield 4 % ee  It has been shown that the activities of hydroamination catalysts increase with the increasing ionic radius of the metal centre.  39  With this in mind, the zirconium precursor  6.13 was examined under the same conditions used for 6.12 (110°C, dg-toluene). The reaction was followed by ' H N M R spectroscopy, which revealed complete conversion to 2-methyl-4,4-diphenylpyrrolidine 6.14 after heating for 1 hour (Equation 6.6). The enantiomeric excess of each of the two pyrrolidine products was determined by derivatizing the heterocycle 6.14 with (-)-Mosher's acid chloride.  42  'HNMR  spectroscopic analysis of the diastereomers formed showed that a nominal enantiomeric excess (4%) was achieved during the catalytic process. While catalytic formation of the N-heterocycle 6.14 is encouraging, there are several possible explanations for the low enantioselectivity obtained with the zirconium precatalyst 6.13. This low value may be a result of the ineffective transmission of chiral information by the camphor chiral unit. Alternatively, the presence of the dialkylamido donors in the chiral [NCN] ligand set presents the potential for aminolysis of the Zr-N bond by the amine precursor. Although it is anticipated that the hydroamination reaction with the aminoalkene and 6.14 would proceed to eliminate toluene (Path 1, Figure 6.6), the presence of an excess amount of aminoalkene at high temperatures could react to form a metal derivative with a new M - N amido bond and an amido-amino substituted  192  References begin on page 203.  Chapter Six: Synthesis and Applications  scam  of Chiral Group 4 [NCN]  [ N C N H ] ligand array (Path 2, Figure 6.6).  Complexes  As a result of this protonolysis, the  transfer of chiral information during the catalytic process may be disrupted.  Figure 6.6.  6.4.  Aminolysis of a Zr-N bond in  scam  [NCN]Zr(CH Ph) . 2  2  Conclusions and Future Work  In this chapter, the synthesis of a chiral camphor-based [NCN] ligand set was investigated. Coordination of this ligand to titanium and zirconium was accomplished by aminolysis and alkyl elimination reactions, respectively. The complexes 6.12 and 6.13 were investigated in the asymmetric intramolecular hydroamination of an aminoalkene in an attempt to promote selectivity in the N-heterocycle synthesized. While the titanium complex.6.12 showed no activity, the zirconium complex 6.13 was an efficient catalyst  193  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  for the intramolecular formation of a substituted pyrollidine.  Examination of the  steroselectivity in the N-heterocyclic product revealed nominal enantioselective excess. Chiral group 4 metallocene complexes have attracted a great deal of attention as precursors for stereoregular a-olefin polymerization.  It is well established that the  tacticities of synthesized polyolefins are highly dependent on the structure of the precatalyst.  When activated, achiral complexes such as Cp2ZrCl2 produce atactic  polymers, whereas C2-symmetric and C -symmetric chiral complexes produce isotactic s  and syndiotactic polymers, respectively.  45  Given the potential C2 symmetry of 6.13, the  ability of activated 6.13 to form isotactic polypropylene would be of interest. This chapter has demonstrated that the chiral dianionic, tridentate [NCN] ligand is well-suited for the stabilization of titanium and zirconium complexes.  A n analogous  bidentate chiral amido-NHC ligand would be of great interest, in particular for late transition-metal-mediated imidazolium  chloride  asymmetric catalysis. precursor  has been  The synthesis of a chiral aminoinvestigated.  Thermolysis  of 1-  mesitylimidazole and 6.9 at 160°C for 1 hour produces the desired imidazolium compound 6.15 in near quantitative yield (Equation 6.7). The *H N M R spectrum (Figure 6.7) shows an iminium resonance at 9.48 ppm in addition to signals for the cyclohexylamine, aryl, and ethylene spacer groups.  194  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  (6.7)  6.16  (ppm)  Figure 6.7.  *H N M R spectrum of [ N C H ] H - C l (6.15) in d -DMSO (* denotes contamination with H 2 O and § denotes a trace amount of E t 2 0 ) . scam  6  195  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Deprotonation of 6.14 with one equivalent of KN(SiMe ) proceeds immediately 3  2  at room temperature to give the chiral N H C 6.16 in near quantitative yield (Equation 6.7). The *H N M R spectrum shown in Figure 6.8 features a loss of the iminium resonance at 9.50 ppm, which is diagnostic for N H C formation.  Unfortunately, the  1 3  C resonance  expected for the divalent carbon atom of the N H C ligand was not observed in the 13  C{'H} N M R spectrum.  -ary!C//  -aryl//  8.5  8.0  7.5  7.0  -NC//  -imid//  6.5  6.0  5.5  5.U  4.5  1 4.0  3.5  3  2  3.0  2.5  2.0  1.5  l.C  (ppm)  Figure 6.8.  ' H N M R spectrum of  scam  [ N C ] H (6.16) in C D . 6  6  The coordination of the chiral bidentate N H C 6.16 remains unexplored and could yield a number of potentially chiral metal complexes.  Enantioselective catalysis  involving these ligands, in particular with late transition metals, offers a vast potential, which will be explored in the near future.  196  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  6.5.  Experimental Section  6.5.1. General Considerations  Unless otherwise stated, general procedures were performed as described in Section 2.5.1.  6.5.2. Materials and Reagents  A l l chemicals were purchased from a chemical supplier and used as received. (-)(l^,2',S,4i?)-2-(l,7,7-trimethylbicyclo[2.2.1]-hept-2-ylideneamino)ethanol  (6.7)  was  prepared by a literature method.  6.5.3. Synthesis and Characterization of Complexes 6.8 - 6.13, 6.14 - 6.15  Synthesis of  (^-(lif^'.S'^^^^l^J-trimethylbicyclo^^.ll-hept^-ylideneamino)-  ethyl ammonium chloride (6.8) To a stirred solution of 6.7 (3.25 g, 16.5 mmol) in 50 mL CHC1 in a 100 mL 3  Schlenk flask was added S O C l (5.89 g, 49.5 mmol) dropwise. The orange solution was 2  carefully heated at 80°C for 4 hours, cooled to room temperature, and the solvent removed in vacuo to yield a brown powder. This solid was triturated with acetone to yield a white crystalline solid that was recovered by filtration and recrystallized from MeOH. Yield = 3.87 g, 93%. 'H NMR (CDC1 ): 5 0.88 (s, 3H, -C// ), 1.09 (s, 3H, -CH ), 1.15 (m, 2H, -camphorC// ), 3  3  3  2  1.25 (s, 3H, -CH ), 1.63-1.97 (m, 4H, -camphorC// ), 2.22 (m, 1H, - camphorC/7), 3.13 3  2  (m, 1H, - camphorC//), 3.42 (m, 2H, -NHC// ), 4.12 (m, 2H, -C// C1), 8.31 (br s, 1H, 2  2  N//H), 9.45 (br s, 1H, -N//H). '^{'H} NMR (CDCI3): 6 12.8 (-CH ), 20.0 (-CH ), 20.8 (-CH ). 26.7 (-CH ), 34.9 (3  3  3  2  CH ), 36.7 (-CH ), 38.8 (-CH), 44.8 (-CH C1),.47.5.(-CHCH ), 49.1 (-C(CH ) ), 49.5 (2  2  2  3  3  2  CH N), 67.2 (-CHN). 2  [<x] = -67.0° (c 0.01; MeOH). D  197  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Anal Calcd. for C H 3 C 1 N : C, 57.14; H , 9.19; N, 5.55. Found: C, 57.52; H , 9.06; N , 1 2  2  2  5.32.  Synthesis of (li?,2'5,4^)-2-(l,7,7-trimethylbicyclo[2.2.1]-hept-2-ylideneamino)-ethyl chloride (6.9) A 250 mL Schlenk flask was charged with 6.8 (3.85 g, 14.2 mmol), 100 mL distilled H 0 , and 100 mL E t 0 . A n aqueous solution (10 mL) of K C 0 (2.16 g, 15.6 2  2  2  3  mmol) was slowly added and the biphasic solution stirred for 1 hour. The E t 0 layer was 2  removed and the aqueous layer washed with 2 portions of E t 0 (50 mL). The ethereal 2  solutions were combined, dried with MgSO-4, and filtered. Upon removal of the solid in vacuo a colourless oil was recovered. Yield = 3.06 g, 100%. 'H NMR (CDC1 ): S 0.81 (s, 3H, -CH ), 0.92 (s, 3H, -C// ), 1.03 (s, 3H, -CH ), 1.17 (m, 3  3  3  3  2H, -camphorC// ), 1.48-1.71 (m, 5H, -camphorC// and -camphorC//), 2.54 (m, 1H, 2  2  camphorC//), 2.91 (m, 2H, - N H C / / ) , 3.63 (m, 2H, -CH C\). 2  2  "Cf/H} NMR (CDCI3): 8 12.3 (-CH ), 20.6 (-CH ), 20.7 (-CH ), 27.4 (-CH ), 37.0 (3  3  3  2  CH ), 38.7 (-CH ), 44.9 (-CH C1), 45.3 (-CH), 46.9 (-CHCH3), 48.7 (-C(CH ) ), 49.8 (2  2  2  3  2  CH N), 66.2 (-CHN). 2  Synthesis of (-)-  scam  [NCHN]H -Cl (6.10) (scam = (l/?,2'S,4#)-2-(l,7,7-trimethylbicyclo2  [2.2.1]-hept-2-ylideneamino) A 500 mL Schlenk flask was charged with 6.9 (1.12 g, 5.2 mmol), imidazole (177 mg, 2.6 mmol), NEt (0.37 mL, 5.3 mmol), and 250 mL of p-dioxane. The slurry was 3  heated to 120°C and stirred overnight. Upon cooling to room temperature, the solvent was removed in vacuo and 50 mL CH C1 added. Filtration of this solution yielded a 2  2  white solid, which was washed several times with CH C1 . The solid was dried in vacuo 2  2  overnight as it is mildly hygroscopic. Yield = 252 mg, 21%). J  H NMR (CD3OD): 8 0.83 (s, 6H, -CH ), 0.90 (s, 6H, -CH ), 0.93 (s, 6H, -CH ), 1.11 3  3  3  (m, 4H, -camphorC/^), 1.56-1.72 (m, 10H, -camphorC// and -camphorC//), 2.71 (br m, 2  2H, - camphorC//), 3.06 (br m, 4H, -NC// ), 4.35 (br m, 4H, - N C / / ) , 7.68 (s, 2H, 2  2  imid//), 9.05 (br s, 1H, -NC//N).  198  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  C{'H} NMR (CD3OD): 5 14.7 (-CH ), 21.2 (-CH ), 21.9 (-CH ), 29.1 (-CH ), 38.3 (-  ,3  3  3  3  2  CH ), 38.9 (-CH ), 46.2 (-CH), 47.7 (-CH), 48.3 (-CH N), 49.0 (-CHCH3), 51.3 (-CH N), 2  2  2  2  67.9 (-C(CH ) ), 126.4 (-imidC), 138.6 (-NCHN). 3  2  [a] = -83.5° (c. 0.01; MeOH). D  Anal Calcd. for C27H46CIN4: C, 70.17; H , 10.03; N , 12.12. Found: C, 70.02; H , 9.68; N , 12.35. Synthesis of (lif,2'5',4i?)-2-(l,7,7-trimethylbicyclo[2.2.1]-hept-2-ylideneamino)ethyl imidazole (6.11) The CH C1 filtrate that was obtained in the synthesis of 6.10 was recovered and 2  2  the solvent removed in vacuo to yield a dark oil. *H analysis of this residue revealed the formation of 6.11 in about -85% purity. H NMR (CDCI3): 5 0.73 (s, 3H, -CH ), 0.86 (s, 3H, -C//3), 0.94 (s, 3H, -CH ), 1.05 (m, l  3  3  2H, -camphorC// ), 1.48-1.74 (m, 5H, -camphorC// and -camphorC//), 2.52 (m, 1H, 2  2  camphorC//), 2.95 (m, 1H, - camphorC//), 2.54 (m, 2H, - N  cam  C / / ) , 4.14 (m, 2H, - N 2  i m i d  C/7 ), 7.00 (s, 1H, -imid//), 7.08 (s, 1H, -imid//), 7.69 (s, 1H, -NC//N). 2  Alternative synthesis of (-)- [NCHN]H -Cl (6.10) scam  2  A 25 mL Schlenk flask was charged with 6.9 (262 mg, 1.2 mmol) and crude 6.11 (300 mg, 1.2 mmol) and slowly heated to 160°C for 1 hour. The reaction mixture was cooled to room temperature and THF added to give a white solid (6.10) which was collected by filtration and washed with several portions of THF. Yield = 505 mg, 91%.  Synthesis of [NCN]Ti(NMe ) (6.12) scam  2  2  A suspension of 6.10 (296 mg, 0.64 mmol) in THF (5 mL) was cooled to -30°C in a 50 mL Erlenmeyer flask and a THF (5 mL) solution of KN(SiMe ) (127 mg, 0.64 3  mmol) was slowly added dropwise.  2  The solution was left to stand at -30°C for 15  minutes without stirring. A THF (5 mL) solution of Ti(NMe )4 (143 mg, 0.64 mmol) was 2  slowly added dropwise and the entire mixture slowly warmed to room temperature and stirred overnight. The solvent was removed and the yellow residue extracted with hexane  199  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  (2 xlO mL). The solvent was removed in vacuo and H M D S O added to yield a bright orange powder. Yield = 143 mg, 40%. ' H N M R ( C D ) : 8 0.82 (s, 6H, -CH ), 0.92 (s, 6H, -CH ), 1.03 (m, 4H, -camphorC// ), 6  6  3  3  2  1.18 (s, 6H, -CH ), 1.41-1.70 (m, 10H, -camphorC// and camphorC// ), 2.45 (m, 2H, 3  2  camphorC//), 2.70-2.91 (m, 4H, - N C / / ) , 3.32 (s, 12H, - N ( C / / ) , 3.85 (m, 4H, - N C / / ) , 2  3  2  2  6.52 (s, 2H, -imid//)  C{ H)  l3  l  N M R ( C D ) : 8 13.2 (-CH ), 20.6 (-CH ), 21.7 (-CH ), 28.5 (-CH ), 36.9 (6  6  3  3  3  2  CH ), 37.3 (-CH ), 45.1 (-CH), 45.9 (-NCH ), 47.8 (-CH), 47.9 (-CHCH ), 48.2 (-NCH ), 2  2  3  3  51.0 (-NCH ), 66.8 (-C(CH ) ), 120.4 (-imidQ, 190.5 (-TiC 2  3  2  carbe  2  ne).  Satisfactory elemental analysis has yet to be obtained.  Synthesis of  scam  [ N C N ] Z r ( C H P h ) (6.13) 2  2  A suspension of 6.10 (286 mg, 0.62 mmol) in THF (5 mL) was cooled to -30°C in a 50 mL Erlenmeyer flask and a THF (5 mL) solution of K N ( S i M e ) (136 mg, 0.62 3  mmol) was slowly added dropwise.  2  The solution was left to stand at -30°C for 15  minutes without stirring. A THF (5 mL) solution of Zr(CH Ph) (282 mg, 0.62 mmol) 2  4  was slowly added dropwise and the entire mixture slowly warmed to room temperature and stirred overnight. The solvent was removed and the yellow residue extracted with hexane (2 xlO mL). The solvent was removed in vacuo and H M D S O added to yield a bright yellow powder. Yield = 295 mg, 68%. ' H N M R ( C D ) : 8 0.86 (s, 6H, -C// ), 0.96 (s, 6H, - C / / ) , 1.11 (m, 4H, -camphorC// ), 6  6  3  3  2  1.16 (s, 6H, - C / / ) , 1.50-1.71 (m, 8H, -camphorC// and camphorC// ), 2.20 (m, 2H, 3  2  camphorC//), 2.26-2.51 (m, 10H, - camphorC//, ZrC//2, and N C / / ) , 3.11 (m, 4H, 2  N C / / ) , 6.90 (s, 2H, -imid//), 6.95-7.01 (m, 6H, -Ar//), 7.19 (t, J = 8 Hz, 4H, -Ar//) 2  C{ H}  13  l  N M R ( C D ) : 8 15.2 (-CH ), 20.0 (-CH ), 20.9 (-CH ), 27.7 (-CH ), 37.4 (6  6  3  3  3  2  CH ), 38.2 (-CH ), 44.9 (-CH), 45.1 (-CH), 46.3 (-CHCH ), 49.3 (-NCH ), 51.8 (-NCH ), 2  2  3  2  2  66.2 (-C(CH ) ), 77.3 (-ZrCH ), 118.5 (-ArQ, 119.7 (-imidQ, 128.6 ( - A r Q , 130.1 (3  2  2  A r Q , 148.2 ( - A r Q , 193.0 (-ZrC  carbene  ).  Anal Calcd. for C i H N Z r : C, 70.53; H , 8.37; N , 8.03. Found: C, 70.22; H , 8.56; N , 4  58  4  8.16.  200  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  Synthesis of (-)-  scam  [NCH]H-Cl (6.15)  A 25 mL Schlenk flask was charged with 6.9 (1.05 g, 4.9 mmol) and 1mesitylimidazole (0.906 mg, 4.9 mmol) then slowly heated to 160°C for 1 hour. The reaction mixture was cooled to room temperature and THF added to give a white solid (6.15) which was collected by filtration and washed with several portions of THF. Yield = 1.87 g, 95%. *H N M R (rf -DMSO): 8'0.72 (s, 6H, -CH ), 0.75 (s, 6H, -CH ), 0.82 (s, 6H, -CH ), 0.99 6  3  3  3  (m, 4H, -camphorC//), 1.30-1.68 (m, 4H, -camphorC// and camphorCrY ), 2.00 (s, 3H, 2  o-ArCH ), 2.32 (s, 3H, -/>ArCH ), 2.48 (m, 1H, - camphorC//), 2.87 (m, 2H, -NC// ), 3  3  2  4.35 (m, 2H, - N C / / ) , 7.13 (s, 2H, -ArH), 7.90 (br s, 1H, -imid//), 8.07 (br s, 1H, 2  imid//), 9.50. C{ H}  n  l  N M R (<4-DMSO): 8 13.0 (-CH ), 18.6 (-CH ), 22.6 (-CH ), 28.2 (-CH ), 35.6 (3  3  3  2  CH ), 38.3 (-CH ), 45.1 (-CH), 47.0 (-CH), 48.1 (-CHCH ), 48.9 (-NCH ), 51.9 (-NCH ), 2  2  3  2  2  67.1 (-C(CH ) ), 118.0 (-imidQ, 119.1 (-imidQ, 127.8 (-ArQ, 130.2 ( - A r Q , 131.2 (3  2  A r Q , 139.4 (-ArQ, 142.1 (-NCHN). [<x] = -41.3° (c 0.01; MeOH). D  Satisfactory elemental analysis has yet to be obtained.  Synthesis of  s c a m  [ N C ] H (6.16)  A THF solution (5 mL) of KN(SiMe ) (390 mg, 2.0 mmol) was slowly added 3  2  dropwise to 6.15 (786 mg, 2.0 mmol) dissolved in 5 mL THF, creating a slightly yellow suspension. The suspension was stirred for Vi hr and the solvent removed in vacuo. The pale yellow residue was extracted with toluene (20 mL) and the solution filtered through celite. Removal of the solvent yielded a white solid which was washed several times with hexane and dried in vacuo. Yield = 702 mg, 96%. ' H N M R (C D ): 8 0.89 (s, 6H, -CH ), 1.00 (s, 6H, -CH ), 1.12 (m, 2H, -camphorC// ), 6  6  3  3  2  1.29 (s, 6H, -CH ), 1.49.-1.92 (m, 4H, -camphorC//and camphorC// ), 2.18 (s, 6H, -o3  2  ArCH ), 2.21 (s, 3H, -/>ArCH ), 2.60 (m, 1H, - camphorC//), 2.91 (m, 2H, - N C / / ) , 4.09 3  3  2  (m, 2H, - N C / / ) , 6.46 (br s, 1H, -imid//), 6.72 (br s, 1H, -imid//), 6.85 (s, 2H, -ArH). 2  13  C{'H} N M R (C D ): 8 12.2 (-CH ), 17.9 (-CH ), 20.7 (-CH ), 27.6 (-CH ), 36.9 (6  6  3  3  3  2  CH ), 38.8 (-CH ), 45.5 (-CH), 46.7 (-CH), 48.4 (-CHCH ), 49.6 (-NCH ), 51.0 (-NCH ), 2  2  3  201  2  2  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  66.7 (-C(CH ) ), 119.3 (-imidQ, 120.0 (-imidQ, 128.8 (-ArQ, 135.1 (-ArQ, 136.9 (3  2  A r Q , 138.9 (-ArQ. Satisfactory elemental analysis has yet to be obtained.  Procedure for Intramolecular Hydroamination A J. Young's tube was charged with a ferrocene internal standard sealed in a glass capillary tube, catalyst (0.025 mmol), and the amino alkene (0.5 mmol) and dissolved in c/ -toluene (~ 1 ml). The N M R tube was heated to 110°C and the progress of the reaction 5  was monitored by *H N M R spectroscopy at regular intervals. The N M R yields were determined by comparing the integration of the internal standard with a well-resolved signal for the heterocyclic product.  The ' H N M R spectrum of 2-methyl-4,4-  diphenylpyrrolidine recovered during 6.13-mediated hydroamination is identical to reported values.  47  Enantioselective Excess Determination  42  The N M R solution was transferred to a 50 mL Erlenmeyer flask and the tube rinsed with several portions of C H C I 3 . To this solution was added (-)-Mosher chloride and ~ 1 mL triethylamine. The solution was stirred for 15 minutes and solvent removed in vacuo. The residue was dissolved in C D C I 3 and the enantiomeric excess was determined by ' H N M R spectroscopy.  202  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  6.7.  (1)  References  Jacobsen, E. N . ; Pfaltz, A.; Yamamoto, H.; Editors Comprehensive Asymmetric Catalysis I-III, Volume J; Springer: Berlin, Germany, 1999.  (2)  Cesar, V.; Bellemin-Laponnaz, S.; Gade, L. H . Chem. Soc. Rev. 2004, 33, 619.  (3)  Roland, S.; Mangeney, P. Top. Organomet. Chem. 2005,15, 191.  (4)  Herrmann, W. A.; Goossen, L . J.; Koecher, C ; Artus, G. R. J. Angew. Chem., Int. Ed. Engl. 1997, 35, 2805.  (5)  Enders, D.; Gielen, H . J. Organomet. Chem. 2001, 617-618, 70.  (6)  Enders, D.; Gielen, H.; Breuer, K. Tetrahedron: Asymmetry 1997, 8, 3571.  (7)  Enders, D.; Breuer, K.; Runsink, J.; Teles, J. H . Helv. Chim. Acta 1996, 79, 1899.  (8)  Enders, D.; Breuer, K.; Teles, J. H. Helv. Chim. Acta 1996, 79, 1217.  (9)  Knight, R. L . ; Leeper, F. J. J. Chem. Soc, Perkin Trans. 1 1998, 1891.  (10)  Kerr, M . S.; Rovis, T. Synlett 2003, 1934.  (11)  Kerr, M . S.; Read de Alaniz, J.; Rovis, T. J. Am. Chem. Soc. 2002, 124, 10298.  (12)  Culkin, D. A . ; Hartwig, J. F. Acc Chem. Res. 2003, 36, 234.  (13)  Lee, S.; Hartwig, J. F. J. Org. Chem. 2001, 66, 3402.  (14)  Seo, H.; Kim, B. Y . ; Lee, J. H.; Park, H.-J.; Son, S. U . ; Chung, Y. K . Organometallics  2003, 22, 4783.  (15)  Fraser, P. K.; Woodward, S. Tetrahedron Lett. 2001, 42, 21Al.  (16)  Alexakis, A.; Benhaim, C ; Rosset, S.; Humam, M . J. Am. Chem. Soc. 2002,124, 5262.  (17)  Feringa, B. L. Acc Chem. Res. 2000, 33, 346.  (18)  Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem., Int. Ed. 1985, 97, 1.  (19)  Seiders, T. J.; Ward, D. W.; Grubbs, R. H. Org. Lett. 2001, 3, 3225.  (20)  Jensen, D. R.; Sigman, M . S. Org. Lett. 2003, 5, 63.  (21)  Bappert, E.; Helmchen, G. Synlett 2004, 1789.  (22)  Chianese, A. R.; L i , X . ; Janzen, M . C ; Faller, J. W.; Crabtree, R. H . Organometallics  2003, 22, 1663.  203  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  (23)  Clyne, D. S.; Jin, J.; Genest, E.; Gallucci, J. C.; RajanBabu, T. V . Org. Lett. 2000, 2, 1125.  (24)  Albrecht, M . ; Crabtree, R. H.; Mata, J.; Peris, E. Chem. Commun. 2002, 32.  (25)  Van Veldhuizen, J. J.; Gillingham, D. G.; Garber, S. B.; Kataoka, O.; Hoveyda, A . H. J. Am. Chem. Soc. 2003, 125, 12502.  (26)  Van Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A . H. J. Am. Chem. Soc. 2002, 124, 4954.  (27)  Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000.122, 8168.  (28)  Perry, M . C ; Cui, X . ; Powell, M . T.; Hou, D.-R.; Reibenspies, J. H.; Burgess, K . J. Am. Chem. Soc. 2003, 125, 113.  (29)  Powell, M . T.; Hou, D.-R.; Perry, M . C ; Cui, X . ; Burgess, K. J. Am. Chem. Soc. 2001.123, 8878.  (30)  Gade, L. H.; Cesar, V.; Bellemin-Laponnaz, S. Angew. Chem. Int. Ed. 2004, 43, 1014.  (31)  Glorius, F.; Altenhoff, G.; Goddard, R.; Lehmann, C. Chem. Commun. 2002, 2704.  (32)  Bolm, C ; Focken, T.; Raabe, G. Tetrahedron: Asymmetry 2003, 14, 1733.  (33)  Enders, D.; Kallfass, U. Angew. Chem. Int. Ed. 2002, 41, 1743.  (34)  Pfaltz, A.; Blankenstein, J.; Hilgraf, R.; Hormann, E.; Mclntyre, S.; Menges, F.; Schonleber, M . ; Smidt, S. P.; Wustenberg, B.; Zimmermann, N . Adv. Synth. Catal. 2003, 345, 33.  (35)  Foster, P.; Chien, J. C. W.; Rausch, M . D. J. Organomet. Chem. 1997, 545-546, • 35.  (36)  Squire, M . D.; Burwell, A.; Ferrence, G. M . ; Hitchcock, S. R. Tetrahedron: Asymmetry 2002, 13, 1849.  (37)  Pohlki, F.; Doye, S. Chem. Soc. Rev. 2003, 32, 104.  (38)  Mueller, T. E.; Beller, M . Chem. Rev. 1998, 98, 675.  (39)  Roesky, P. W.; Mueller, T. E. Angew. Chem. Int. Ed. 2003, 42, 2708.  (40)  Hultzsch, K. C. Adv. Synth. Catal. 2005, 347, 367.  (41)  Gribkov, D. V.; Hultzsch, K . C. Chem. Commun. 2004, 730.  204  References begin on page 203.  Chapter Six: Synthesis and Applications of Chiral Group 4 [NCN] Complexes  (42)  Knight, P. D.; Munslow, I.; O'Shaughnessy, P. N . ; Scott, P. Chem. Commun.  2004, 894. (43)  O'Shaughnessy, P. N . ; Knight, P. D.; Morton, C ; Gillespie, K. M . ; Scott, P. Chem. Commun. 2003, 1770.  (44)  Collin, J.; Daran, J.-C; Schulz, E . ; Trifonov, A. Chem. Commun. 2003, 3048.  (45)  Nakayama, Y.; Shiono, T. Molecules 2005,10, 620.  (46)  Danopoulos, A. A.; Wright, J. A.; Motherwell, W. B. Chem. Commun. 2005, 784.  (47)  Bexrud, J. A.; Beard, J. D.; Leitch, D. C ; Schafer, L . L. Org. Lett. 2005, 7, 1959.  205  References begin on page 203.  Chapter Seven  Thesis Summary and Future Work This thesis has investigated the chemistry of two different ligand sets on early transition metals. In chapter 2, the reactivity of a tantalum [NPN] dinitrogen complex with several transition metal hydrides was investigated.  The addition of Schwartz's  reagent, ([Cp2Zr(Cl)H] ), led to the unanticipated reduction of the N - N unit without Zr-H x  addition.  Examination of the product revealed the formation of a phosphinimide  derivative with insertion of a "Cp2Zr" fragment into the N - N bond.  A series of  experiments determined that the origin of the "Cp2Zr" was from the reductive elimination of H from [Cp2ZrH2]2- A n independent reaction with a "Cp2Zr" source verified that this 2  species induced N - N bond cleavage. This type of dinitrogen reduction was extended to include the insertion of a "Cp2Ti" fragment into the N - N bond and represents a new approach in dinitrogen chemistry to cleave an N2 ligand. Early transition metal chemistry with a unique diamido-N-heterocyclic carbene ligand set was pursued in chapter 3 . Ligands with an ethylene spacer between the N heterocyclic ring and the amido donor were successfully synthesized. Aminolysis and alkyl elimination reactions with group 4 transition metal precursors afforded a successful way to synthesize group 4 [NCN] complexes. The central position of the N H C in this tridentate architecture renders the carbene stable to dissociation from the metal centre in strongly coordinating solvents.  206  The application and reactivity of group 4 [NCN] complexes was the focus of chapter 4. Fundamental processes such as olefin polymerization, migratory insertion, and dinitrogen activation were examined and revealed the N H C moiety remains coordinated to the metal centre and does not participate in a manner that would alter the N H C donor. Activation of a zirconium-dimethyl derivative with [Ph3C][B(CeF5)4] in the presence of ethylene yielded a moderately active polymerization catalyst.  Migratory insertion of  simple organic molecules, such as isocyanides, carbon monoxide and cumulenes, into the hafnium-sp -carbon bond of several hafnium-alkyl derivatives yielded the expected insertion products.  In some examples, further C-C bond coupling was observed to  generate new eneamidolate and enediolate metallacycles.  Despite many attempts, no  early transition metal dinitrogen complexes were recovered utilizing the [NCN] ligand set. In chapter 5, the coordination of the [NCN] ligand set to tantalum(V) was examined in anticipation that a dinitrogen complex could be synthesized.  While  tantalum-amide and -halide complexes were isolated with an intact [NCN] architecture, reduction of these complexes in the presence of dinitrogen resulted in a complicated mixture of products.  Attempts to synthesize tantalum alkyl complexes resulted in the  isolation of compounds where the ligand has undergone C-H bond activation at one of the backbone positions.  Density functional calculations and isotopic labeling studies  examined the mechanism of this C - H bond activation process and suggested the intermediacy of an alkylidene species. The research described in this thesis has provided insight into the use of two different ligand sets in different areas of early transition metal chemistry. Future research with [NPN] chemistry will be aimed at the addition of other reduced transition metal and main group complexes to 2.5, in an attempt to extend the functionalization of coordinated nitrogen atoms with other elements. In light of the inability to obtain an E T M dinitrogen complex stabilized by a [NCN] ancillary ligand, other transition metals may assist in accomplishing this elusive goal. Further research utilizing the chiral tridentate [NCN] and bidentate [NC] ligands may also yield a highly active and selective E T M or L T M catalyst. In conclusion, the research presented herein has provided solid groundwork for future research in both [NPN] and [NCN] chemistry.  207  Appendix A: X-ray Crystal Structure Data  Appendix A  X-ray Crystal Structure Data A.l.  General Considerations  In all cases, suitable crystals were selected and mounted on a glass fibre using Paratone-N oil and frozen to -100°C. Measurements for structures 2.10, 3.5, 3.17, 3.22, 3.24C H N, 3.30, 4.22, 5.1 and 5.2 were made on a Rigaku/ADSC C C D area detector 5  5  with graphite monochromated Mo-Ka radiation by either Dr. Brian O. Patrick or Dr. Christopher Carmichael. Data was processed using the d*TREK' module, part of the CrystalClear software package, version 1.3.6 SPO, and corrected for Lorentz and 2  polarization effects and absorption. Neutral atom scattering factors for all non-hydrogen atoms were taken from Cromer and Waber. Anomalous dispersion effects were included 3  in F | . ca  4  C  Measurements for structure 6.8 were made on a Bruker X8 area detector with graphite monochromated M o - K a radiation by Howard Jong. Data was determined to be a two component twin using the Twinsolve module of the CrystalClear software package, version 1.3.6 SPO.  2  Measurements for structures 3.8, 3.38, 4.7, 4.8, 4.11, 4.16, 4.17,  4.18, 4.23, 5.3, 5.7, and 5.10 were made on a Bruker X8 area detector with graphite monochromated M o - K a radiation by either Brian O. Patrick or Howard Jong. Data was  208  References located on page 210.  Appendix A: X-ray Crystal Structure Data  processed and integrated using the Bruker SAINT software package and corrected for 5  absorption effects using the multi-scan technique (SADABS).  6  Neutral atom scattering  factors for all non-hydrogen atoms were taken from Cromer and Waber. Anomalous 3  dispersion effects were included in F i ; the values for A / " and Af"' were those of c a  Creagh and McAuley. Creagh and Hubbell.  7  c  4  The values for the mass attenuation coefficients are those of  8  A l l structures were solved by direct methods using the program SIR97. A l l non9  hydrogen atoms were refined anisotropically by least square procedures on F using 2  SHELXL-97.  10  Hydrogen atoms were included but not refined; their positional  parameters were calculated with fixed C - H bond distances of 0.99 A for sp C, 0.98 A for 2  sp C, and 0.95 A for aromatic sp C, with U\ set to 1.2 times the U of the attached sp 3  so  eq  2  3  or sp C and 1.5 times the U values of the attached sp C atom. Methyl hydrogen eq  torsion angles were determined by electron density. Structure solution and refinements were conducted using the WinGX software package, version 1.64.05." illustrations were created using ORTEP-III for Windows.  209  Structural  12  References located on page 210.  Appendix A: X-ray Crystal Structure Data  A.2.  References  1)  Pflugrath, J. W. Acta Cryst. 1999, D55, 1718.  2)  CrystalClear: A n Integrated Program for the Collection and Processing of AreaDetector Data, Rigaku Corporation, 2002.  3)  Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; Kynoch Press, 1974; Vol. IV.  4)  Ibers, J. A.; Hamilton, W. C. Acta Cryst. 1964, 77, 781.  5)  SAINT Software User Guide, Version 7.03A, Bruker Analytical X-ray Systems, Inc., Madison, WI, 1997.  6)  Sheldrick, G. M . S A D A B S , Version 2.05, Bruker Analytical X-ray Systems, Inc., Madison, WI, 2003.  7)  Creagh, D. C ; McAuley, W. J. In Internation Tables for Crystallography; Wilson, A . J. C , Ed.; Kluwer Academic Publishers; Boston, 1992; V o l . C, pp 219-222.  8)  Creagh, D. C ; Hubbell, J. H . In Internation Tables for Crystallography; Wilson, A. J. C , Ed.; Kluwer Academic Publishers; Boston, 1992; Vol. C, pp 200-206.  9)  Altomare, A . ; Burla, M . C ; Cammali, G.; Cascarano, M . ; Giacovazzo, C ; Guagliardi, A.; Moliterni, A . G. G.; Polidori, G.; Spagna, A . J. Appl. Crystallogr.  1999, 32, 115. 10)  Sheldrick, G. M . SHELXL-97: Programs for Crystal Structure Analysis (Release 97-2), University of Gottingen, Gottingen, Germany, 1998.  11)  Farrugia, L . J. J. Appl. Cystallogr. 1999, 32, 837.  12)  Farrugia, L . J. J. Appl. Cystallogr. 1997, 30, 565.  210  References located on page 210.  Appendix A: X-ray Crystal Structure Data  A.3.  Tables of Crystallographic Data  Crystallographic and structure refinement for [N(LA-P=N)N]Ta(|a-H) ((xMes (NCHN)H -C1 (3.5), and (NCN)H N(ZrCp ))-Ta[NPN] (2.10), (3.8).  Table A . l .  2  Mes  2  2  2  ( N C N ) H (3.8)  [NP(N)N]Ta(uH) (u-N)(Ta[NPN]) (ZrCp ) (2.10)  Mes  (NCHN)H -Cl (3.5)  M e s  C 8H N P Si4  C H C1N4  C 5H 4N4  Ta Zr 1482.65  427.02  390.56  Purple, plate 0.4x0.2x0.1  Colourless, plate 0.25x0.15x0.05  Colourless, prism 0.40 x 0.40 x 0.20  Orthorhombic  Monoclinic  Pccn  P2fc  13.4310(10) 38.984(3) 28.4871(19) 90 90 90 14915.6(18) 8 • 1.320 5888 3.205  7.5827(13) 25.577(4) 12.453(2) 90 91.802(10) 90 2414.0(7) 4 1.175 920 0.177  Orthorhombic P22,2, 8.8133(2)A 9.2024(2) 14.0787(3) 90 90 90 1141.83(4) 2 1.136 424 0.068  0.7238-1.0000  0.7870-1.0000  0.8403-1.0000  55.76 93218  54.98 19828  55.72 13829  17760  9450  4303  0.563 666  0.0820 289  0.0306 139  0.0766  0.0510  0.0370  0.0889  0.1056  0.0463  1.221  0.979  0.969  2  2  2  2  Formula  5  7 4  6  2 5  2  2  3 5  3  2  Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  b,A c,A a, deg P, deg y, deg  v,A z  ?  Pcalc, g Cm"  3  Fooo p, (MoKa), cm" transmission factors 2 0 , deg total no. of reflns no. of unique reflns Rint no. of variables R. ( F , I > 2a(I)) Rw(F ,all data) Gof 1  max  2  2  Ri = H|Fo| -  1F 11 C  /  S|FQ|;  R = (Sw( F | 2  w  0  211  F \Y / Sw  2,2x1/2  2  C  F  2 2 0  )  References located on page 210.  Appendix A: X-ray Crystal Structure Data  Crystallographic and structure refinement for [NCN]Zr(NEt )2 (3.17), [ N C N H ] T i ( N M e ) (3.22), and [NCN]ZrCl (py) (3.30).  A.2.  Table  2  Mes  tol  2  [NCN]Zr(NEt ) (3.17)  3  2  [NCN]ZrCl (py) (3.30) C H 9Cl N Zr  Formula  C gH44N6Zr  [NCNH]Ti(NMe ) (3.22) C ,H N Ti  Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  567.92  569.69  609.69  Colourless, platelet 0.40x0.20x 0.05  Red, prism 0.40 x 0.40 x 0.20  Red, prism 0.05 x 0.04x0.03  Monoclinic  Monoclinic  Monoclinic  P2Jn  P2\lc  P2 ln  9.8762(14) 12.3743(19) 24.325(4) 90 93.812(9) 90 2963(37) 4 1.273 1200 0.398  13.1845(12) 18.7121(17) 13.2384(11) 90 98.130(4) 90 3233.2(5) 4 1.170 1232 0.295  8.2213(8) 31.764(3) 10.8884(11) 90 91.757(3) 90 2842.0(5) 4 1.425 1248 0.602  0.8765-1.0000  0.8516-1.0000  0.8419-1.0000  55.00 24721  55.12 26981  55.76 25486  6345  9771  6283  0.0871 151  0.0826 368  0.0793 336  0.0743  0.0384  0.0751  0.1168  0.0584  0.1036  1.034  0.958  tol  2  c,A  a, deg  P,  deg y, deg v,A  ?  z  pcalc, g  2  3  2  b,A  Cm"  3  Fooo p, (MoKa), cm" transmission factors 2 0 , deg total no. of reflns no. of unique reflns Rint no. of variables R. ( F , I > 2c(I)) R (F , all data) Gof  tol  Mes 2  5 1  7  3  2  29  2  2  5  x  1  max  2  2  w  1.088  Rt = SlJFoi - [Fell / £ | F | ; R = (£w(|F [ - j F 2  0  w  0  212  2 c  f I £wlF f )  l / 2  0  References located on page 210.  Appendix A: X-ray Crystal Structure Data  Table A.3.  Crystallographic and structure refinement for [NCN]Zr(CH SiMe3)2 ^CN]Hf(n -XyNCCH )(CH ) (3.30), Mesr[NCN]HfBu (3.38), and (4.7). tol  2  Mes  z  2  b,A c,A a, deg P, deg y, deg  v,A z  ?  pcalc, g Cm"  3  Fooo  p., (MoKa), cm" transmission factors 2 0 , deg total no. of reflns no. of unique reflns Rint no. of variables R. ( F , I > 2a(I)) R (F ,all data) Gof  3  '[NCN]Zr ( C H S i M e ) (3.30)  Mes  C H46N Si Zr  C 3H5oHfN4-l/2C H 0  C 6H47HfN5-C H 0  598.10  726.33  800.39  Yellow, block 0.25 x 0.25 x 0.2  colourless, plate 0.15x0.15x0.15  colourless, plate 0.40x0.30x 0.10  Monoclinic  Monoclinic  Monoclinic  PlxIc 13.105(3) 12.676(3) 19.448(4) 90 99.398(2) 90 3198.6(6) 4 1.242 1264 0.442  C2/c 19.9312(3) 13.7149(3) 28.0013(6) 90 113.0590(10) 90 7042.7(2) 4 1.355 2952 2.991  C2/c 32.883(5) 11.614(5) 23.793(5) 90 112.217(5) 90 8412(4) 4 1.378 3600 2.521  0.7550-1.0000  0.8448-1.0000  0.7118-1.0000  53.24 27267  56.30 97131  55.24 115842  7173  8473  9958  0.0374 333 .  0.0396 377  0.0388 479  0.0301  0.0217  0.0285  0.0629  0.0576  0.0454  0.821  1.066  2  Formula Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  3  29  3  4  [NCN]HfBu (3.38) 2  2  [NCN]Hf(n X y N C C H ) ( C H ) (4.7) 3  2  3  4  8  3  3  4  8  1  max  2  2  w  1.021  Rx = £ 1FQ| - F | | / I | F | ; R = (£w(jF |- F 2  c  0  w  0  213  2 C  ) I £wF | )' l  2  2  / 2  0  References located on page 210.  Appendix A: X-ray Crystal Structure Data  Crystallographic and structure refinement for [ N C N ] H f ( T i - X y N C C H ) 2 (4.8), [NCN]Hf(OC(CH )=C(CH )NXy) (4.11), and [NCN]Hf) C«OC( Bu)=C( Bu)0) (4.16).  Table A.4.  Mes  2  3  Mes  Mes  3  i  3  2  i  2  [NCN]Hf(r| X y N C C H ) (4.8)  [NCN]Hf(OC(CH ) =C(CH )NXy) (4.11)  C9oHii Hf N] -  C H47HfN50-C H 0  ( [NCN]Hf) (pOC( Bu)=C( Bu)0) (4.16) C oH oHf N 04-4C H  CH C1 1803.82  801.35  1786.99  Colourless, irregular 0.20x 0.07x 0.04  Yellow, irregular 0.10x0.05x0.03  Colourless, tablet 0.15 x 0.07x0.04  Triclinic P-l 15.6616(8) 16.3972(7) 21.5514(10) 70.757(2) 73.887(2) 68.167(2) 4774.1(4) 2 1.255 1844 2.275  Monoclinic  Triclinic  Pljc  P-\  10.9435(6) 20.0210(11) 17.3179(8) 90 92.451(2) 90 3790.9(3) 4 1.404 1636 2.790  12.377(5) 18.530(5) 21.408(5) 107.656(5) 103.930(5) 100.104(5) 4374(2) 2 1.357 1840 2.425  0.8093-1.0000  0.7300-1.0000  0.6694-1.0000  48.10 108780  41.20 25826  46.92 44117  19273  6703  11428  0.0649 988  0.1030 420  0.1051 993  0.0656  0.0479  0.0473  0.0963  0.1058  0.1106  Mes  3  Formula  2  2  Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  b,A c,A a, deg P, deg Y, deg  v,A z  ?  Pcalc, g Cm" Fooo p., (MoKa),  3  cm transmission factors 2 0 , deg total no. of reflns no. of unique reflns Rint no. of variables R. ( F , I > 2a(I)) R ( F , all data) Gof max  2  2  W  Mes  2  3  3  2  2  37  2  2  5  Mes  2  i  i  2  7  10  2  8  6  6  2  0.999 0.982 1.281 ; R = ( £ w ( | F | F | ) / S w |F ty." R, = E | | F | - F | | / I | F | 2  0  C  0  w  0  214  2  c  2  0  References located on page 210.  Appendix A: X-ray Crystal Structure Data  [NCN]Hf(Me)(n Crystallographic and structure refinement for [NCN]Hf(Me)(n - PrNC(Me)N Pr) (4.18), and 'BuNC(Me)O) (4.17), [NCN]Zr(Cl)(OBu) (4.22) Mes  A.5.  Table  Mes  3  3  i  i  Mes  [NCN]Hf(Me)(ii BuNC(Me)0) (4.17)  Mes  l  Formula Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A c,A  a, deg P, deg y, deg ?  pcalc, g C m "  3  .  Fooo  p, (MoKa), cm transmission factors 26 x, deg ma  total no. of reflns no. of unique reflns Rint  no. of variables Ri ( F , I > 2a(I)) Rw (F , all data) Gof 2  2  R  t  [NCN] Hf(Me)(n PrNC(Me)N'Pr)  M e s  i  J  Mes  [NCN]Zr(Cl)(OBu)  (4.22)  C32H47HfN 0  (4.18) C 4H HfN  696.24  723.31  588.33  Colourless, prism 0.3 x 0.2x0.15  Colourless, plate 0.35 x 0.25 x0.1  Yellow, irregular 0.4x0.4x0.35  3  5  b,A  v,A z  3  5 2  C29H41CI  6  N OZr 4  Orthorhombic  Triclinic  Triclinic  Pbca  P-\  P-\  10.1327(2) 21.6299(4) 28.8509(6) 90 90 90 6323.2(2) 8 1.463 2832 3.331  10.4245(2) 19.3938(4) 19.9828(4) 113.8580(10) 104.8770(10) 96.0180(10) 3469.92(12) 1.385 1480 3.037  10.367(5) 10.894(5) 13.550(5) 80.965(5) 81.615(5) 80.095(5) 1477.7(11) 2 1.322 616 0.490  0.7831-1.0000  0.6466-1.0000  0.7971-1.0000  55.68 58871  55.88 94064  55.74 13213  7501  16394  6026  0.0448 363  0.0378 763  0.0331 332  0.0227  0.0237  0.0488  0.0379  0.0407  0.0561  1.028  1.028  4  = S|]FQ1 - ] F l | / £ [ F ; R e  0  w  = (Sw( F  215  1.090 2 0  - 1F |) / £ w | F 2  C  2  2 0  l  f  l  References located on page 210.  Appendix A: X-ray Crystal Structure Data  A.6.  Table  Crystallographic and structure refinement for [NCN]Hf(Me)(r| N N M e ) ( 4 . 2 3 ) , [NCNH]Ta(NMe ) (5.1), and [NCNH]Ta(CHPh) (CH Ph) (5.2). Mes  tol  Mes  2  2  2  [NCN]Hf(Me)(n NNMe ) (4.23) C H HfN 641.17  tol  782.85  [NCNH] Ta(CHPh) (CH Ph) (5.2) C H N Ta, 839.85  Colourless, prism 0.25x0.2x0.05  Yellow, fiber 0.4x0.25x0.15  Orange, prism 0.2x0.1 x0.05  Monoclinic P2 lm 8.1361(4) 22.1536(10) 8.5276(4) 90 113.3560(10) 90 1411.10(12) 2 1.509 648 3.723  Monoclinic PlxIc 12.669(5) 11.681(5) 25.201(5) 90 87.021(5) 90 3724(2) 4 1.396 1608 2.986  Monoclinic PlxIc 11.0925(10) 27.769(3) 13.3194(14) 90 96.253(4) 90 4078.3(7) 4 1.368 1708 2.730  0.7458-1.0000  0.6390-1.0000  0.8017-1.0000  55.82 19552  55.00 13436  55.66 105524  3452  7557  9567  0.0400 174  0.0245 421  0.0619 474  0.0257  0.0294  0.0255  0.0312  0.0438  0.0463  2  2  b,A c, A a, deg P, deg y, deg  v,A z  ?  pcalc, g C m "  3  Fooo p, (MoKa), cm transmission factors 20max,  deg  total no. of reflns no. of unique reflns Rint  no. of variables Ri ( F , I > 2a(I)) R ( F , all data) Gof 2  2  W  4  2  Mes  Formula Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  2  2 8  4 2  6  x  [NCNH]Ta(NMe ) 2  (5.1)  2  C H57N Ta 36  C  0  46  8  1.044 1.087 R, = S | | F | - | F | | / I | F | ; R = (2w(|F 0  w  216  M e s 4  2 0  2  50  1.011 - |F ) / E w F | ) 2  C  2  2  2  4  i y i  0  References located on page 210.  Appendix A: X-ray Crystal Structure Data  T a b l e A.7.  Crystallographic and structure refinement for [NCN]Ta(NMe )3 (5.3), [ N C C N ] T a ( C H B u ) (5.7), and [NCCN]Ta(Cl)(CH Bu) (5.10). 2  Mes  t  Mes  2  2  [NCN]Ta(NMe ) (5.3) C ,H N Ta 693.67 2  3  4 2  2  [NCCN]Ta(CH Bu) (5.7) C H N Ta 710.76 Mes  tol  Formula Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A  t  3 5  7  5 3  4  [NCCN]Ta(Cl) (CH Bu) (5.10) C H C1N 675.08  Mes  t  2  3  2  l  2  30  42  4  Orange, irregular 0.25x0.18x0.12  Yellow, irregular 0.35x0.2x0.1  Yellow, irregular 0.12 x 0.05 x 0.05  Monoclinic  Monoclinic  Triclinic  C2/c 15.668(5) 11.495(5) 19.926(5) 90 102.002(5) 90 3510(2) 4 1.313 1400 3.159  P2\ln  3384.93(7) 4 1.395 680 3.275  P-l 9.3783(8) 11.5711(10) 14.6775(11) 109.568(3) 90.206(3) 94.935(3) 1494.3(2) 2 1.500 1456 3.791  0.8542-1.000  0.7666-1.0000  0.8698-1.0000  55.46 39215  55.92 31089  55.84 49582  4086  7008  8005  0.0315 182  0.0678 334  0.0316 373  R. (F ,I> 2a(I))  0.0285  0.0357  0.0181  R (F ,all data) Gof  0.0307  0.0518  0.0271  b,A c, A a, deg P, deg y, deg  v,A z  ?  Pcalc, g C m "  3  Fooo p, (MoKa), cm" transmission factors  9.67930(10) 22.4522(3) 16.0990(2) 90  104.6490(10) 90  1  20max, deg  total no. of reflns no. of unique reflns Rim  no. of variables 2  2  w  ,  1.122 1.056 R, = I |F | - |Fc|| / S|F |; R = (Sw( F 0  0  w  217  '  2 0  1.072 - F ) / Ew|F | ) 2  c  2  2  2  1/2  0  References located on page 210.  Appendix A: X-ray Crystal Structure Data  TableA.8.  Crystallographic and structure refinement for (-)-(li?,2'S',4i?)-2-(l,7,7trimethylbicyclo[2.2. l]hept-2-ylamino)ethyl ammonium chloride (6.8). (-)-(lR,2'S,4R)-2-(l,7,7trimethylbicyclo[2.2.1]hept-2-ylamino)ethyl ammonium chloride (6.8)  Formula Formula weight Colour, Habit Crystal size, mm Crystal system Space group a, A b,A c,A a, deg  C H 4C1 N 12  Triclinic Pl 10.661(2) 10.659(2) 14.141(3) 108.308(7) 114.205(7) 92.053(8) 1366.0(8) 4 1.231 548 0.448  P,  ?  zPcalc, g  Cm"  2  Colourless, prism 0.40x0.20x0.10  deg y, deg  v,A  2  253.22  3  Fooo  p., (MoKa), cm" transmission factors 1  0.5679-1.0000 51.50 34817  20max, deg  total no. of reflns no. of unique reflns  18462 0.0802 559  Rint  no. of variables Ri (F ,I> 2a(I)) Rw (F , all data) Gof 2  0.1523  2  0.1873  R, =  1.659 2 |F | - |F || / I|F |; R = (2w( F | - |F ) / Ew F 2  0  C  0  w  0  218  2  C  2  22 0  )  1 / 2  References located on page 210.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  Appendix B  Evaluating the Formation of a Tantalum Metallaaziridine Complex by Density Functional Calculations B.l.  Evaluation of a a-Bond Metathesis Mechanism  In the calculated a-bond metathesis pathway (Figure B.l), the lowest energy trimethyl complex (A, 0.0 kcal/mol, Table B.l) is converted to a methane adduct of the ligand activated metallaziridine dimethyl complex, (B, -7.9 kcal/mol), via the a-bond metathesis transition state (TS-A-B, 49.6 kcal/mol). The calculated structures of A, TSA-B, and B are provided in Figure B.2. In the transition state TS-A-B, the breaking Ta-C bond distance is 2.96 A , while the forming and breaking C-H bond distances are 1.36 and 1.47 A , respectively. The Ta-H distance in TS-A-B is 2.79 A , which indicates that there is very little interaction between the migrating hydrogen and the tantalum centre in this transition state. Separating methane from the methane adduct complex B generates the metallaaziridine complex C and free methane (-10.5 kcal/mol). The metallaaziridine complex C is able to change conformations to the most stable metallaaziridine complex D via the low barrier isomerization transition state (TS-C-D, -10.4 kcal/mol). Overall the reaction is exergonic, with the free energy of the metallaziridine D and CH4 products being 18.6 kcal/mol lower in energy that the starting trimethyl complex A. However, the  219  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  high energy point on this pathway, the transition state T S - A - B , is 49.6 kcal/mol higher in energy than the starting trimethyl complex A , which is too large of an energy difference between the starting complex and the transition state for this transformation to readily occur without heating the solution, which indicates that this pathway may not be operating under the experimental conditions employed in this study.  TS-A-B (49.6)  These isomers vary in the conformation of the 6 member rings  Gas-phase relative free energies at the B3LYP/BS1 level of theory based on the energy of separated 1 set to 0.0 kcal/mol are provided in parentheses in kcal/mol. Electronic energies, corrected zero-point energies, enthalpies, and free energies are provided in Table B . l . a  Figure B . l .  Relative energies of the intermediates and transition states in a potential a bond metathesis mechanism.  220  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  Table B . l .  Gas-phase relative energies (kcal/mol) of the intermediates and transition states in a a-bond metathesis mechanism.  Structure A TS-A-B B C + CH TS-C-D + C H D + CH  AE 0.00 55.33 1.99 2.36 2.89 -5.85 W  e  4  4  4  AE 0.0 49.7 -1.3 -1.1 -1.0 -9.3  ( b )  A H  o(c;  AG 0.0 49.6 -7.9 -10.5 -10.4 -18.6  0 ( d )  0  0.0 49.9 0.6 -0.2 -0.4 -8.4  (a) based on the gas-phase relative electronic energy of A set to 0.00 kcal/mol (b) based on the gas-phase relative zero point corrected energy of A set to 0.0 kcal/mol (c) based on the gas-phase relative enthalpy of A set to 0.0 kcal/mol (d) based on the gas-phase relative free energy of A set to 0.0 kcal/mol  TS-A-B Figure B.2. B.2.  B  JIMP Pictures of the one-step a-bond metathesis pathway. 1  Investigation of an Alkylidene Intermediate Followed by C-H Bond Activation  In the calculated two-step pathway for metallaaziridine formation (Figure B.3), in which a-H abstraction is followed by alkylidene mediated C - H activation, the starting trimethyl complex (A, 0.0 kcal/mol, Table B.2) is initially converted to the methaneadduct methylidene-methyl complex (E, -10.3 kcal/mol) via the a-H abstraction transition state (TS-A-E, 36.4 kcal/mol) (Figure B.4). Separating methane from the adduct-complex yields the methylidene-methyl complex and free methane (F + CH4, 14.8 kcal/mol). The a-H abstraction sequence (A -» T S - A - E -» E -» F + C H ) is 4  exergonic by -14.8 kcal/mol, thus indicating that this step is an energetically favorable process. The a-H abstraction transition state (TS-A-E) is 36.4 kcal/mol higher in energy  221  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  than the starting trimethyl complex A, which shows a-H abstraction is energetically favored over a-bond metathesis for the trimethyl complex A by 13.5 kcal/mol.  TS-A-E  (36.4)  F-J  A  These isomers vary in the conformation of the 6 member rings  D  Gas-phase relative free energies at the B3LYP/BS1 level of theory based on the energy of separated 1 set to 0.0 kcal/mol are provided in parentheses in kcal/mol. Electronic energies, corrected zero-point energies, enthalpies, and free energies are provided in Table 1. 3  Figure  B.3.  Relative energies of the intermediates and transition states in a potential two-step a-H abstraction/alkylidene mediated C-H activation mechanism.  222  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  Table  B.2.  Gas-phase relative energies (kcal/mol) of the intermediates and transition states in a mechanism involving a-H abstraction followed by alkylidene mediated C-H bond activation.  Structure  AE  A TS-A-E + CH  + CH F + CH  E  4  4  4  TS-F-G + CH G + CH4  4  TS-G-H + C H  H + CH  4  4  TS-H-I + C H  4  I + CH4 TS-I-J + C H J + CH TS-J-D + C H D + CH (a) based on the (b) based on the (c) based on the (d) based on the 4  4  4  4  AEc/  W e  AG°  b)  W  0.0 0.0 0.0 0.00 36.4 35.6 36.0 38.30 -10.3 -2.8 -4.7 -1.90 -14.8 -3.6 -4.8 -1.56 -4.3 5.4 4.8 8.09 -12.5 -2.1 -3.0 -0.01 -3.1 7.0 6.3 9.69 -7.3 3.7 2.7 5.67 -6.5 3.6 2.9 6.35 -6.7 4.0 3.0 6.20 -5.7 4.6 3.7 7.65 -7.0 5.2 3.8 7.63 17.3 26.2 25.8 31.43 -18.6 -8.4 -9.3 -5.85 gas-phase relative electronic energy of A set to 0.00 kcal/mol gas-phase relative zero point corrected energy of A set to 0.0 kcal/mol gas-phase relative enthalpy of A set to 0.0 kcal/mol gas-phase relative free energy of A set to 0.0 kcal/mol  A series of low energy rearrangements ( F - > T S - F - G - > G - > T S - G - H -> H -> TS-H-I -> I -> TS-I-J  J) positions the  CH2CH2 carbene-amido  linker in the proper  position for alkylidene mediated C-H activation of the ligand backbone. In the ligand CH bond activation process, the methylidene unit of the rearranged methylidene-methyl complex (J, -7.0 kcal/mol, Figures B.3 and B.4) abstracts a proton from the ligand backbone via the alkylidene mediated C - H activation transition state (TS-J-D, 17.3 kcal/mol) to yield the ligand activated metallaziridine product D (Figures B.3 and B.4). Overall, the final products D and C H are lower in energy than all of the methylidene4  methyl complexes (F-J), thus indicating that the metallaaziridine complex and C H 4 are the favored products for methane elimination from the trimethyl complex A in agreement with the experimental observations.  In addition, the energy difference between the  lowest energy methylidene-methyl complex ( F ) and the alkylidene mediated C - H activation transition state (TS-H-D) is 32.1 kcal/mol, which indicates that the alkylidene mediated C-H bond activation occurs more readily than the initial a-H abstraction step. It should also be noted that the barrier for the reaction to proceed in the reverse direction 223  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  from lowest energy methylidene-methyl complex (F), for example the energy difference between F and C H and the a-H abstraction transition state (TS-A-E), is 51.2 kcal/mol, 4  which implies that endocyclic C-H activation of the ligand backbone is highly favored over C-H activation of alkanes in solution.  •  A  TS-A-F  J  Figure B.4.  B.3.  TS-J-D  E  D  JIMP Pictures of a-H abstraction by a methyl group to generate a [NCN]Ta(=CHR')R alkylidene intermediate. 1  Thermodynamic Considerations for the Formation of Metallated Ta [NCCNJ Derivatives In addition to studying the mechanism of the ligand activation, part of the  motivation for the DFT investigation was to address the question, why are the ligand activated metallaaziridine products formed instead of the trialkyl derivatives? For our model complexes, the metallaaziridine product D and separated CH4 are favored relative to the trimethyl complex A both in terms of both enthalpy and entropy (Table B . l ) . Although we expected that formation of two molecules ( D + CH4) instead of one molecule (A) would be entropically favored, it was not obvious why the metallaaziridine  224  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  product D and C H were enthalpically favored over the trimethyl complex A, especially 4  because D contains a three-membered ring, which is a potential source of ring strain. A n examination of the bond lengths and angles in the trimethyl complex A (Figure B.5) and the metallaaziridine product D (Figure B.6) revealed several features that contribute to. D and C H being enthalpically favored relative to A: (1) The Ta4  carbene bond is much shorter in D (2.248 A ) than in A (2.381 A ) , indicative of a much stronger bond; (2) The Ta-CH3 bonds in D (2.173 and 2.219 A ) are shorter than the TaC H bonds in A (2.238, 2.248, and 2.252 A ) ; and (3) The Ta-N bonds in D (1.982 and 3  2.065 A ) are, on average, shorter than the Ta-N bonds in A (2.020 and 2.053 A ) . Furthermore, the ring strain due to the metallaaziridine fragment in complex D is reduced relative to the strain in organic three-membered rings because D can be viewed as a sixcoordinate cf Ta complex in which Ta-L a-bonding occurs through ligand orbital interactions with Ta sd hybrids. In six coordinate, cf early transition metal complexes 5  such as WrLj, formation of localized, electron pair bonds draws from all s and d orbitals to form six sd hybrids, which have energy minimas at angles of 63° and 117 . ' 5  0  2 3  The  calculated C4-Tal-N2 angle in the metallaaziridine ring of D is 38.2°, which represents less than a 25° distortion from the smaller angle energy minima.  225  References begins on page 233.  Appendix B: Evaluating Calculations  the Formation  of Tantalum  Metallaaziridine  Complex  by Density  Functional  Figure B.5.  JIMP view of A. Selected bond distances ( A ) and angles (deg): T a l - C l 2.381, Tal-C2 2.252, Tal-C3 2.248, Tal-C4 2.238, T a l - N l 2.053, T a l N2 2.020, C l - T a l - C 2 139.6, C l - T a l - C 3 142.0, C2-Tal-C3 76.4.  Figure B.6.  JIMP view of D. Selected bond distances ( A ) and angles (deg): T a l - C l 2.248, Tal-C2 2.219, Tal-C3 2.173, Tal-C4 2.257, T a l - N l 2.065, T a l N2 1.982, C l - T a l - C 2 130.5, Cl-Tal-C3 122.7, C2-Tal-C3 106.1, C4Tal-N2 38.2.  1  1  226  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  In addition, formation of the metallaaziridine ring in D facilitates the close proximity of two Ta substituents, which provides more space around the Ta centre for the remaining substituents to adopt more favorable bonding positions. Natural Bond Orbital  4  (NBO) analyses of the trimethyl complex A, and the metallaaziridine product D, indicate that shortening of the Ta-carbene and Ta-Me bonds in D relative to A results from changes in the occupancy of the a-bonding and a*-anti-bonding orbitals. The occupancies of the Ta-carbene and Ta-Me3 a-bonding orbitals in D are higher than the occupancies of the corresponding a-bonding orbitals in A, while the occupancies of the Ta-carbene and Ta-Me3 a*-anti-bonding orbitals in D are lower than the occupancies of the corresponding a-bonding orbitals in A (Table B.3).  Table B.3.  N B O Occupancies of bonding and anti-bonding orbitals in the trimethyl complex A and the metallaaziridine complex D.  A  D  Tal-Cl a  1.853  1.933  Tal-C2a  1.833  1.946  Tal-C3 a  1.795  1.892  T a l - C l a*  0.168  0.091  Tal-C2a*  0.126  0.094  Tal-C3 a*  0.129  0.103  Examination of the second order perturbation theory analysis of the N B O orbitals of A reveals the origin of the differences in the orbital occupancies between A and D (Table B.4). Strong donation from the a-bonding orbitals to the trans Ta-C a* orbitals (Table B.4, Figure B.7) is shown by the large interaction terms for A. It should be noted that in D, the corresponding donation from the Ta-C a-bonding orbitals the Ta-C a* orbitals is significantly reduced (Table B.4, Figure B.8) because the more favorable C l Ta-Me bond angles of D can avoid the mixing of bonding and anti-bonding orbitals observed in A. Thus, it appears that formation of the metallaaziridine ring is a key  227  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  component that allows the remaining methyl and carbene substituents in D to adopt preferable bonding positions.  Table B.4.  Important second order perturbation theory analysis N B O donor acceptor interactions AEy (kcal/mol) that contribute to shorter Ta-carbene and Ta-Me bonds in the metallaaziridine product D relative to the trimethyl complex A.  N B O Donor orbital  N B O Acceptor orbital  AEy (kcal/mol)  A  D  Tal-Cl a  Tal-C2 o*  26.13  1.02  Tal-Cl a  Tal-C3 o*  31.50  2.64  Tal-C2 a  T a l - C l a*  38.32  1.81  Tal-C3 a  T a l - C l a*  54.62  3.02  228  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations Tal-Cl a  F i g u r e B.7.  Tal-C2a  Tal-C3 a  Gaussview representations of selected N B O bonding and antibonding orbitals in the trimethyl complex A .  229  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  Tal-Cl a  Figure B.8.  Tal-C2o  Tal-C3 a  Gaussview representations of selected N B O bonding and antibonding orbitals in the trimethyl complex D .  The other factor that causes the Ta-carbene distance to be shorter in the metallaaziridine complex D than in the trimethyl complex A is the formation of the fivemembered ring. To gauge how much of the shortening of the Ta-carbene bond in D relative to A is a result of the five-membered ring pulling the carbene toward the Tacentre, calculations were conducted on model complexes in which atoms linking the  230  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  carbene unit to the amido donors were removed. In the first calculation, both  CH2CH2  linkages  generate  in A  were  removed  and replaced  with  H  atoms  to  (H N2C3)Ta(NH2)2(Me)3 , A ' (Figure B.9). Optimization of A ' resulted in a Ta-carbene 4  bond length of 2.378 A, which is only 0.003 A shorter than for A , and indicates that the two six-membered rings do not significantly influence the Ta-carbene distance. In the second calculation, the C H 2 C H 2 linkage between the carbene and amido units, and the C H 2 linkage between the carbene and the metallaaziridine ring were removed to generate (H N C3)Ta(NH )(NHCH2)(Me)2, D' (Figure B.9). The optimized Ta-carbene distance 4  2  2  in D' is 2.275 A, which is 0.027 A longer than is observed in D. Thus, the calculations suggest that approximately 20% of the Ta-carbene bond shortening observed in D can be attributed to the five-membered ring pulling the carbene toward the Ta-centre, while the remaining shortening can be attributed to electronic effects brought upon by the formation of the metallaaziridine ring (vide ante).  D'  A' Figure B.9.  JIMP Pictures of A ' and D'.  231  References begins on page 233.  Appendix B: Evaluating the Formation o f Tantalum Metallaaziridine Complex by Density Functional Calculations  B.4.  General Considerations  A l l calculations were performed using the Gaussian 03 suite of programs.  5  Optimized gas-phase geometries were obtained using the Becke3 exchange functional,  6  in combination the Lee, Yang, and Parr correlation functional, i.e. the B 3 L Y P method, 7  as implemented in Gaussian 03. The basis set (BS1) used for geometry optimizations and energy calculations was implemented as follows: for tantalum, the valence double-^ LANL2DZ " 8  10  basis set was supplemented with a set of 6p functions for transition metals  developed by Couty and H a l l , " while for all hydrogen, carbon, and nitrogen atoms, the 612 17  31G(d',p') basis sets " were used. A l l structures were calculated in singlet spin states using the restricted B 3 L Y P method. Calculating the harmonic vibrational frequencies and noting the number of imaginary frequencies confirmed the nature of all intermediates (NImag = 0) and transition state structures (NImag = 1). A l l gas-phase relative free energies are reported in kcal mol" , with the energy of [NCN]TaMe3 ( [NCN] = 1  H  H  (HNCH2CH2)2N2C3H ) set to 0.0 kcal mol" . Relative electronic energies, zero-point 1  2  corrected energies, and enthalpies are provided in the supplemental information. For the computational investigation, [NCN] was used in place of the experimental ligand (pH  M e - C H 4 N C H 2 C H 2 ) N 2 C H 2 ( [NCN]) in order to reduce the computational demands, Tol  6  2  3  while still providing two amide donors and one 7V-heterocyclic carbene donor to the tantalum centre.  Natural Bond Orbitals (NBO) calculations were conducted with  Gaussian N B O Version 3.1. ' 4  18-21  232  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Complex by Density Functional Calculations  B.5. References  (1)  Manson, J.; Webster, C. E.; Hall, M . B. In JIMP Development Version 0. l.vlU (built for Windows PC and Redhat Linux 7.3) Department of Chemistry, Texas  A & M University, College Station, T X 77842, 2006. (2)  Landis, C. R.; Cleveland, T.; Firman, T. K. J. Am. Chem. Soc. 1995, 77 7, 1859.  (3)  Bayse, C. A.; Hall, M . B. J. Am. Chem. Soc. 1999, 727, 1348.  (4)  Reed, A . E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.  (5)  Frisch, M . J.; Trucks, G. W.; Schlegel, H . B.; Scuseria, G. E.; Robb, M . A . ; Cheeseman, J. R.; Montgomery, J. A . J.; Vreven, T.; Kudin, K . N . ; Burant, J. C ; Millam, J. M . ; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M . ; Scalmani, G.; Rega, N . ; Petersson, G. A.; Nakatsuji, H.; Hada, M . ; Ehara, M . ; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M . ; Nakajima, T.; Honda, Y . ; Kitao, O.; Nakai, H.; Klene, M . ; L i , X . ; Knox, J. E.; Hratchian, H . P.; Cross, J. B.; Adamo, C ; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A . J.; Cammi, R.; Pomelli, C ; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V . G.; Dapprich, S.; Daniels, A . D.; Strain, M . C ; Farkas, O.; Malick, D. K.; Rabuck, A . D.; Raghavachari, K . ; Foresman, J. B.; Ortiz, J. V . ; Cui, Q.; Baboul, A . G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M . A.; Peng, C. Y.; Nanayakkara, A . ; Challacombe, M . ; Gill, P. M . W.; Johnson, B.; Chen, W.; Wong, M . W.; Gonzalez, C ; Pople, J. A . Gaussian  03, Revision B.4; Gaussian, Inc.: Pittsburgh,  PA, 2003.  (6)  Becke, A . D. J. Chem. Phys. 1993, 98, 5648.  (7)  Lee, C ; Yang, W.; Parr, R. G. Phys. Rev. B: Condens. Matter 1 9 8 8 , 37, 785.  (8)  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1 9 8 5 , 82, 270.  (9)  Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1 9 8 5 , 82, 284.  (10)  Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1 9 8 5 , 82, 299.  (11)  Couty, M . ; Hall, M . B. J. Comput. Chem. 1 9 9 6 , 7 7, 1359.  (12)  Ditchfield, R.; Hehre, W. J.; Pople, J. A. J. Chem. Phys. 1 9 7 1 , 54, 724.  233  References begins on page 233.  Appendix B: Evaluating the Formation of Tantalum Metallaaziridine Calculations  Complex by Density Functional  (13)  Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257.  (14)  Hariharan, P. C ; Pople, J. A . Theor. Chim. Acta 1973, 28, 213.  (15)  Petersson, G. A.; Al-Laham, M . A . J. Chem. Phys. 1991, 94, 6081.  (16)  Petersson, G. A.; Bennett, A.; Tensfeldt, T. G.; Al-Laham, M . A.; Shirley, W. A.; Mantzaris, J. J. Chem. Phys. 1988, 89, 2193.  (17)  Foresman, J. B.; Frisch, JE. Exploring Chemistry with Electronic Structure Methods, 2nd Ed. (Gaussian, Inc, Pittsburgh, PA), p. 110. The 6-31G(d',p) basis set has the d polarization functions for C, N, O, and F taken from the 6-31 IG(d) basis set, instead of the original arbitrarily assigned value of 0.8 used in the 631G(d) basis set.  (18)  Foster, J. P.; Weinhold, F. J. Am. Chem. Soc. 1980, 102, 7211.  (19)  Reed, A . E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.  (20)  Reed, A . E.; Weinhold, F. J. Chem. Phys. 1985, 83, 1736.  (21)  Carpenter, J. E.; Weinhold, F. Theochem 1988, 46, 41.  234  References begins on page 233.  

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.831.1-0061126/manifest

Comment

Related Items