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Intermolecular C-H activation effected by CP*W(NO)-containing complexes Tsang, Jenkins Yin Ki 2008

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INTERMOLECULAR C-H ACTIVATION EFFECTED BY CP*W(NO)-CONTAINING COMPLEXES by Jenkins Yin Ki Tsang B. Sc. (Combined Honours), University of British Columbia, 2002 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in The Faculty of Graduate Studies (Chemistry) THE UNIVERSITY OF BRITISH COLUMBIA February 2008 © Jenkins Yin Ki Tsang 2008 11 Abstract Thermolysis of Cp*W(NO)(CH2CMe3)2 (2.1) in halo, methoxy, or phenylethynyl- substituted benzenes leads to the formation of the alkylidene intermediate Cp*W(NO)(=CHCMe3) which selectively activates ortho C-H bonds of the organic substrates. The ortho-regioselectivity diminishes as the size of the substituent increases from F (97 %) to C-=CPh (51 %). In the solid-state structure of all complexes the ortho- substituent is not coordinated to the metal centre; rather, the metal centre is engaged in agostic interactions with a neopentyl methylene C-H bond. Mechanistic studies on the chlorobenzene reaction reveal that the ortho-C-H-activation product is preferentially formed via thermal isomerization from the meta / para-C-H-activation isomers. Reactions between Cp*W(NO)(CH2EMe3)Cl (E = C or Si) and a variety of bis(allyl)magnesium reagents lead to the expected formation of Cp*W(NO)(alkyl)(allyl) complexes. Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCH2) (3.5), Cp*W(N0)(CH2CMe3)(ri 3 - CH2CMeCH2) (3.6), Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCHMe) (3.7), Cp*W(N0)(CH2CMe3)(rI 3-CH2CHCHPh) (3.8) and Cp*W(N0)(CH2SiMe 3 )(r1 3 - CH2CHCHMe) (3.9) have thus been synthesized in moderate yields. The solid-state molecular structures of 3.5 and 3.7-3.9 feature a 6-7C distorted ally! ligand in the endo conformation. Complex 3.5 reacts with pyrrolidine at RT to form Cp*W(NO)(NC4H8)(CHMeCH2NC4H8) (3.10), a nucleophilic-attack product. Complexes 3.6-3.9 effect the concurrent N-H and a-C-H activation of pyrrolidine at RT and form iii alkyl-amido complexes analogous to the previously known Cp*W(N0)(CH2EMe)(NC4H7-2-CMe2CH=CH2) (3.12). Thermolysis of Cp*W(N0)(CH2CMe3)(r1 3-CH2CHCHMe) (3.7) at RT leads to the loss of neopentane and the formation of the i 2-diene intermediate Cp*W(N0)(i 2 - CH2=CHCH=CH2) (A) which has been isolated as a PMe 3 adduct. In the presence of saturated organic substrates, C-H activation occurs exclusively at the methyl positions of the molecule. Reactions between intermediate A and unsaturated substrates lead to coupling between the coordinated i 2-diene and the unsaturation on the organic molecule. Treatment of Cp*W(N0)(n-051111)(r1 3-CH2CHCHMe) (4.1) with I2 at -60 °C produces n- 05H i 1 1 in moderate yields. Thermolysis of Cp*W(N0)(CH2CMe3)(i 3-CH2CHCHPh) (3.8) in benzene at 75 °C for one day leads to the exclusive formation of Cp*W(N0)(H)(r1 3 -PhCHCHCHPh) (5.1). Trapping, labelling, and monitoring experiments suggest that 5.1 is formed via 1) the loss of neopentane and the generation of the allene intermediate Cp*W(N0)(n 2 - CH2=C=CHPh), 2) the C-H activation of benzene resulting in a phenyl phenylallyl complex, and 3) the thermal isomerization of this latter species to 5.1. iv Table of Contents Abstract^ Table of Contents^  iv List of Tables  xiii ^ List of Figure   xviii Abbreviations^ xxi Acknowledgements ^ xxiii Co-Authorship Statement ^ xxvi Chapter 1^Intermolecular C-H Activation of Hydrocarbon Substrates Initiated by Organometallic Species^  1 1.1^Introduction^  1 1.1.1 Organometallic Chemistry — an Overview^  1 1.1.2 C-H Activation by Transition-Metal Complexes -- an Overview^ 2 1.1.3 Types of Organometallic C-H Activation Mechanisms^ 6 1.1.3.1^Oxidative Addition^  6 1.1.3.2^Sigma-Bond Metathesis  8 1.1.3.3^Metalloradical C-H Activation^  8 1.1.3.4^1,2-Addition Across M-E Multiple Bonds^ 9 1.2^C-H Activating Compounds Discovered by the Legzdins Group^ 10 1.2.1 The Tungsten-Acetylene System^  10 1.2.2 The Tungsten-Alkylidene System  11 V1.2.3 The Molybdenum-Alkylidene System^  12 1.2.4 The Tungsten-Allene System^  13 ^ 1.3^Outline and Format of This Thesis    16 1.4^References and Notes^  19 Chapter 2^Ortho-Selective C-H Activation of Substituted Benzenes Effected by a Tungsten Alkylidene Complex Without Substituent Coordination^ 2.1^Introduction^ 2.2^Results and Discussion^ 23 23 25 2.2.1 C-H Activation of Monosubstituted Benzenes^ 25 2.2.2 C-H Activation of Disubstituted Benzenes 30 2.2.3 Spectroscopic Properties of the C-H Activation Products^ 33 2.2.4 X-Ray Crystallographic Analyses of Selected C-H Activation Products^ 36 2.2.5 Mechanistic Studies^ 42 2.2.6 Representative Reactivity of C-H Activated Complex 2.2a^ 44 2.3 Conclusion^ 47 2.4 Experimental Procedures^ 48 2.4.1 General Considerations 48 2.4.2 Representative Procedure for Effecting Preparative Thermolyses of Cp*W(NO)(CH2CMe3)2 (2.1) in Organic Substrates^ 49 2.4.3 Preparation of Cp*W(NO)(CH2CMe3)(C6H 4F) (2.2a-c)^ 50 vi 2.4.4 Preparation of Cp*W(NO)(CH2CMe 3)(C6H4C1) (2.3a-c)^ 51 2.4.5 Preparation of Cp*W(NO)(CH2CMe 3)(C6H4Br) (2.4a-c)^ 52 2.4.6 Preparation of Cp*W(NO)(CH2CMe3)(C6H4OMe) (2.5a-c)^ 53 2.4.7 Preparation of Cp*W(N0)(CH2CMe3)(0-C6H4CCC6H5) (2.6a) and Cp*W(N0)(r1 3 ,1 1 -(CMe3)HCCPh=CPh-CPh=CPh) (2.6d)^ 54 2.4.8 Preparation of Cp*W(N0)(11 3 0-1 1 -(Me3 C)HC-CEt=CEt-CEt=CEt) (2.7)^  56 2.4.9 Preparation of Cp*W(N0)(CH 2CMe 3)(C6H3-2,3-F2) (2.8a) and Cp*W(N0)(CH2CMe3)(C6H3-3,4-F2) (2.8b)^  57 2.4.10 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2,3-C12) (2.9a) and Cp*W(NO)(CH2CMe3)(C6113-3,4-C12) (2.9b)^  58 2.4.11 Preparation of Cp*W(N0)(CH2CMe3)(C 6H3-2,4-F2) (2.10a) and Cp*W(N0)(CH2CMe3)(C6H3-2,6-F2) (2.10c)^  59 2.4.12 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2,4-C12) (2.11a) and Cp*W(N0)(CH2CMe3)(C6H3-3,5-C12) (2.11b)^  60 2.4.13 Preparation of Cp*W(NO)(CH2CMe3)(C6H3-2-F-5-0) (2.12a) and Cp*W(NO)(CH2CMe3)(C6113-2-C1-5-F) (2.12b)^ 61 2.4.14 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2-F-5-0Me) (2.13a) and Cp*W(N0)(CH2CMe3)(C6H3-2-0Me-5-F) (2.13b)^ 62 2.4.15 Preparation of Cp*W(N0)(CH2CMe3)(C6113-2-0Me-5-C1) (2.14a) and Cp*W(N0)(CH2CMe3)(C6H3-2-C1-5-0Me) (2.14b)^ 63 2.4.16 Attempted Thermolysis of 2.1 in Iodobenzene, Trifluoromethoxybenzene, and Acetophenone^ 65 vii 2.4.17 Preparation of [Et4N] +[Cp*W(NO)(CH2CMe3)(CN)(o-C6H4F)] - ([Et4N] +[2.15] -)^  65 2.4.18 Preparation of Cp*W(N0)(r1 2-C(--- 0)CH2CMe3)(0-C6H4F) (2.16)^ 66 2.4.19 X-Ray Crystallography^  67 2.5^References and Notes^ 70 Chapter 3^Synthesis and Characterization of New Cp*W(NO)(CH2CMe3)(allyl) Complexes and Their Reactivity with Cyclic Amines^ 74 3.1^Introduction^  74 3.2^Results and Discussion^  79 3.2.1 Synthesis and Spectroscopic Properties of New Compounds^ 79 3.2.2 Thermal Stabilities of New Compounds^  87 3.2.3 Reactions of New Complexes with Pyrrolidine and Piperidine^ 88 3.2.3.1^Reactions Between Cyclic Amines and (3.5)^ 88 3.2.3.2^Reactions Between Cyclic Amines and 3.6-3.9^ 91 3.2.3.3^Mechanistic Insights on the Concurrent N-H and a-C-H Activation Process^  94 3.3^Conclusion^  95 3.4^Experimental Procedures^  96 3.4.1 General Considerations  96 3.4.2 Preparation of Cp*W(N0)(CH2CMe3)(r1 3-CH2CHCH2) (3.5)^ 98 3.4.3 Preparation of Cp *W(N0)(CH2CMe3)(1 3-CH2CMeCH2) (3.6)^ 100 viii 3.4.4 Preparation of Cp*W(N0)(CH2CMe3)(113-CH2CHCHMe)  (3.7)^ 100 3.4.5 Preparation of Cp*W(N0)(CH2CMe3)(113-CH2CHCHPh)  (3.8)^ 101 3.4.6 Preparation of Cp*W(N0)(CH2SiMe3)(113-CH2CHCHMe) (3.9)^ 102 3.4.7 Preparation of Cp*W(NO)(NC4H8)(CHMeCH2NC4H8) (3.10)^ 103 3.4.8 Preparation of Cp*W(N0)(NC5H10)(CHMeCH2NC5H10) (3.11)^ 104 3.4.9 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-Me2CCH=CH2) (3.12) Revisited^  105 3.4.10 Preparation of Cp*W(N0)(CH2CMe3)(NC5H9-2-Me2CCH=CH2) (3.13) Revisited^  106 3.4.11 Preparation of Cp *W(N0)(CH2CMe3)(NC4117-2-CH2CMe=CH2) (3.14)^  107 3.4.12 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-CHMeCH=CH2) (3.15)^  109 3.4.13 Preparation of Cp *W(N0)(CH2CMe3)(NC4H7-2-CHPhCH=CH2) (3.16)^  110 3.4.14 Preparation of Cp*W(N0)(CH2SiMe3)(NC41-17-2-CHPhCH=CH2) (3.17)^  111 3.4.15 X-Ray Crystallography^  112 3.5^References and Notes^  115 Chapter 4^Facile Aliphatic C-H Bond Activation Initiated by Cp*W(N0)(CH2CMe3)(13-CH2CHCHMe)^ 119 4.1^Introduction^  119 ix 4.2^Results and Discussion^  121 4.2.1 Thermal Instability of Cp*W(N0)(CH2CMe3)(T1 3 -CH2CHCHMe) (3.7)^  121 4.2.2 C-H Activation of n-Pentane -- a Serendipitous Discovery^ 121 4.2.3 Investigations into the Reactive Intermediate – Trapping and Labeling Studies^  124 4.2.4 Aliphatic C-H Activation -- Scope of Substrate^ 130 4.2.4.1^C-H Activation of Linear and Branched Hydrocarbons^ 130 4.2.4.2^C-H Activation of Heteroatom-Containing Saturated Substrates^  131 4.2.4.3^Attempted C-H Activation of Unsaturated Substrates^ 133 4.2.5 Attempted Aryl C-H Activation of Aromatic Substrates^ 138 4.2.6 Attempted Functionalization of C-H Activated Fragments^ 142 4.3^Conclusion^  143 4.4^Experimental Procedures^  145 4.4.1 General Considerations  145 4.4.2 Preparation of Cp*W(N0)(n-05H11)(1 3-CH2CHCHMe) (4.1)^ 146 4.4.3 Preparation of Cp*W(NO)(r1 2 -CH2=CH—CH=CH2)(PMe3) (4.2)^ 148 4.4.4 Preparation of Cp*W(N0)(n -C7Hi5)(T1 3 -CH2CHCHMe) (4.3)^ 149 4.4.5 Preparation of Cp*W(N0)(CH2(cyclohexyl))(r1 3-CH2CHCHMe) (4.4)^  150 4.4.6 Preparation of Cp*W(N0)(CH2CH2CH3)(T1 3-CH2CHCHMe) (4.5)^ 150 4.4.7 Preparation of Cp*W(N0)(CH2CH3)(r1 3 -CH2CHCHMe) (4.6)^ 151 x4.4.8 Preparation of Cp*W(N0)(CH3)(71 3 -CH2CHCHMe) (4.7)^ 152 4.4.9 Preparation of Cp*W(N0)(CH2SiMe3)(113-CH2CHCHMe) (3.9) -- C-H Activation Route^  153 4.4.10 Preparation of Cp*W(NO)((CH2)4C0(r1 3 -CH2CHCHMe) (4.8)^ 153 4.4.11 Preparation of Cp*W(N0)(CH2CH2OCH2CH3)(r1 3-CH2CHCHMe) (4.9)^  154 4.4.12 Preparation of Cp *W(N0)(CH2CH2N(CH2CH3)2)(T1 3 -CH2CHCHMe) (4.10)^  155 4.4.13 Preparation of Cp *W(N0)(11 3 ,1) 1 -CH2CHCHCH2C011(C4H8)C,H) (4.11)^  156 4.4.14 Preparation of Cp*W(NO)(1 3 ,i 1 -CH2CHCHCH2C(CH3)20) (4.12)^ 157 4.4.15 Preparation of Cp *W(NO)(r1 3 ,11 1 -CH2CHCHCH2C(CH2CH3)20) (4.13)^  157 4.4.16 Preparation of Cp *W(NO)(r1 3 ,11 1 -CH2CHCHCH2CCH3---CCH3) (4.14)^  158 4.4.17 Preparation of Cp*W(N0)(r1 I -CH2C(CH3)C(CH3)2)(r1 3-CH2CHCHMe) (4.15)^  159 4.4.18 Preparation of Cp*W(N0)(CH2C6H5)(r1 3-CH2CHCHMe) (4.16)^ 160 4.4.19 Reaction between 4.1 and 12^  161 4.4.20 X-Ray Crystallography  163 4.5^References and Notes^  167 xi Chapter 5^Preliminary Investigations on C-H Bond Activation Initiated by ^ Cp*W(N0)(CH2CMe3)(1 3-CH2CHCHPh)    172 5.1^Introduction^  172 5.2^Results and Discussion^  173 5.2.1 Thermal Properties of Cp*W(N0)(CH2CMe3)(r1 3-CH2CHCHPh) (3.8)   173 5.2.2 Reaction with Benzene   173 5.2.3 Reaction with Other Hydrocarbons ^ 179 5.3^Conclusion^ 181 5.4^Experimental Procedures^  181 5.4.1 General Considerations   181 5.4.2 Preparation of Cp*W(N0)(H)(r1 3-PhHCCHCHPh) (5.1)^ 183 5.4.3 Preparation of Cp*W(N0)(H)(ri 3-CH2C(3-cyclohexenyl)CHPh) (5.2)^  184 5.4.4 X-Ray Crystallography   185 5.5^References and Notes^  187 Chapter 6^Conclusion and Future Work^  188 6.1^Research Summary^  188 6.2^Future Directions  190 6.3^References and Notes   193 xii Appendix A Crystallographic Data Refinement, Structural Solution, Tables of Bond Lengths and Bond Angles for Structurally Characterized Complexes Described in this Thesis^ 194 List of Tables Table A.1^Crystal Data, Data Refinement, and Structural Solution for Compounds 2.2a, 2.5a and 2.6a^  195 Table A.2^Crystal Data, Data Refinement, and Structural Solution for Compounds 2.7, 2.10c and 2.16^  196 Table A.3^Crystal Data, Data Refinement, and Structural Solution for Compounds 3.5, 3.7 and 3.8^  197 Table A.4^Crystal Data, Data Refinement, and Structural Solution for Compounds 3.9 A / B, 3.10 and 3.14^  198 Table A.5^Crystal Data, Data Refinement, and Structural Solution for Compounds 4.1, 4.2 and 4.6^  199 Table A.6^Crystal Data, Data Refinement, and Structural Solution for Compounds 4.11, 4.13 and 4.14^  200 Table A.7^Crystal Data, Data Refinement, and Structural Solution for Compounds 4.15 and 4.16^  201 Table A.8^Crystal Data, Data Refinement, and Structural Solution for Compounds 5.1 and 5.2^  202 Table A.9^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.2a^  203 Table A.10 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.2a^  203 xiv Table A.11 Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.5a^  204 Table A.12 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.5a^  204 Table A.13 Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.6a^  205 Table A.14 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.6a^  205 Table A.15 Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.7^  206 Table A.16 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.7^  206 Table A.17 Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.10c^  208 Table A.18 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.10c^  208 Table A.19 Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.16^  209 Table A.20 Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.16^  209 Table A.21 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.5^  211 XV Table A.22 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.5^  211 Table A.23 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.7^  213 Table A.24 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.7^  213 Table A.25 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.8^  214 Table A.26 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.8^  214 Table A.27 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.9 A / B^  215 Table A.28 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.9 A / B^  215 Table A.29 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.10^  217 Table A.30 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.10^  217 Table A.31 Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.14^  219 Table A.32 Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.14^  219 xvi Table A.33 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.1^  220 Table A.34 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.1^  220 Table A.35 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.2^  221 Table A.36 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.2^  221 Table A.37 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.6^  222 Table A.38 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.6^  222 Table A.39 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.11^  223 Table A.40 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.11^  223 Table A.41 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.13^  225 Table A.42 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.13^  225 Table A.43 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.14^  226 xvii Table A.44 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.14^  226 Table A.45 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.15^  227 Table A.46 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.15^  227 Table A.47 Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.16^  228 Table A.48 Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.16^  228 Table A.49 Bond Distances (A) in the Solid-State Molecular Structure Determined for 5.1^  229 Table A.50 Bond Angles (°) in the Solid-State Molecular Structure Determined for 5.1^  229 Table A.51 Bond Distances (A) in the Solid-State Molecular Structure Determined for 5.2^  231 Table A.52 Bond Angles (°) in the Solid-State Molecular Structure Determined for 5.2^  231 xviii List of Figures Figure 1.1^Solid-state molecular structure of Cp*W(N0)(CH 2CMe3)(NC4H7-2- Me2CH=CH2) with 50% probability thermal ellipsoids shown^ 15 Figure 2.1 ^ ^Solid-state molecular structure of Cp*W(N0)(11 3 ,i I -(Me3C)HC -CEt=CEt-CEt=CEt) (2.7) with 50% probability thermal ellipsoids shown^  29 Figure 2.2^Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(o-C6H4F) (2.2a) with 50% probability thermal ellipsoids shown^ 37 Figure 2.3^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(o-C6H 40Me) (2.5a) with 50% probability thermal ellipsoids shown   38 Figure 2.4^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(o -C6H4CCC6H5) (2.6a) with 50% probability thermal ellipsoids shown^  39 Figure 2.5^Solid-state molecular structure of Cp *W(N0)(CH2CMe3)(2,6-C6H3F2) (2.10c) with 50% probability thermal ellipsoids shown^ 41 Figure 2.6^The relative amounts of the three isomers of Cp*W(NO)(CH2CMe3)(C 6H4C1) (2.3a-c) during the first 8 h of thermolysis of Cp*W(NO)(CH2CMe 3)2 (2.1) in chlorobenzene^ 44 Figure 2.7^Solid state molecular structure of Cp*W(N0)(r1 2-C(=0)CH2CMe3)(o- C6H4F) (2.16) with 50% probability thermal ellipsoids shown^ 46 Figure 3.1^Conformational and stereochemical isomerism in Cp'-containing transition metal allyl complexes^  74 XiX Figure 3.2^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(rl 3 - CH2CHCH2) (3.5) with 50% probability thermal ellipsoids shown^ 81 Figure 3.3^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(rl 3 - CH2CHCHMe) (3.7) with 50% probability thermal ellipsoids shown ^ 82 Figure 3.4^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(rl 3 - CH2CHCHPh) (3.8) with 50% probability thermal ellipsoids shown^ 83 Figure 3.5 ^ ^Solid-state molecular structure of Cp*W(NO)(CH2SiMe3)(1 3 _ CH2CHCHMe) (3.9), major isomer, with 50% probability thermal ellipsoids shown^ ... 84 Figure 3.6^Solid-state molecular structure of Cp*W(NO)(CH2SiMe3)(rl 3 _ CH2CHCHMe) (3.9), minor isomer, with 50% probability thermal ellipsoids shown^  85 Figure 3.7^Solid-state molecular structure of Cp*W(NO)(NC4H8)(CHMeCH2NC4H8) (3.10) with 50% probability thermal ellipsoids shown^ ... 89 Figure 3.8^Solid-state molecular structure of Cp*W(NO)(CH2CMe3)(NC4H 7-2- CH2CMe=CH2) (3.14) with 50% probability thermal ellipsoids shown.. 93 Figure 4.1^Solid-state molecular structure of Cp*W(NO)(n-0 5H„)(rl 3 - CH2CHCHMe) (4.1) with 50% probability thermal ellipsoids shown... 123 Figure 4.2^Solid-state molecular structure of Cp*W(NO)(r1 2-CH2=CHCH =CH2)(PMe3) (4.2) with 50% probability thermal ellipsoids shown^ 126 Figure 4.3^Solid-state molecular structure of Cp*W(NO)(CH2CH3)(r1 2_ CH2CHCHMe) (4.6) with 35 % probability thermal ellipsoids shown ^ 132 XX Figure 4.4^Solid-state molecular structure of Cp*W(NO)(r1 3 ,11 1 - CH2CHCHCH2C0H(C 4H8)CaH) (4.11) with 50% probability thermal ellipsoids shown^  135 Figure 4.5 ^ ^Solid-state molecular structure of Cp*W(N0)(i 3 ,1-1 1 - CH2CHCHCH2C(CH2CH3)20) (4.13) with 50 % probability thermal ellipsoids shown^  136 Figure 4.6^Solid-state molecular structure of Cp*W(NO)(r1 3,i 1 - CH2CHCHCH2CCH3=CCH3) (4.14) with 50 % probability thermal ellipsoids shown^  137 Figure 4.7^Solid-state molecular structure of Cp*W(N0)(i1 1 - CH2C(CH3)C(CH3)2)(11 3-CH2CHCHMe) (4.15) with 50% probability thermal ellipsoids shown^  139 Figure 4.8^Solid-state molecular structure of Cp*W(N0)(CH2C6H5)(1 3 - CH2CHCHMe) (4.16) with 50% probability thermal ellipsoids shown. 141 Figure 5.1^Solid-state molecular structure of Cp*W(N0)(H)(i 3 -PhHCCHCHPh) (5.1) with 50% probability thermal ellipsoids shown^ 174 Figure 5.2^Solid-state molecular structure of Cp*W(N0)(H)(1 3 -CH2C(3- cyclohexenyl)CHPh) (5.2) with 50% probability thermal ellipsoids Shown^  177 Abbreviations xxi o^degree (of angle or temperature ) a^the position once removed from a reference point (e.g. a metal centre) A ^ Angstrom, 10 0 m APT^attached proton test Ar^aryl ligand atm^atmosphere (s) P ^the position twice removed from a reference point (e.g. a metal centre) br^broad (as in a spectral feature) `13u^tert-butyl °C^degree Celsius '3C^carbon-13 13C{ 1 H}^proton-decoupled 13C calcd^calculated cm i^wavenumbers COSY^correlation spectroscopy Cp^11 5 -05H 5 ; cyclopentadienyl Cp*^T 5 -05Me5 ; 1,2,3,4,5- pentamethylcyclopentadienyl Cp'^Cp or Cp* .5^chemical shift in ppm d^doublets or day (s) D, d^21-1, deuterium, deuteron DFT^density-functional theory A^heat 16e^sixteen-electron 18e^eighteen-electron EI-MS^electron-impact mass spectrometry eqv^(chemical) equivalent 11^hapto, denotes ligand hapticity 19F^fluorine-19 FT-IR^Fourier-transform infrared spectroscopy g^gram (s) h^hour (s) HMBC^heteronuclear multiple-bond correlation HMDS^hexamethyldisiloxane hv^irradiation HSQC^heteronuclear single quantum coherence Hz^Hertz isopropyl^ v^stretching frequency J coupling constant^o^ortho VAB^n-bond J between atoms A and^obs^obscured (as in a spectral B^ feature) K degree Kelvin^ ORTEP^Oakridge Thermal Ellipsoid L ligand^ Program LREI^low resolution electron impact^31p^phosphorus-3 1 m^multiplet^ p^para m^meta Ph^phenyl; C 6I-1 5 Me^methyl; CH3^ppm^parts per million mg^milligram (s) q^quartet mL^millilitre (s)^ R^hydrocarbyl ligand mmol^millimole (s) R2, R1^residuals (statistics) mol^mole^ RT^room temperature MS^mass spectrum / mass^s^singlet, strong spectrometry^ t^triplet M+^parent molecular ion^THE^tetrahydrofuran m/z^mass-to-change ratio vs^versus NOE^nuclear Overhauser effect^VT^variable-temperature Npt^neopentyl; CH 2CMe3 Acknowledgments I would like to thank many people for their various contributions to the successful completion of the research described in this Thesis. Dr. Legzdins, a.k.a. Peter, I would like to thank you for accepting me into the group and providing intellectual and mental support throughout my graduate career. Your leadership and unique mix of grumpiness and humor have made my lab experience tremendously enjoyable. Many thanks to previous group members Drs. Craig Pamplin, Trevor Hayton, Chikako Fujita-Takayama, Ian Blackmore, Mr. Steve Ng, Mr. Michael Jin and Ms. Kajin Lee. Craig, thanks for being a caring and cheerful mentor during your time. Trevor, thank you for your no-nonsense demeanor and for reminding me about "my commitment to science" during trying times. Steve and Chikako, thanks for laying the groundwork that allowed me to bring my allyl projects close to fruition. Michael, thanks for mislabeling solvents accidentally on purpose inside the glove box. Ian and Kajin, thank you so much for synthesizing starting materials for everybody in the lab. Also, thanks to Ian for introducing me to casino Blackjack back in Kelowna. I would also like to thank current and recently-departed group members — Ms. Miriam Buschhaus, Dr. Peter Graham, Mr. Scott Semproni, Mr. Simon Kim and Mr. Chris Semiao. Miriam, thank you so much for your help in X-ray crystallography. Without you spending precious time inspecting my well and poorly-diffracting crystals I certainly would not have been able to structurally characterize so many compounds, and xxiv to make sense of some otherwise indecipherable NMR spectra that I encountered throughout my research. Peter and Scott, thanks for your intellectual and experimental work on my "pentanophile" project, particularly the methane, ethane and toluene reactions, and letting me discuss the results here. Simon, thanks for your intellectual and technical contributions to another portion of the "pentanophile" project — the reactions with the unsaturated substrates. Chris, I thank you for independently synthesizing the "Luis pentanophile" Cp*W(N0)(CH2SiMe3)(r1 3 -CH2CHCHMe) (3.9). I also want to thank you for initiating lively discussions during lunch group gatherings, and for being the prime advocator for our "mental-health" tradition — our after-hour poker tournaments, which have become a fixture throughout summer 2007. I would also like to thank a few staff members in the Department of Chemistry. I would like to thank Dr. Nick Burlinson, Liane Darge, Marietta Austria, Zorana Danilovic and Dr. Maria Ezhova for their help in NMR spectroscopy. I would like to thank Mr. Marshall Lapawa for his expertise on MS and elemental analysis services. Also, I would like to thank Dr. Brian Patrick for his work in X-ray crystallography. Ms. Judy Wrinskelle and Mr. John Ellis also deserve recognition for their invaluable assistance throughout my Ph. D. study. I would also like to thank Drs. Mike Fryzuk and Derek Gates for serving on my committee and proofreading my Thesis. Truly, without the contributions of all these great people I would not have been able to put together the three satisfying projects that I present in this Thesis. XXV I would also like to thank my parents, Jeff and Fanny, for giving me a great start to my life and bringing me up according to tough standards. Without your guidance I certainly would not have amounted to this much today. I would like to thank my brother Clinton for tolerating my level of tidiness at home where we live together. Last but not least I would like to thank my girlfriend Arielle for, well, being my girlfriend — for the love, trust and support that you provided in the past four years, and hopefully for many more years to come. xxvi Co-Authorship Statement Portions of chapter 2 have been published. Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P.; Patrick, B. 0. Ortho-Selective C-H Activation of Substituted Benzenes Effected by a Tungsten Alkylidene Complex without Substituent Coordination. Organomtallics 2006, 25, 4215-4225. In this full article I, Jenkins Y. K. Tsang, am the first author and am responsible for the research idea, experimental work, characterization and data analysis other than those related to X-ray crystallography. Ms. Miriam S. A. Buschhaus is responsible for acquiring and analyzing crystallographic data for compounds 2.2a, 2.5a, 2.10c and 2.16. Dr. Brian 0. Patrick is the departmental crystallogtapher and is responsible for acquiring and analyzing crystallographic data for compounds 2.6a and 2.7. Dr. Peter Legzdins is my research supervisor, the principal investigator of this project, to whom correspondence should be addressed to. Portions of chapter 3 have been published as a communication. Tsang, J. Y. K.; Fujita-Takayama, C.; Buschhaus, M. S. A.; Patrick, B. 0.; Legzdins, P. Concurrent N-H and a-C-H Bond Activations of Pyrrolidine and Piperidine under Ambient Conditions by 18e Tungsten Ally! Nitrosyl Complexes. J. Am. Chem. Soc. 2006, 128, 14762-14763. In this communication Dr. Chikako Fujita-Takayama is responsible for the original discovery of the concurrent N-H and a-C-H bond activation reaction. I, Jenkins Y. K. Tsang, am the first author and am responsible for the follow-up research, namely, expanding the chemistry to other organometallic ally! complexes, mechanistic studies, characterization of new compounds and data analysis other than those related to X-ray xxvii crystallography. Ms. Miriam S. A. Buschhaus is responsible for acquiring and analyzing crystallographic data for compounds 3.7, 3.8, 3.9, 3.10 and 3.14. Dr. Brian 0. Patrick is the departmental crystallogtapher and is responsible for acquiring and analyzing crystallographic data for compound 3.5. Dr. Peter Legzdins is my research supervisor, the principal investigator of this project, to whom correspondence should be addressed to. Portions of chapter 4 have been published as a communication. Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P. Selective Activation and Functionalization of Linear Alkanes Initiated under Ambient Conditions by a Tungsten Allyl Nitrosyl Complex. J. Am. Chem. Soc. 2007, 129, 5372 —5373. In this communication I, Jenkins Y. K. Tsang, am the first author and am responsible for the research idea, experimental work, characterization and data analysis other than those related to X-ray crystallography. Ms. Miriam S. A. Buschhaus is responsible for acquiring and analyzing crystallographic data for compounds 3.7, 4.1 and 4.2. Dr. Peter Legzdins is my research supervisor, the principal investigator of this project, to whom correspondence should be addressed to. CHAPTER 1 Intermolecular C-H Activation of Hydrocarbon Substrates Initiated by Organometallic Species 1.1^Introduction The research described in thesis deals with the synthesis, characterization, and reactivity of organometallic complexes. Hence, it is only appropriate to begin with a brief overview of organometallic chemistry and the subfield of C-H activation by organometallic complexes. 1.1.1 Organometallic Chemistry — an Overview' Organometallic chemistry, as its name suggests, is an intermediate field between inorganic and organic chemistry. A compound is deemed to be "organometallic" if it contains at least one bond between a metal atom and a carbon atom. There are multiple branches of organometallic chemistry research, an important one being the development of new processes that will transform organic compounds to more useful entities. One such subfield is the polymerization of small olefinic hydrocarbons such as ethylene and propylene2 (Scheme 1.1). The resulting polyolefins are extremely useful materials and have found their way into common plastic items that people encounter in their daily lives. Another prominent subfield of organometallic chemistry is the application of olefin-metathesis processes in organic synthesis 3 (Scheme 1 21.2). It is noteworthy that in both cases the chemical transformations are catalytic in nature. Scheme 1.1 C2H4 L Ti—RL nTi — R^n  „ ,^LnTi LnTi R L'2n4 J U (^ etc. R^R Scheme 1.2 H ^H Ln Ru.----=CH2^LnRu—C H2^LnRu----C H2 Ri...^„Fl ....^ LoH •.' R ' Ln Ru=CH2 C2H4 Ln Ru R R' L nRu=CH2 L Ru—CH2 R^R' R'^R' )=( R 1.1.2 C-H Activation by Transition-Metal Complexes – an Overview Another prominent subfield of organometallic chemistry is the so-called "C-H activation"4 '5 of organic molecules, which formally involves the cleavage of a C-H bond 3by a metal-containing species to form an organometallic product. C-H activation is a significant organometallic process for the following two reasons: 1) Hydrocarbons, especially linear saturated alkanes, are very unreactive in general, since they are held together by localized, strong C-C and C-H bonds (bond energy ca. 90 —110 kcal/mol). 6 '7 In addition, hydrocarbons have non-polarized bonds, and they are very poor Lewis acids or bases. 8 Alkanes do react at forcing conditions, such as high temperatures, as in the case of combustion, but the products from this reaction are CO2 and H2O, neither of which are chemically interesting. Alkanes can also be induced to react in the presence of highly reactive species such as superacids or free radicals, but these reactions often offer very poor product selectivity. 6 2) Hydrocarbons are the primary feedstock of the petrochemical industry. However, there exist few methods that can effect the conversion of alkanes into commodity chemicals with excellent regioselectivity. Methane, in particular, is the major component of natural gas (ca 80%), one of the most abundant hydrocarbons on Earth, and is relatively cheap. Current industrial processes for the conversion of methane gas into methanol or higher alkanes require high temperatures (>900 °C) and careful pressure control. A few processes that involve the C-H activation and functionalization of methane by transition-metal containing species have been reported. For example, a platinum complex in the presence of fuming sulfuric acid at 100 °C catalyzes the oxidation of methane to methyl bisulfate in up to 70% yield. 1° Similarly, cisplatin and related Pt(II) complexes catalyze the transformation of methane into methano1. 11 In other examples, certain lanthanum-based catalysts have been shown to produce methyl chloride from the mixture of methane, HCl and oxygen at temperatures between 400-500 °C. 12 In addition, methane can be catalytically oxidized into acetic acid by peroxodisulfate oxidants in the presence of vanadium-containing species and trifluoroacetic acid at 80-100 °C 13 However, these discoveries are not yet competitive with current industrial and commercial processes. The ultimate goal in C-H activation is the catalytic conversion of hydrocarbons into more functionalized and potentially more useful chemicals. The initial C-H activation of hydrocarbons by metal-containing species can be viewed as the first step towards the conversion of hydrocarbons into commodity chemicals. Regioselectivity is not a concern for methane because it only bears one type of C-H bond, although it arises as a key issue during the C-H activation of higher linear and branched aliphatic hydrocarbons as well as most aromatic hydrocarbons. The next steps involve the modification, functionalization, and release of the activated hydrocarbyl fragment in a well defined manner. The final step of a potential catalytic cycle would be the regeneration of the C-H activating species. Some of the more successful examples of catalytic processes in which C-H activation plays a key role are 1) catalytic alkane dehydrogenation in the presence of a 4 PCP = C6H3-2,6-(CH2P('Pr)2)2 Scheme 1.4 5% Cp*Rh(r14-C6Me6) O ^150 °C B–H O' B sacrificial alkene by an iridium complex bearing a pincer ligand 14 (Scheme 1.3), and 2) catalytic synthesis of alkylboronate esters from alkane by Cp* -containing complexes' 5 (Scheme 1.4). Scheme 1.3 (PCP)Ir ^ (PCP)Ir N R tB u H^ H — H (PCP)Ir' (PCP)Ir-  tBu^ Bu 5 tB u "I' H2 61.1.3 Types of Organometallic C-H Activation Mechanisms Transition-metal-mediated C-H activation usually occurs via one of the following pathways: 1) oxidative addition of C-H bonds onto a metal centre, 2) r-bond metathesis with a M-C bond, 3) metalloradical activation, and 4) 1,2-addition across metal-carbon or metal nitrogen multiple bonds. 1.1.3.1 Oxidative Addition Oxidative addition was the first mode of C-H activation to be identified. 16 Oxidative addition of a C-H bond involves the formal 2e oxidation of an electronically unsaturated metal centre via the cleavage of a C-H bond and the concurrent formation of a metal-carbon and a metal-hydrogen bond (Scheme 1.5). Scheme 1.5  LnM + R—H ----). R Lnik H X+2 oxidation state X The oxidative addition of C-H occurs in the presence of d-electrons on the metal centre, and hence this process is more common for low-valent transition metals. Numerous transition-metal-containing species are known for this process, with the Cp*Ir(L) system, where L is a 2e donating ligand, being one of the first well- / H^ — H cT-alkane complex  Me3P .....^H n-arene complex 7 characterized examples. This work has since been extended in several directions. 17-19 The 20overall transformation probably proceeds via an intermediate species, such as a a- alkane complex or a n-arene complex (Scheme 1.6). Scheme 1.6 A Me3P.. ...... Rh\ -RH R^H When there are several types of C-H bonds present in a hydrocarbon, a mixture of products is often the result of C-H activation. The regioselectivity of the process depends on factors such as the steric accessibility of the bond or the stability of the resulting metal-carbon bonds. Customary trends for regioselectivity are 1) primary > secondary > tertiary C-H bonds, 2) aromatic (sp2) > aliphatic / benzylic (sp a) C-H bonds, and 3) meta / para > ortho aromatic C-H bonds. -0(-SC-- CH3 R—II -CH4 1.1.3.2 Sigma-Bond Metathesis Another mechanism of transition-metal-assisted C-H activation is sigma-bond metathesis, which involves the exchange of an alkyl group, R, that is already present on the metal with the alkyl group, R', from the hydrocarbon substrate (Scheme 1.7). 8 Scheme 1.7 6.____ RH CH3 Metal-hydrido complexes, as opposed to metal-alkyl species, are also known to perform sigma-bond metathesis. In these cases dihydrogen, rather than methane, is lost. 21 '22 Sigma-bond metathesis is less common than oxidative addition and is typically observed for early transition-metal / lanthanide complexes. 23-25 1.1.3.3 Metalloradical C-H Activation Rhodium (II) porphyrin complexes exist in a monomer-dimer equilibrium and can reversibly break C-H bonds.26 '27 The hydrocarbyl and the hydrido fragments end up on 9distinct metal centres. The proposed mechanism is depicted in Scheme 1.8, with methane being shown as a representative example. Scheme 1.8  _1 H H C H — Rh(tmp) H 2(tmp)Rh + CH4 tmp = tetramesitylporphyrinato (tmp)RhC H3 + (tmp)RhH 1.1.3.4 1,2-Addition Across M-E Multiple Bonds The addition of a C-H bond across metal-element multiple bonds is a fairly recent discovery. Examples have been observed for C-H addition across 1) metal-imido (M=NR)28 (Scheme 1.9), metal-carbene (M=CRR') 29 and metal-carbyne (MaCR) linkages. 30 In these systems M is often an early transition metal. The product selectivity is generally similar to that observed for the oxidative-addition pathway (vide supra). Scheme 1.9 —ZrI A -THF tN Bu °C ''''' ''NO 50 -SiMe4 —Si- 10 1.2^C-H Activating Compounds Discovered by the Legzdins Group 1.2.1 The Tungsten-Acetylene System The tungsten-acetylene system is the earliest C-H activating system to have been discovered in the Legzdins laboratories. 31 The precursor for the tungsten-acetylene system is the alkyl-vinyl complex, Cp*W(NO)(CH 2SiMe3)(CPh=CH2), which loses tetramethylsilane at slightly elevated temperatures (Scheme 1.10). A labeling study with C6D6 yields the phenyl-vinyl complex with deuterium incorporation at the (3-position of the vinyl ligand, thereby implying the existence of the phenylacetylene intermediate. In the presence of linear alkanes, metallocyclic-allyl complexes are formed as the n-alkane is doubly-activated at the 1 and 2 positions and is coupled to the vinyl ligand. Scheme 1.10 70°C - cme4ON""iW 11 1.2.2 The Tungsten-Alkylidene System The tungsten-alkylidene system was first discovered when a sample of the bis(neopentyl) complex, Cp*W(NO)(CH2CMe3)2 , was thermolyzed in benzene at 70 °C, leading to the formation of the known alkyl-aryl complex Cp*W(NO)(CH2CMe3)(C 6H5). Subsequent trapping experiments resulted in the isolation of Cp*W(NO)(=CHCMe3)(PMe3) and implied the existence of the alkylidene intermediate, 29d whose rich chemistry is depicted in Scheme 1.11. Other alkylidene precursors behave similarly. For example, the neopentyl-benzyl complex, Cp*W(NO)(CH2CMe3)(CH 2C6H5), loses neopentane, also at 70 °C, to form the transient C-H-activating benzylidene intermediate Cp*W(NO)(=CHC 6H5). 32 Scheme 1.11 12 1.2.3 The Molybdenum-Neopentylidene System Like its tungsten congener, the molybdenum bis(neopentyl) complex, Cp*Mo(NO)(CH2CMe3)2, initiates the C-H activation of hydrocarbons by losing neopentane and forming the alkylidene intermediate, Cp*Mo(N0)(=CHCMe 3). 33 The chemistry involving the two systems is generally similar, notable exceptions being that 1) the Mo system operates at RT and is much more sensitive to air and moisture, and 2) during the reaction with benzene the novel benzyne intermediate, Cp*Mo(N0)(r1 2-C6H4), is formed, and it can be trapped by the Lewis base pyridine (Scheme 1.12). The benzyne intermediate is also capable of C-H activation, as evidenced by the gradual formation of the known diphenyl complex Cp*Mo(NO)(C6H 5)2 34 when the neopentyl-phenyl complex Cp*Mo(NO)(CH 2CMe3)(C6H5) is dissolved in C6H6 for one week. Scheme 1.12  ---- Mo— NO 50 °C, -CMe4 ON.. ON.... ^ - PMe3 C H2D W ON W c6 D5 + ON zW C6D5C6D6 ON W" 13 1.2.4 The Tungsten-Allene System The tungsten-allene system is the newest member of the family of C-H activating intermediates synthesized in the Legzdins laboratories. The precursor in this case is the neopentyl-allyl complex, Cp*W(NO)(CH2CMe3)(11 3-CH2CHCMe2), which loses neopentane at 50 °C and subsequently activates hydrocarbon C-H bonds 35 (Scheme 1.13). An i 2 -allene intermediate has been trapped by PMe3, although labeling studies (thermolysis in C 6D 6) also result in deuterium incorporation in the terminal methyl groups, thereby suggesting the presence of n 2-diene type intermediates. Scheme 1.13 Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCMe2) also exhibits intriguing reactivities towards various organic heterocycles. Treatment with pyridine, THF, and pyrrolidine 50 °C ON.,......W4....,^H major product ^. ON..-..W- /) N 0 14 leads to entirely different results36 (Scheme 1.14). All three depicted products have been characterized by X-ray crystallography in addition to conventional spectroscopic techniques. The most remarkable transformation is probably the reaction between Cp*W(N0)(CH2CMe3)(1) 3-CH2CHCMe2) and pyrrolidine, a reaction that occurs readily at RT to form the 18e neopentyl-amido complex, Cp*W(N0)(CH2CMe3)(NC 4H7-2- Me2CH=CH2), the solid-state molecular structure of which is shown in Figure 1.1. Scheme 1.14 NH --* (C/ or 7 d (n=2)^ 0 quantitative 17 h (n=1) n ( r3:-' W1RT N major product 15 Figure 1.1^Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(NC4H7-2- Me2CH=CH2) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-N(2) = 1.940(2), N(2)-C(6) = 1.485(3), N(2)-C(9) = 1.496(4) , C(9)-C(10) = 1.560(4), C(10)-C(13) = 1.510(4), C(13)-C(14) = 1.316(4), W(1)-N(1) = 1.761(2), N(1)-O(1) = 1.239(3), W(1)-N(1)-0(1) = 169.4(2), C(10)-C(13)- C(14) = 127.4(3), C(9)-C(10)-C(13) = 111.2(2), N(1)-W(1)-N(2) = 98.61(10), N(1)- W(1)-C(1) = 98.41(11), W(1)-N(2)-C(6) = 119.91(18), C(6)-N(2)-C(9) = 106.1(2), W(1)- N(2)-C(9) = 132.32(17). 16 1.3^Outline and Format of This Thesis Chapter 2 deals with the regioselectivity of the C-H activation of various substituted benzenes initiated by the well-studied tungsten bis(neopentyl) complex, Cp*W(NO)(CH2CMe3)2. Particular attention is focused on substrates that feature substituents with lone pairs of electrons. This research was inspired by 1) the previous work by former group members Dr. Craig S. Adams and Elizabeth Tran, who activated a series of alkyl-substituted benzenes and discovered that the regioselectivity is essentially determined by steric factors, and 2) multiple reports in the chemical literature that feature selective ortho C-H activation by various organometallic systems. In this chapter the regioselectivity of the C-H activation reactions is outlined and compared to those obtained by other organometallic C-H activating systems. New compounds are subjected to conventional spectroscopic studies, and the data obtained are discussed. A selected reaction has been studied mechanistically, and the results are presented and rationalized. An attempt to derivatize an activated aryl fragment is also described. The research described in chapters 3 to 5 is an effort to address multiple questions from previous projects pertaining to the compound Cp*W(N0)(CH2CMe3)(ri 3 - CH2CHCMe2). Specifically, the heterocycle chemistry summarized in Scheme 1.10 has been deemed intriguing enough to warrant further investigation. Among the three types of transformations, the one involved pyrrolidine deserves special attention because 1) the process takes place at RT, and the neopentyl ligand is not lost, which means that an if- olefin intermediate is unlikely to be responsible for this transformation, and 2) the 17 pyrrolidine reaction, unlike the other two, is relatively "clean" — the reaction yields a single discernible organometallic product, whereas in the case of pyridine and THF, the compounds whose structures are presented are formed among a large number of other as yet unidentified products. In chapter 3 the synthesis of a new series of alkyl-allyl compounds is described. All new compounds are studied spectroscopically. Each of the new compounds is reacted with pyrrolidine as well as a variety of organic amines, in an effort to establish the generality of the reaction between Cp*W(N0)(CH2CMe3)(r1 3 -CH2CHCMe2) and pyrrolidine. Mechanistic insights for the observed types of reactivity are also presented. The thermal chemistry of Cp*W(N0)(CH2CMe3)(i 3-CH2CHCHMe) is discussed thoroughly in chapter 4. Cp*W(N0)(CH2CMe3)(r1 3 -CH2CHCHMe), one of the newly synthesized alkyl-allyl complexes, is thermally unstable at RT and is able to initiate C-H activation at this temperature. Unlike most other C-H activating systems, Cp*W(N0)(CH2CMe3)(r1 3-CH2CHCHMe) is extremely adept at activating aliphatic C-H bonds. All new compounds have been characterized by conventional spectroscopic techniques, and the scope of tolerable substrates for this chemistry is discussed. Attempts to functionalize the activated n-pentyl fragment are also described, and a catalytic cycle involving the C-H activation by Cp*W(N0)(CH2CMe3)(r1 3 -CH2CHCHMe) as the initial step is proposed. 18 In the final chapter the results presented in chapters 2 through 4 are summarized. The strengths and weaknesses of this Thesis are discussed, and new research ideas are proposed. The current state of the research in the Legzdins laboratories is addressed, and the preliminary investigation of the thermal chemistry of Cp*W(N0)(CH 2CMe3 )(r1 3 - CH2CHCHPh), another member of this new series of allyl-alkyl complexes, is reported. This Thesis is formatted with chapters 2 through 5 possessing five major sections. If X is the chapter number, then the Sections appear as X.1 Introduction, X.2 Results and Discussion, X.3 Epilogue, X.4 Experimental Procedures, and X.5 References and Notes. Subsections of these categories are numbered using legal outlining, e.g. X.1.1, X.1.2, X.1.2.1, X.1.3, etc. All compounds discussed in each chapter are catalogued numerically, e.g. in chapter X, compounds appear as X.1, X.2, etc, with the exception of Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCMe2), Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCHMe) and Cp*W(N0)(CH2CMe3)(113-CH2CHCHPh) which are denoted as 3.1, 3.7 and 3.8, respectively, since they make their first appearance in Chapter 3 of this Thesis. These three complexes retain the same catalogue number when they are mentioned again in subsequent chapters. Schemes and figures are similarly sequenced and referenced. 19 1.4^References and Notes (1) Crabtree, R. H. The Organometallic Chemistry of the Transition Metals, 3 rd ed; Wiley and Sons: Toronto, ON, 2001 (2) For leading reviews on the topic of olefin polymerization, see: (a) Bochmann, M. E.1 Chem. Soc., Dalton Trans.1996, 255. (b) Gibson, V. C. Spitzmesser, S. K. Chem. Rev. 2003, 103, 283. (c) Angermund, K.; Fink, G.; Jensen, V. R.; Kleinschmidt, R. Chem. Rev. 2000, 100, 1457. (3) For leading reviews on the topic of olefin metathesis, see: (a) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18. (b) Schrock, R. R.; Czekelius, C. Adv. Synthesis & Cat. 2007, 349, 55. (4) Shilov, A. E.; Shul'pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes; Kluwer Academic Publishers: Dordrecht, The Netherlands, 2000. (5) Activation and Functionalization of Alkanes; Hill, C. L., Ed.; Wiley-Interscience: New York, NY, 1989. (6) Labinger, J. A.; Bercaw, J. E. Nature 2002, 417, 507. (7) Crabtree, R. H. Chem. Rev. 1985, 85, 245. (8) Arndtsen, B. C.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. (9)^Gonzales, J. M.; Oxgaard, J.; Periana, R. A.; Goddard, W. A., III. Organometallic 2007, 26, 1505 and references cited therein. 20 (10) Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Science 1998, 280, 560. (11) Paul, A.; Musgrave, C. B. Organometallic 2007, 26, 793 and references cited therein. (12) Podkolzin, S. G.; Stangland, E. E.; Jones, M. E.; Peringer, E.; Lercher, J. A. Am. Chem. Soc. 2007, 129, 2569. (13) Kirillova, M. V.; Kuznetsov, M. L.; Reis, P. M.; da Silva, J. A. L.; Frausto da Silva, J. J. R.; Pombeiro, A. J. L. J. Am. Chem. Soc. 2007, 129, 10531 and references cited therein. (14) Liu, F.; Pak, E. B.; Singh, B.; Jensen, C. M.; Goldman, A. S. J. Am. Chem. Soc. 1999, 121, 4086. (15) (a) Waltz, K. M.; Hartwig, J. F. Science 1997, 277, 211. (b) Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Science 2000, 287, 195. (16) Jones, W. D.; Feher, F. J. J. Am. Chem. Soc. 1986, 108, 4814. (17) (a) Jaonwicz, A. H.; Bergman, R. G. J. Am. Chem. Soc. 1983, 105, 3929. (b) Hoyano, J. K.; Graham, W. A. G. J. Am. Chem. Soc. 1982, 104, 3723. (18) Peterson, T. H.; Golden, J. T.; Bergman, R. G. J. Am. Chem. Soc. 2001, 123, 455. (19) (a) Ghosh, C. K.; Graham, W. A. G. J. Am. Chem. Soc. 1987, 109, 4726. (b) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91. (c) Jones, W. D.; Hessell, E. T. J. Am. Chem. Soc. 1993, 115, 554. (20) For a recent study of cr-alkane complexes, see: Vetter, A. J.; Flaschenriem, C.; Jones, W. D. J. Am. Chem. Soc. 2005, 127, 12315. 21 (21) Vidal, V.; Theolier, A.; Thivolle-Cazat, J.; Basset, J. M.; Corker, J. J. Am. Chem. Soc. 1996, 118, 4595. (22) Niccolai, G. P.; Basset, J. M. Appl. Cat. A 1996, 146, 145. (23) Thompson, M. E.; Baxter, S. M.; Bulls, R.; Burger, B. J.; Nolan, M. C.; Santarsiero, B. D.; Schaefer, W. P.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 203. (24) Booij, M.; Deelman, B.-J.; Duchateau, R.; Postma, D. S.; Meetsma, A.; Teuben, J. H. Organometallics 1993, 12, 3531. (25) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51. (26) Sherry, A. E.; Wayland, B. B. J Am. Chem. Soc. 1990, 112, 1259. (27) Wayland, B. B.; Ba, S.; Sherry, A. E. J. Am. Chem. Soc. 1991, 113, 5305. (28) (a) Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1993, 12, 3705. (b) Lee, S. Y.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 5877. (c) With, J.; Horton, A. D. Angew. Chem., Intl. Ed. Engl. 1993, 32, 903. (d) Schaller, C. P.; Cummins, C. C.; Wolczanski, P. T. J. Am. Chem. Soc. 1996, 118, 591. (e) Bennett, J. L.; Wolczanski, P. T. J. Am. Chem. Soc. 1997, 119, 10696. (f) Schaller, C. P.; Wolczanski, P. T. Inorg. Chem. 1993, 32, 131. (g) Schaefer, D. F. II; Wolczanski, P. T. J. Am. Chem. Soc. 1998, 120, 4881. (29) (a) Coles, M. P.; Gibson, V. C.; Clegg, W.; Elsegood, M. R. J.; Porrelli, P. A. J. Chem. Soc., Chem. Commun. 1996, 1963. (b) van der Heijden, H.; Hessen, B. J. Chem. Soc., Chem. Commun. 1995, 145. (c) Cheon, J.; Oogers, D. M.; Girolami, G. S. J. Am. Chem. Soc. 1997, 119, 6804. (d) Adams, C. S.; Legzdins, P.; Tran, E. J. Am. Chem. Soc. 2001, 123, 612. 22 (30) (a) Bailey, B. C.; Fan, H.; Huffman, J. C.; Baik, M.-H.; Mindiola, D. J. I Am. Chem. Soc. 2007, 129, 8781. (b) Bailey, B. C.; Huffman, J. C.; Mindiola, D. J. .I. Am. Chem. Soc. 2007, 129, 5302. (c) Bailey, B. C.; Fan, H.; Baum, E. W.; Huffman, J. C.; Baik, M.-H.; Mindiola, D. J. I Am. Chem. Soc. 2005, 127, 16016. (31) (a) Debad, J. D.; Legzdins, P.; Lumb, S. A.; Batchelor, R. J.; Einstein, F. W. B. I Am. Chem. Soc. 1995, 117, 3288. (b) Debad, J. D.; Legzdins, P.; Lumb, S. A.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1999, 18, 3414. (32) Adams, C. S. C-H Activation of Hydrocarbons by Tungsten Alkylidene and Related Complexes. Ph. D. Thesis, University of British Columbia, Vancouver, BC, October 2001. (33) Wada, K.; Pamplin, C. B.; Legzdins, P. 1 Am. Chem. Soc. 2003, 125, 7035. (34) Dryden, N. H.; Legzdins, P.; Rettig, S. J. Veltheer, J. E. Organometallics 1992, 11,2583. (35) Ng, S. H. K.; Adams, C. S.; Hayton, T. W.; Legzdins, P.; Patrick, B. O. 1 Am. Chem. Soc. 2003, 125, 15210. (36) Fujita-Takayama, C. Unpublished observations. 23 CHAPTER 2 Ortho-Selective C-H Activation of Substituted Benzenes Effected by a Tungsten Alkylidene Complex Without Substituent Coordination 2.1^Introduction * A major goal of researchers working on the field of C-H activation chemistry is to effect the transformation in a regioselective manner. Particularly important from a synthetic point of view is the selective activation of strong C-H bonds in the presence of potentially more reactive functional groups. One of the notable successes in this area has been the activation of aryl C-H bonds ortho to a substituent that is capable of acting as a Lewis base (Scheme 2.1). 1 '2 Scheme 2.1 M The substituent (X) can play one of two roles in these processes. It may first coordinate to the metal center and thereby direct and facilitate the activation to the ortho C-H linkage. Such is the case during the C-H activation of some haloarenes ia ' 2b as well as the well-known Ru(0)-catalyzed "site-directed" addition of the ortho C-H bonds of * Portions of this Chapter have been published. Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P.; Patrick, B. 0. Ortho-Selective C-H Activation of Substituted Benzenes Effected by a Tungsten Alkylidene Complex without Substituent Coordination. Organomtallics 2006, 25, 4215-4225. [Ru] /Y +[Ru] 24 aromatic ketones to olefins developed by Murai and coworkers, a particular example of which is shown in Scheme 2.2. 3 This chelate-assisted mechanism has been supported by a separate DFT study. 4 Scheme 2.2 Alternatively, the substituent X in eq 2.1 may simply stabilize the product complex by coordination to the metal center after the C-H activation process has been effected. Such is the case during the selective addition of the ortho C-H bonds of nitrobenzene and acetophenone to a (PCP)Ir center recently reported by Goldman and coworkers."' In either case, the end result of the transformations summarized in Scheme 2.1 is that X occupies a position in the metal's coordination sphere that may well be needed for subsequent derivatization of the activated arene. Our contributions to this area of chemistry began with the discovery of the ability of Cp*M(NO)(CH2CMe3)2 (2.1) (Cp* = i 5-05Me5) to lose neopentane (CMe4) via a- hydrogen elimination and generate the C-H activating species Cp*W(N0)(=CHCMe3 ) (A) under mildly elevated temperatures. 5 Intermediate A has been demonstrated to react with benzene and alkyl-substituted benzenes to form discernible products, with the 25 regioselectivity between the various aryl positions primarily determined by steric factors. 6 In this chapter we present the results of our investigations of the reactivity between A and a series of mono- and dihalo or pseudohalobenzenes, and we compare these results with related studies conducted previously by the Legzdins group and others. We have established that contrary to previous Legzdins group results,6 A exhibits good selectivity for C-H activation of these substituted benzenes at the ortho position, and that functional groups as weakly basic as a bond or a fluorine atom can serve as the ortho-directing group. Most interestingly, this selectivity is thermodynamic in nature and does not involve coordination of the ortho-directing substituent to the tungsten center. 2.2^Results and Discussion 2.2.1 C-H Activation of Monosubstituted Benzenes Scheme 2.3 summarizes the C-H bond activations that occur when Cp*W(NO)(CH2CMe3)2 (2.1) is thermolyzed in various monosubstituted benzenes. Thus, thermolysis of 2.1 in a monohalobenzene C6H5X (X = F, Cl, or Br) at 70 °C for 40 h results in the formation of the ortho-, meta- and para-activated isomers Cp*W(NO)(CH2CMe3)(C6H4X) (X = F, 2.2a-c; X = Cl, 2.3a-c; X = Br, 2.4a-c) with the ortho-activated isomer being formed in the greatest amount in all cases. There is no evidence for the occurrence of concomitant C-X activations during these transformations. 2 We have previously shown that steric factors play a significant role in determining the regioselectivities of C-H activation of alkylated arenes effected by A.6 26 For example, thermolysis of 2.1 in toluene (PhCH3) results in the formation of the ortho-, meta-, and para-activated isomers in an o:m:p ratio of 1:59:40, in addition to organometallic products (-19%) resulting from the benzylic C-H activation of toluene. Similarly, thermolysis of 2.1 in a, a, a-trifluorotoluene (PhCF 3) affords an o:m:p ratio of 0:65:35. These results demonstrate that a bulky group effectively discourages ortho C-H activation. In the case of the haloarenes, however, A exhibits a preference for ortho C-H activation in spite of the steric hindrance imposed by the halogen substituent. Hence, there must be an electronic factor operative as well during these activations (vide infra). Scheme 2.3  70 °C wi ...... NO _ cme4 PhX FW - NO X Compound X ortho : meta : para 2.2a-c F 97:^2 : 1 2.3a-c CI 75 : 18 : 7 2.4a-c Br 63 : 25 : 12 2.5a-c OMe 87: 7 : 6 2.6a-c C=- CPh 51^: 33 : 16 During these activations by the tungsten complex, fluorobenzene gives excellent regioselectivity (97% ortho), whereas chlorobenzene (75% ortho) and bromobenzene (63% ortho) are less selective in this regard. This trend of F > Cl > Br contrasts with the selectivity exhibited by RPNP)Ir(cyclooctene)] +BF4" (PNP = 2,6-bis-(di-tert- butylphosphinomethyl)pyridine). la The cationic iridium complex displays a pronounced preference for the ortho C-H bonds of bromobenzene, the o:m:p ratio being 70:20:10 27 when the iridium reactant has been completely consumed; prolonged heating of the final reaction mixture at 60 °C results in the quantitative formation of the ortho-activated complex. On the other hand, the iridium complex shows no regioselectivity towards the C-H bonds of fluorobenzene and forms a statistical mixture of the ortho-, meta-, and para-activated isomers. la Thermolysis of 2.1 in anisole also results in the formation of the ortho-, meta-, and para-activated isomers Cp*W(N0)(CH2CMe3)(C61-140Me) (2.5a-c) with excellent selectivity for the ortho-activated isomer 2.5a (87%). It is noteworthy that no organometallic product resulting from C-H activation of the methoxy group is evident in the final reaction mixture. Meanwhile, a C=-C bond can also behave as an ortho- director, le although thermolysis of 2.1 in molten diphenylacetylene results in a slightly more complex mixture, with four organometallic complexes formed in different amounts (Scheme 2.4). The principal product is the ortho-activated isomer Cp*W(N0)(CH2CMe3)(2-C6H4C-CPh) (2.6a, 51%). Two of the other complexes are believed to be the meta- and para-activated isomers on the basis of the chemical shifts and multiplicities of agostic and nonagostic neopentyl methylene proton signals evident in the 1 H NMR spectrum of the crude product mixture (vide infra). However, significant overlapping of characteristic signals in the aryl region prevents definitive structural elucidation of these two complexes by 1 H NMR spectroscopy. These two compounds, as well as complexes 2.2b-c, 2.3b-c, 2.4b-c and 2.5b-c, also appear to decompose on various chromatographic columns. Interestingly, a minor fourth complex can be successfully isolated in 5% yield from the product mixture by chromatography since it A Ph 2.6a-c^2.6d 28 elutes in a narrow orange band ahead of all the other complexes. Crystallization from pentane yields plates, and a preliminary X-ray crystallographic analysis has revealed the identity of this fourth complex to be Cp*W(N0)(1 3 ,11 1 -(Me3C)HC-CPh=CPh-CP11=CPh) (2.6d). Unfortunately, the quality of the X-ray diffraction data is such that a meaningful discussion of the intramolecular metrical parameters of 2.6d is not possible. Nevertheless, the atom connectivity in this compound has been unambiguously established, and it reveals that two diphenylacetylene molecules have been coupled within the coordination sphere of the tungsten center as shown in Scheme 2. Complex 2.6d probably results from the [2+2] cycloaddition of one diphenylacetylene molecule to the W=C alkylidene linkage in transient intermediate A followed by a ring-expansion reaction involving the addition of a second diphenylacetylene molecule, before isomerization to the final allyl-vinyl complex. In any event, the formation of 2.6d establishes that acetylenic C=C bonds are not totally immune from reacting with the W=C alkylidene linkage in A. 7 Scheme 2.4 In comparison, thermolysis of 2.1 in 3-hexyne affords only the coupled product analogous to 2.6d, namely Cp*W(NO)(r1 3 ,1 1 -(Me3 C)HC-CEt=CEt-CEt=CEt) (2.7), while 29 compounds resulting from C-H activations of 3-hexyne are apparently not formed. Even though its formation was apparently quantitative according to NMR spectroscopy, Complex 2.7 was isolated in only 20% yield, because of its high solubility in common organic solvents, and apparent significant decomposition during chromatographic purification. Complex 2.7 has been subjected to a single-crystal, X-ray crystallographic analysis, and its solid-state molecular structure is shown in Figure 2.1. Figure 2.1.^Solid-state molecular structure of Cp*W(N0)(r1 3 ,1 1 -(Me3C)HC-CEt=CEt- CEt=CEt) (2.7) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W1 -N1 = 1.785(4), N1-01 = 1.216(5), WI-Cul = 2.328(4), W1 -C16 = 2.294(4), W1 -C19 = 2.396(4), W1 -C25 = 2.192(4), C11-C16 =- 1.456(6), C16-C19 = 1.408(6), C19-C22 = 1.498(6), C22-C25 = 1.336(6), WI -N1-01 = 170.2(4), C16-C19-C22 = 119.2(3). o-C6H4X2 X= For CI^ )("" -NO *W - NOo A 30 2.2.2 C-H Activation of Disubstituted Benzenes Thermolyses of 2.1 in o-difluorobenzene and o-dichlorobenzene both lead to ortho-selective C-H activation, the principal products being Cp*W(N0)(CH2CMe3)(2,3- C6H3F2) (2.8a) and Cp*W(N0)(CH2CMe3)(2,3-C6H3C12) (2.9a), respectively (Scheme 2.5). The product ratios of 98:2 and 82:18 for 2.8a:28b and 2.9a:2.9b, respectively, are consistent with the regioselectivities observed during the C-H activation of the respective monohalobenzenes (vide supra). Scheme 2.5 a^b ^Compound X^a : b 2.8a-b^F^98 : 2 2.9a-b^CI^82 : 18 Not surprisingly, thermolyses of 2.1 in m-difluorobenzene and m-dichlorobenzene lead to different product ratios (Scheme 2.6). In the case of m-difluorobenzene, the major organometallic product is the ortho-para-activated isomer Cp*W(N0)(CH 2CMe 3)(2,4- C6H3F2) (2.10a, 84%). The steric hindrance provided by the second fluorine atom accounts for the relatively low yield of the ortho-ortho-activated isomer, Cp*W(N0)(CH2CMe3)(2,6-C6H3F2) (2.10c, 16%), which can be separated from the m-C6H4X2 X= F or CI ; NO ,)::::^ ....../: -NO +^-NO +^X X A 31 major product by careful column chromatography on alumina. The meta-meta-activated isomer 2.10b is not present in any detectable amount. The distribution of products from this reaction suggests that the well-known acidity of the ortho protons in fluoroarenes does not play a significant role during these transformations, because if it did, then isomer 2.10c would have been expected to be the major organometallic product. ld Thermolysis of 2.1 in m-dichlorobenzene, on the other hand, also affords the ortho-para- activated isomer, Cp*W(N0)(CH 2CMe3)(2,4-C6H3 C12) (2.11a), as the major product (89%). The other product is the meta-meta-activated isomer, Cp*W(N0)(CH2CMe3)(3,5 -C6H3C12) (2.11b, 11%), while the very hindered ortho-ortho- position of m-dichlorobenzene is not activated at all. For comparison, it may be noted that we have previously shown that the thermolysis of 2.1 in mesitylene results exclusively in benzylic C-H activation products and no aryl C-H activation products. 6 Scheme 2.6 b X a : b : c F 84 : 0 : 16 CI 89 : 11 : 0 a Compound 2.10a-c 2.11a-c Thermolyses of 2.1 in p-disubstituted benzenes have been conducted to determine how the functional groups on the same molecule compare with each other as the ortho- 32 directing group for C-H activations, and they have established that the ortho-directing abilities of the substituents diminish in the order F > OMe > Cl, just as for the monosubstituted benzenes (vide supra). Thus, as shown in Scheme 2.7, thermolysis of 2.1 in p-chlorofluorobenzene produces Cp*W(N0)(CH2CMe3)(C6H3-2-F-5-C1) (2.12a) and Cp*W(N0)(CH2CMe3)(C6H3-2-C1-5-F) (2.12b) in an 85:15 ratio. Similarly, thermolysis of 2.1 in p-fluoroanisole affords Cp*W(N0)(CH2CMe3)(C6H3-2-F-5-OMe) (2.13a) and Cp*W(N0)(CH2CMe3)(C6H3-2-OMe-5-F) (2.13b) in a 71:29 ratio, while thermolysis of 2.1 in p-chloroanisole results in a 77:23 product ratio of the two isomers, Cp*W(N0)(CH2CMe3)(C6H3-2-OMe-5-C1) (2.14a) and Cp*W(N0)(CH2CMe3)(C6H3-2- C1-5-0Me) (2.14b) respectively. Complete separation of the two isomers in each of the two latter reactions (i.e. 2.13a and 2.13b, and 2.14a and 2.14b) can be achieved by careful chromatography on activated alumina. Complexes 2.13a and 2.13b can be identified by their 19F NMR spectra; however, no convenient spectroscopic method (e.g. a 1D selective NOE experiment) has yet been found that differentiates between 2.14a and 2.14b. The identities of the two isomers have thus been inferred from the observed product ratios, as well as from the colors and the solubility properties of the two complexes. All other complexes bearing an o-methoxyphenyl ligand in this study are magenta-purple and are only slightly soluble in n-pentane while all complexes bearing an o-chlorophenyl ligand are red and much more soluble in the same solvent. -NO + p-C6H4XY^....... A Scheme 2.7 33 a^b Compound X^Y^a : b 2.12a-b^F^CI^85 : 15 2.13a-b^F^OMe 71 :29 2.14a-b^OMe CI^77 : 23 2.2.3 Spectroscopic Properties of the C-H Activation Products The i H NMR spectra of all the nitrosyl complexes resulting from aryl C-H activation feature two diastereotopic methylene proton signals, with one signal appearing below 6 = 0 ppm and the other appearing between 6 = 4 to 6 ppm. These signals are much more upfield and downfield, respectively, than where methylene proton signals usually appear. The chemical shifts of these signals and their 1./Hc coupling constants (vide infra) suggest that there are agostic interactions between the tungsten centers and one of the methylene C-H bonds in these compounds. 8 This is a remarkable and unexpected feature regarding the ortho-activated complexes. It is not unreasonable to expect that the ortho halogen atoms in complexes 2.2a, 2.3a or 2.4a, or the methoxy oxygen atom in 2.5a, or the carbon-carbon triple bond in 2.6a would be coordinated to the formally 16-electron metal center in these products. However, the 1 H NMR data indicate that these Lewis-basic groups are not coordinated to tungsten in their respective 34 complexes, otherwise the metal centers would have no need to engage in agostic interactions with methylene C-H bonds to acquire additional electron density. For each of the complexes containing an o-fluorophenyl ligand, the agostic methylene proton signal appears as a doublet of doublets, the coupling constants being in the range of 11 Hz and 6 Hz respectively. While the larger coupling is due to 2JHH , the smaller coupling can only be attributed to long-range interaction between this proton and the ortho fluorine atom. Such long-range coupling between an aryl ortho-fluoro group and an alkyl proton is rare, but not unprecedented. 941 Interestingly, the non-agostic methylene proton does not couple to the fluorine atom at all. Hence, the long-range coupling observed during this study may actually be occurring through space." For comparison, the 1 H NMR spectrum of [Et 4Nr[Cp*W(N0)(CH2CMe 3)(CN)(o-C 6H4F)] - ([Et4N]+ [15f, vide infra), in which the o-fluorophenyl group and the neopentyl group are trans to each other in the tungsten's coordination sphere, does not exhibit such H-F coupling. Long-range H-F coupling has been found to be regiospecific in certain cases, particularly when the o-fluorophenyl group is not freely rotating.' ° The phenomenon of long-range H-F coupling has been very useful for structure elucidation in a few cases. For example, complex 2.10c can be unambiguously identified by the appearance of its agostic methylene proton signal in its I li NMR spectrum, namely a doublet of triplets reflecting coupling of the agostic proton to the other methylene proton as well as to two apparently equivalent ortho fluorine atoms. In a similar manner complexes 2.12a and 2.13a can be readily differentiated from their isomers by the 35 appearance of the agostic methylene proton signals, namely doublets of doublets for 2.12a and 2.13a versus doublets for 2.12b and 2.13b. Gated- 13C NMR spectra have been recorded for several of the compounds, and they display features that are consistent with their 1 H NMR data and their proposed molecular structures. Specifically, the methylene carbon signals in the proton-coupled spectra appear as doublets of doublets, with the magnitude of the two 1./cH coupling constants being in the range of 120 Hz and 90 Hz, respectively. We have previously established that such coupling constants are diagnostic of agostic C-H interactions with the metal centers in complexes of this type. 8 Products obtained from the thermolysis of 2.1 in fluorinated arenes have also been characterized by 19F NMR spectroscopy. Typically the signals due to the fluorine atoms that are ortho to W appear between 0 to — 20 ppm (with reference to CF 3 COOH) while the signals due to the fluorine atoms that are meta or para to W occur between —40 to —50 ppm. The only exception to this generalization is the 19F NMR spectrum of compound 2.8a that exhibits signals attributable to the ortho and meta fluorine atoms at —31.6 and —62.8 ppm, respectively. Such an upfield shift is commonly observed for compounds containing mutually ortho fluoro groups, as in the parent o-difluorobenzene and other o-difluorosubstituted arenes. Overall, the 19F NMR data for the new complexes synthesized during the current investigation are consistent with their structural assignments. 36 2.2.4 X-Ray Crystallographic Analyses of Selected C-H Activation Products In order to establish the metrical parameters of the solid-state molecular structures of these types of alkyl aryl complexes, we have performed single-crystal X-ray crystallographic analyses on several representative compounds prepared during this study. The solid-state molecular structures of piano-stool complexes 2.2a and 2.5a are very similar, and they are shown in Figures 2.2 and 2.3, respectively. Both the fluoro and methoxy groups are located trans to the nitrosyl ligand (as opposed to the neopentyl ligand) in an orientation that brings these groups into the vicinity of the low-energy vacant orbital that is situated between the W-alkyl and W-aryl linkages in such 16- electron Cp'W(NO)(alkyl)(aryl) compounds (Cp' = Cp or Cp*). 12 However, the W-F and W-0 distances in the two complexes are 3.222 and 3.110 A, respectively, significantly longer than typical W-0 and W-F bonding distances found in other crystallographically characterized compounds. 13 Meanwhile, the neopentyl W-C-C angles of the two complexes are relatively wide at 130.9(2) and 129.7(2) °, respectively, and are indicative of agostic interactions between the tungsten centers and a methylene proton on the neopentyl ligands. 8 Complexes containing halobenzene ligands bound to the metal centers via the halogens have been previously described in the literature. 2b ' 14 It is thus somewhat surprising that the electron-deficient metal centers in 2.2a and 2.5a interact with a C-H bond rather than the lone pairs on the F or 0 atoms in order to acquire additional electron density. Likewise, the C=C bond in 2.6a (Figure 2.4) does not 37 Figure 2.2. Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(0-C6H4F) (2.2a) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W1-N1 = 1.775(2), W1-C7 = 2.101(3), W1-C1 = 2.162(3), W1-Fl = 3.222, N1-01 = 1.228(3), Wl-N1-01 = 169.4(2), Wl-C7-C8 = 130.9(2), W1-C1-C2 = 121.5(2). 38 Figure 2.3. Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(o-C6H40Me) (2.5a) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W1-N1 = 1.765(3), Wl-C8 = 2.122(4), W1-C1 = 2.149(3), W1-01 = 3.110, N1-02 = 1.223(4), Wi-N1-02 = 171.6(3), Wl-C8-C9 = 129.7(2), Wl-C1-C2 = 119.7(2), C2-01-C7 = 117.6(3). 39 Figure 2.4. Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(o- C6H4CF=CC6H5) (2.6a) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W1-N1 = 1.767(3), Wl-C15 = 2.118(4), W1- C1 = 2.156(4), Wl-C7 = 3.428, W1-C8 = 4.141, N1-01 = 1.225(5), W1-N1-01 = 170.3(3), W1-C15-C16 = 129.6(3), W1-C1-C6 = 123.5(3), C6-C7-C8 = 173.8(4), C7-C8- C9 = 175.9(4). 40 interact with the W center, the W(1)-C(7) and W(1)-C(8) distances being 3.428 and 4.141 A, respectively. The fact that the phenylethynyl group is slightly bent away from W (C(6)-C(7)-C(8) = 173.8(4) ° , C(7)-C(8)-C(9) = 176.0(4)°) is likely a manifestation of steric congestion around the metal center. Finally, in the solid-state molecular structure of complex 2.10c (Figure 2.5), the fluorine trans to the nitrosyl group (i.e. F(1)) is closer to the W center than is the other fluorine (3.186 vs. 3.398 A), but these W-F distances are still too long for any bonding interactions to be considered. Figure 2.5. Solid-state molecular structure of Cp*W(N0)(CH2CMe3)(2,6-C6H3F2) (2.10c) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W1-N1 = 1.7686(14), W1 -C7 = 2.1002(17), Wl-C1 = 2.1657(17), W1-Fl = 3.186, Wl-F2 = 3.398, N1-01 = 1.2280(19), W1-N1-01 = 169.27(13), W1- C7-C8 = 131.50(12), Wl-C1-C2 = 120.79(13), Wl-C1-C6 = 127.40(13). 41 42 2.2.5 Mechanistic Studies The lack of coordination of substituent lone pairs to tungsten in the C-H activated complexes, as evidenced by their NMR data and solid-state molecular structures, combined with the observed trend of ortho-directing ability not following the presumed Lewis basicity of the substituents, leads us to question whether pre-coordination of the substituted arenes via their heteroatoms to the metal centers is necessary for the subsequent ortho C-H activations. Consequently, the early stages of the thermolysis of 2.1 in chlorobenzene have been monitored by 1 H NMR spectroscopy in order to acquire some mechanistic insights. Figure 2.6 shows the change in product ratios during the first 8 h of the thermolysis of 2.1 in chlorobenzene in a sealed J. Young NMR tube at 70 °C. After just 1 h, the o:m:p ratio is 0.8:2:1, thereby indicating initial selectivity against the ortho isomer. However, the relative amount of the ortho isomer gradually increases throughout the 8-h period while the amounts of the meta and para isomers show signs of leveling off. 15 These observations indicate that the selectivity of the alkylidene intermediate A for forming the ortho-activated isomer is thermodynamic rather than kinetic in nature. The meta and para isomers are formed first kinetically by activations of the most accessible C-H bonds,6 and they then undergo conversion to the thermodynamically more stable ortho form. In these kinetic and thermodynamic aspects this system resembles Goldman's (PCP)Ir-based system which also selectively generates chelated ortho-activated acetophenone and nitrobenzene complexes via intramolecular isomerizations. lb In other experimental and DFT studies, it has been shown that a fluoro substituent considerably strengthens the ortho-M-C linkage in metal-aryl complexes. 16,17 43 This observation has been used to explain the ortho-selectivity of C-Cl activation on 2,4- dichloro- l -fluorobenzene by Cp*Re(C0)3. 1 8 Our ortho-selective C-H activations involve a combination of both steric and electronic factors. The decreasing ortho-selectivity (i.e. F > OMe > Cl > Br > C CPh) does correlate with increasing substituent size, but this cannot be the only factor operative since the corresponding CH3-substituted phenyl complexes do not undergo a similar conversion to the ortho-isomer during the C-H activation of toluene. 6" 5 Hence, the electron-withdrawing and donating properties of the substituents must also influence the outcomes of these transformations even though no straightforward correlation is immediately evident. Isomerization among toluene C-H activation products has been studied in our laboratory, 15 and labeling experiments suggested that the isomerization process occurs via the formation of an arene-alkylidene complex. Meanwhile, the naked 16-e alkylidene intermediate A is not reformed, since no crossover occurs when the chlorobenzene C-H activation products 2.3a-c are heated in benzene. Nevertheless, more work is required to establish definitively why the ortho isomers are the thermodynamically most stable entities for all of the substrates that are studied. •100 ^ 90 -^• 80 - 70 .—. ^- 0 c O 60tocaL 46 cuc.) 50 -c 0o => 40- -iii I;cc 30 - 20 - • • • • • • ■ ■^IP■^•■^•■^• 44 • 1 • 3a ■ 3b • 3c 10 -^■^• •^• • •^•^ • ■ aa 0^ 0 2^4^6^8 Time (h) Figure 2.6. The relative amounts of the three isomers of Cp*W(N0)(CH2CMe3)(C6H4C1) (2.3a-c) during the first 8 h of thermolysis of Cp*W(NO)(CH2CMe3)2 (2.1) in chlorobenzene. 2.2.6 Representative Reactivity of C-H Activated Complex 2.2a Unlike other halobenzene-C-H activating systems, the tungsten alkylidene complex A forms C-H activated compounds that are coordinatively and electronically 45 unsaturated. As a result, they react readily with Lewis bases. For example, treatment of complex 2.2a with tetraethylammonium cyanide (Et 4NCN) and CO produces [Et41\1] ± [Cp*W(N0)(CH2CMe3)(CN)(0-C6H4F)T ([Et4M + [2.15] -) and Cp *W(N0)(1 2- C(=0)CH2CMe3)(0-C6H4F) (2.16), respectively. By analogy to related systems, complex 2.16 is probably formed by initial coordination of CO to the metal center followed by its migratory insertion into the W-CH2CMe3 linkage. 19 '2° The identities of both complexes have been confirmed by conventional spectroscopic methods, and the solid-state molecular structure of 2.16 (Figure 2.7) has been established by a single-crystal X-ray crystallographic analysis. 46 C9 Figure 2.7. Solid state molecular structure of Cp*W(NO)(r1 2-C(=0)CH2CMe3)(o- C6H4F) (2.16) with 50% probability thermal ellipsoids shown and hydrogen atoms having been omitted for clarity. Selected interatomic distances (A) and angles (deg): W1-N1 = 1.788(4), W1-C17 = 2.067(4), Wl-C11 = 2.211(9), W1-02 = 2.219(3), N1-01 = 1.233(5), C17-02 = 1.248(5), C17-C18 = 1.504(6), WI-N1-01 = 168.4(3), W1-C11-C12 = 120.4(5), W1-C17-C18 = 157.3(4), Wi-C17-02 = 79.9(3), W1-02-C17 = 66.5(2), C17-W1-N1 — 95.05(17). 47 2.3^Conclusion We have demonstrated that the C-H activating abilities of the 16-electron tungsten alkylidene intermediate, Cp*W(NO)(=CHCMe3) (A), are not hampered by Lewis-basic substituents on benzenes. Hence, A can be employed to activate ortho C-H bonds of halobenzenes (especially fluorobenzenes) and methoxybenzenes with good selectivity — an important first step in the utilization of Cp*W(NO)-based complexes in organic synthesis. The ortho-directing ability of the benzene functional groups decreases in the order F > OMe > Cl > Br > C.=-CPh, and, to the best of our knowledge, their ability to do so without coordination to the metal center is without precedent. We have also established that the ortho-selectivity is thermodynamic in nature, a feature exhibited by a few other C-H activating systems, 1 'b and it reflects a juxtaposition of steric and electronic effects imparted by the substituents. The fact that the organometallic complexes formed by the C-H activations are both electronically and coordinatively unsaturated suggests that they should exhibit some interesting and useful derivatization chemistry. Studies designed to functionalize and release the activated organic fragments from the metal centers in a well-defined and productive manner are currently in progress. 48 2.4^Experimental Procedures 2.4.1 General Considerations All reactions and subsequent manipulations involving organometallic reagents were performed under anaerobic and anhydrous conditions, either at a vacuum-nitrogen dual manifold or in an inert-atmosphere dry box. General procedures routinely employed in these laboratories have been described in detail elsewhere. 5 '21 Hexamethyldisiloxane (HMDS), pentane, hexanes, benzene-d6, diethyl ether, and tetrahydrofuran (THF) were all dried over sodium/benzophenone ketyl and were freshly distilled prior to use. Haloarenes, methoxyhaloarenes, anisole, and nitromethane were all purchased from Aldrich, and were dried over, distilled from, and stored over CaH 2 in resealable glass vessels. Acetone-d6 was dried over and distilled from Drierite and was stored over 4 A molecular sieves in a resealable glass vessel. Diphenylacetylene was recrystallized from ethanol and dried in vacuo prior to use. Cp*W(NO)(CH2CMe 3)2 (1) was prepared according to the published procedure, but the compound was recrystallized in several batches from HMDS instead of pentane in order to maximize the amount of product recovered from crystallization. 5 All other chemicals were purchased from Aldrich and were used as received. Unless specified otherwise, recrystallizations of newly synthesized complexes were effected overnight at -30 °C. All IR samples were prepared as Nujol mulls sandwiched between NaCl plates, and their spectra were recorded on a Thermo Nicolet Model 4700 FT-IR spectrometer. 49 NMR spectra were recorded at room temperature on Bruker AV-300 or AV-400 instruments, and all chemical shifts and coupling constants are reported in ppm and in Hertz, respectively. 1 H NMR spectra were referenced to the residual protio isotopomer present in C6D 6 (7.16 ppm) or acetone-d 6 (2.04 ppm). 13 C NMR spectra were referenced to C6D6 (128 ppm), and 19F NMR spectra were referenced internally to CF 3 COOH (0 ppm). Elemental and ELMS analyses of the new complexes were performed by Mr. M. Lakha and Mr. M. Lapawa, respectively, in the Department of Chemistry at UBC. 2.4.2 Representative Procedure for Effecting Preparative Thermolyses of Cp*W(N0)(CH2CMe3)2 (2.1) in Organic Substrates Unless noted otherwise, the following general procedure was used to prepare new compounds via thermolysis of Cp*W(N0)(CH2CMe3)2 (2.1). A thick-walled, resealable vessel was charged with the specified amount of 2.1, a magnetic stir bar, and approximately 2-3 mL of the organic substrate. The reaction mixture was subjected to three freeze-pump-thaw cycles before it was heated for 40 h at 70 °C in an oil bath. The volatile organics were then removed in vacuo, and the dried residue was redissolved in C6D6 and was analyzed by IR and NMR spectroscopy. The NMR solvent was removed under reduced pressure, and the crude product was worked up as described in the following paragraphs. Reported yields are not optimized. Minor organometallic products that could not be isolated were characterized by their signals in the aryl region of the 1 H NMR spectrum of the final reaction mixture. In addition, average product ratios were established by integration of appropriate signals in this spectrum, usually the 50 upfield neopentyl methylene proton resonances, or in a few cases the downfield methylene proton resonances when the former signals were inadequately resolved. 1D selective COSY NMR experiments were performed on occasion to locate the aryl proton resonances of some minor products. 2.4.3 Preparation of Cp*W(NO)(CH2CMe3)(C6H 4F) (2.2a-c) Complexes 2a-c were prepared in a ratio of 97:2:1 via the thermolysis of 2.1 (100.0 mg, 0.204 mmol) in fluorobenzene. Complex 2.2a (80 mg, 77%) was obtained as dark-red square plates by crystallization of the crude product mixture from HMDS in three crops. 2.2a: IR (cm -1 ) v(NO) 1592 (s). 1 H NMR (400 MHz, C6D6) 8 —2.96 (dd, 2.114H = 11.0 Hz, 5^= 6.0 Hz, 1H, CH,j,,,H), 1.25 (s, 9H, CMe3), 1.62 (s, 15H, C5Me5), 5.46 (d, 2•411-1= 11.0 Hz, 1H, CHantiH), 6.87 (m, 1H, Ar H), 6.97 (overlapping m, 2H, Ar H), 8.32 (m, 1H, Ar H). 19F { 1 1-1} NMR (282 MHz, C6D6) 8 —5.6. MS (LREI, m/z, probe temperature 100 °C) 515 [M4 ], 458 [M+—CMe3], 444 [M+—CH2CMe3]. Anal. Calcd for C21H30FNOW: C 48.95, H 5.87, N 2.72. Found: C 48.83, H 5.80, N 2.63. 2.2b: 1 1-1 NMR (400 MHz, C6D6) 8 —2.34 (d, 2JHH = 11.0 Hz, 1H, ClisynE1), 1.48 (s, 15H, C5Me5), 4.78 (d, 2JHH = 11.0 Hz, 1H, CI-lanai), 6.75 (m, 1H, Ar H), 7.04 (m, 1H, Ar H), 7.43 (m, 1H, Ar H), 7.54 (m, 1H, Ar H). The signal due to the neopentyl methyl proton was probably obscured by the corresponding signal of 2.2a. 51 2.2c: 1 H NMR (400 MHz, C6D6) 8 —2.16 (d, 2JHH= 11.0 Hz, 1H, CI-Isynfl), 1.50 (s, 15H, C5Me5), 4.50 (d, 2JHH = 11.0 Hz, 1H, CI I antill), 7.59 (m, 2H, Ar H). Again, the signal due to the neopentyl methyl proton of this complex was probably obscured by the corresponding signal of 2.2a. The remaining aryl proton signal expected for this complex was also obscured. 2.4.4 Preparation of Cp*W(NO)(CH2CMe3)(C6H4C1) (2.3a-c) Complexes 2.3a-c were prepared in a ratio of 75:17:8 via the thermolysis of 2.1 (100.0 mg, 0.204 mmol) in chlorobenzene. The dried crude product mixture was redissolved in a minimum of pentane and was transferred to the top of a column (1 x 3 cm) of neutral activated alumina I made up in pentane and supported on a medium- porosity frit. A red band containing 2.3a was eluted from the column with 1:1 ether/pentane while complexes 2.3b and 2.3c apparently decomposed on the column. The solvent was removed from the eluate in vacuo to obtain a red microcrystalline residue. Dark red rods of 2.3a (65 mg, 60%) were obtained by recrystallization of this residue from 1:1 pentane/HMDS in two crops. 2.3a: IR (cm 1 )v(NO) 1589 (s). 1 H NMR (400 MHz, C6D6) 6 —2.48 (d, 2JHH = 11.0 Hz, 1H, CI-1.9„,H), 1.28 (s, 9H, CMe3), 1.61 (s, 15H, C 5Me5), 5.43 (d, 2JHH = 11.0 Hz, 1H, CHant1f1), 6.84 (ddd, 1H, Ar H), 6.98 (ddd, 1H, Ar H), 7.26 (dd, 3JHH = 7.9Hz, 4JHH = 0.8Hz, 1H, Ar H), 8.26 (br d, 3JHH = 6.2 Hz, 1H, Ar H). 13 C { 1 11} NMR (100 MHz, C6D6) 52 6 9.5 (C5Me5), 33.2 (CH2CMe3), 41.8 (CH2CMe 3), 110.6 (C5Me5), 125.8 (Ar C), 128.3 (Ar C), 128.6 (Ar C), 135.8 (CH2CMe3), 138.7 (C1C ipso), 141.7 (Ar C), 178.2 (WCipso). MS (LREI, m/z, probe temperature 100 °C) 531 [Mt], 474 [Mt—CMe3], 460 [Mt -CH2CMe3]. Anal. Calcd for C21H30C1NOW: C 47.43, H 6.09, N 2.63. Found: C 47.33, H 6.10, N 2.53. 2.3b: 1 H NMR (400 MHz, C6D6) 6 —2.43 (d, 2JHH = 11.0 Hz, 1H, CH,),„H), 1.23 (s, 9H, CMe3), 1.47 (s, 15H, C 5Me5), 4.82 (d, 2JHH = 11.0 Hz, 1H, CHant/1-1), 6.93 (t, 1H, Ar H), 7.07 (m, 1H, Ar H), 7.58 (d, 1H, Ar H), 7.78 (br s, 1H, Ar H). 2.3c: 1 H NMR (400 MHz, C6D6) 6 —2.31 (d, 2JHH = 11.0 Hz, 1H, ClisynH), 1.26 (s, 9H, CMe3), 1.48 (s, 15H, C5Me 5), 4.64 (d, 2JHH= 11.0 Hz, 1H, CHantif1), 7.17 (obscured, 2H, Ar H), 7.50 (d, 3JHH = 8.0 Hz, 2H, Ar H). 2.4.5 Preparation of Cp*W(NO)(CH2CMe3)(C6H4Br) (2.4a-c) This reaction was performed and worked up in a manner identical to that described in the preceding section for the thermolysis of 2.1 in chlorobenzene. Complex 2.4a was isolated as dark red rods (57 mg, 46%) by crystallization of the chromatographed product from 1:1 pentane/HMDS solutions in three crops. 2.4a: IR (cm -1 ) v(NO) 1596 (s). 1 H NMR (400 MHz, C6D6) 8 —2.01 (br, 1H, CI-IsynH), 1.28 (s, 9H, CMe3), 1.63 (s, 15H, C5Me5), 5.37 (d, 2JHH = 10.8 Hz, 1H, CHant,H), 53 6.72 (ddd, 1H, Ar H), 7.00 (ddd, 1H, Ar H), 7.48 (dd, 3JHH = 7.8 Hz, 4./HH = 1.0 Hz, 1H, Ar H), 8.21 (br d, 1H, Ar H). 13CeEll NMR (100 MHz, C6D6) S 10.1 (C5Me5), 33.7 (CH2CMe3), 42.3 (CH2CMe3), 111.0 (C5Me5), 113.0 (Ar C), 126.4 (Ar C), 129.0 (Ar C), 132.0, (Ar C), 136.0 (CH2CMe3), 142.7 (Ar C), 182.7 (WCip so). MS (LREI, m/z, probe temperature 100 °C) 575 [Mt], 518 [Mt—CMe3]. Anal. Calcd for C21H30BrNOW: C 43.77, H 5.25, N 2.43. Found: C 43.83, H 5.11, N 2.57. 2.4b 'H NMR (400 MHz, C6D6): 8 —2.46 (d, 2./HH = 11.2 Hz, 1H, Cli„„,H), 1.21 (s, 9H, CMe3), 1.48 (s, 15H, C 5Me5), 4.83 (d, 2JHH= 11.2 Hz, 1H, CHantiH), 6.87 (t, 1H, Ar H), 7.20 (m, 1H, Ar H), 7.64 (d, 1H, Ar H), 7.91 (s, 1H, Ar H). 2.4c: 1 H NMR (400 MHz, C6D6) 8 —2.36 (d, 2JHH = 11.2 Hz, 1H, CI-Isynfl), 1.25 (s, 9H, CMe3), 1.49 (s, 15H, C 5Me5), 4.68 (d, 2JHH= 11.2 Hz, 1H, Cflant,H), 7.31 (d, 3JHH = 8.0 Hz, 2H, Ar H), 7.42 (d, 3JHH = 8.0 Hz, 2H, Ar H). 2.4.6 Preparation of Cp*W(NO)(CH2CMe3)(C6H4OMe) (2.5a-c) Complexes 2.5a-c were prepared via thermolysis of 2.1 (90.0 mg, 0.183 mmol) in anisole. Complex 2.5a (72 mg, 70%) was obtained as purple diamond-shaped plates by crystallization of the final product mixture from an ether/HMDS bilayer in three crops. 2.5a: IR (cm') v(NO) 1564 (s). 'H NMR (400 MHz, C6D6) 8 —2.66 (d, 2JHH = 11.8 Hz, 1H, CHsy„H), 1.33 (s, 9H, CMe3), 1.62 (s, 15H, C5Me5), 3.14 (s, 3H, OMe), 4.90 54 (d, 24-1H = 11.8 Hz, 1H, CHant/H), 6.54 (ddd, 1H, Ar H), 6.97 (ddd, 1H, Ar H), 7.14 (dd, 3JHH = 7.9Hz, 4JHH = 0.8Hz, 1H, Ar H), 8.47 (dd, 3JHH = 8.0 Hz, 4JHH = 0.8Hz, 1H, Ar H). 13C { 1 H} NMR (100 MHz, C6D6) 6 9.9 (C5Me5), 33.9 (CH2CMe3), 41.0 (CH2CMe3), 54.1 (OMe), 109.3 (Ar C), 110.6 (C5Me5), 121.8 (Ar C), 129.2 (CH2CMe3), 141.3 (Ar C), 135.8 (CH2CMe3), 160.0 (Me0C,p,o), 169.3 (WC,p,o). MS (LREI, m/z, probe temperature 100 °C) 527 [Mt], 470 [Mt—CMe3]. Anal. Calcd for C22H33NO2W: C 50.11, H 6.31, N 2.66. Found: C 50.33, H 6.17, N 2.73. 2.5b: 1 H NMR (400 MHz, C6D6) 6 —2.43 (d, 2JHH = 11.0 Hz, 1H, CHsynt1), 1.23 (s, 9H, CMe3), 1.47 (s, 15H, C 5Me5), 4.82 (d, 2JHH= 11.0 Hz, 1H, CHantiH), 6.93 (t, 1H, Ar H), 7.07 (m, 1H, Ar H), 7.58 (d, 1H, Ar H), 7.78 (br s, 1H, Ar H). 2.5c: 1 H NMR (400 MHz, C6D6) 6 —2.31 (d, 2JHH = 11.0 Hz, 1H, CI-1.9„,H), 1.26 (s, 9H, CMe3), 1.48 (s, 15H, C5Me5), 4.64 (d, 2JHH= 11.0 Hz, 1H, CHantiH), 7.17 (obscured, 2H, Ar H), 7.50 (d, 3JHH = 8.0 Hz, 2H, Ar H). 2.4.7 Preparation of Cp*W(N0)(CH2CMe3)(o-C6H4CaCC6H5) (2.6a) and Cp*W(N0)(11 3,1 1 -(CMe3)HCCPh=CPh-CPh=CPh) (2.6d) A resealable vessel was charged with 2.1 (89.0 mg, 0.181 mmol), diphenylacetylene (400.0 mg, 2.24 mmol) and a magnetic stir bar. The vessel was evacuated before being heated in a 70 °C oil bath for 40 h. The volatiles were removed from the final reaction mixture in vacuo, and the remaining residue was dissolved in a 55 minimum amount of pentane. The pentane solution was transferred to the top of a column (2 x 8 cm) of neutral activated alumina I made up in pentane and supported on a medium-porosity frit. The column was washed with pentane (-300 mL) until no white residue (diphenylacetylene) formed when a drop of the eluate was allowed to evaporate. The column was then eluted with 1:4 ether/pentane, whereupon an orange band eluted ahead of a red band. The orange band was collected, and the solvent was removed from it in vacuo. Compound 2.6d (4 mg, 3% based on tungsten) was obtained as orange irregularly shaped plates by recrystallization of the orange residue from pentane. Because of the low yield, only IR and 1 H NMR data were obtained for this compound. After the orange band had been collected, the eluant composition was changed to 1:1 ether/pentane. The red band was next eluted and collected, and the eluate was taken to dryness in vacuo to obtain a red-brown residue. This residue was washed with cold pentane (3 x 5mL) and was redissolved in a minimum of diethyl ether. Pentane was carefully layered on top of this solution, and storage of this mixture overnight in a freezer at -30 °C resulted in the deposition of dark purple diamond-shaped crystals of 2.6a (45 mg, 42%). 2.6a: IR (cm 1 )v(NO) 1568 (s). 1 H NMR (400 MHz, C6D6) 6 —2.24 (br d, 2Airr= 10.6 Hz, 1H, ClisynE1), 1.33 (s, 9H, CMe3), 1.61 (s, 15H, C5Me5), 5.59 (d, 24-1H = 11.0 Hz, 1H, CHantili), 6.95-7.13 (m, 5H, Ar H), 7.51 (br d, 2H, Ar H), 7.67 (br d, 1H, Ar H), 8.34 (br d, 1H, Ar H). 13C { 1 1-1} NMR (100 MHz, C6D6) 6 10.1 (C5Me5), 33.7 (CH2CMe3), 42.4 (CH2CMe3), 95.0 (C=C), 95.9 (CC), 110.9 (C5Me5), 126.9 (Ar C), 128.6 (Ar C), 56 131.7 (Ar C), 133.4 (Ar C), 137.9 (CH2CMe3), 140.6 (Ar C), 185.6 (WCip so). Other aryl carbon signals are probably obscured by the C6D 6 signal. MS (LREI, m/z, probe temperature 100 °C) 597 [M+], 540 [M+—CMe3], 526 [M+—CH2CMe3]. Anal. Calcd for C29H35NOW: C 58.30, H 5.91, N 2.34. Found: C 58.31, H 5.82, N 2.53. 2.6d: IR (cm') v(NO) 1563 (s). 1 H NMR (400 MHz, C6D6): 6 1.21 (s, 9H, CMe 3), 1.39 (s, 15H, C5Me5), 3.76 (s, Me3CCH), 6.60 — 8.39 (m, 20H, Ar H). 2.4.8 Preparation of Cp*W(N0)(1 3, i l -(Me3C)HC-CEt=CEt-CEt=CEt) (2.7) Complex 2.7 was the sole organometallic product formed during the thermolysis of 2.1 (98 mg, 2.0 mmol) in 3-hexyne. The final product mixture was taken to dryness, the residue was redissolved in a minimum of pentane, and this dark brown solution was transferred to the top of a neutral, activated alumina I column (1 x 3 cm) supported on a medium-porosity frit. Elution of the column with 1:5 ether/pentane led to the development of an orange band which was collected. The solvents were removed from the eluate in vacuo, and the residue was redissolved in a minimum of pentane. This pentane solution was stored overnight at —30 °C to induce the deposition of large orange rectangular prisms of 2.7 (25 mg, 22% yield). 2.7: IR (cm -1 ) v(NO) 1583 (s). 'H NMR (400 MHz, C6D6) 8 1.10 (t, 3H, CH2CH3), 1.12 (t, 3H, CH2CH3), 1.14 (t, 3H, CH2CH3), 1.32 (s, 9H, CMe3), 1.48 (m, 1H, CH2), 1.63 (m, 1H, CH2) 1.68 (s, 15H, C5Me5), 2.00 (m, 1H, CH2), 2.25 (m, 1H, CH2), 2.30 (m, 1H, 57 CH2), 2.35 (s, 1H, allyl CH), 2.96 (m, 2H, CH2), 3.24 (m, 1H, CH2). 13C^NMR (100 MHz, C6D6) 6 10.5 (C5Me5), 13.9 (CH2CH3), 14.9 (CH2CH3), 20.0 (CH2CH3), 20.7 (CH2CH3), 26.6 (CH2CH3), 26.7 (CH2CH3), 28.0 (CH2CH3), 28.7 (CH2CH3), 34.4 (CH2CMe3), 36.6 82.1 (CH(CMe3)), 83.4 (ally! C), 106.3 (C5Me5), 130.6 (ally! C), 143.8 (vinyl C), 159.2 (vinyl C). MS (LREI, m/z, probe temperature 100 °C) 583 [M+). Anal. Calcd for C24145NOW: C 55.58, H 7.77, N 2.40. Found: C 55.77, H 7.67, N 2.50. 2.4.9 Preparation^of^Cp*W(N0)(CH2CMe3)(C6H3-2,3-F2)^(2.8a)^and Cp*W(N0)(CH2CMe3)(C6H3-3,4-F2) (2.8b) Complexes 2.8a and 2.8b were prepared via thermolysis of 2.1 (100.0 mg, 0.204 mmol) in o-difluorobenzene. Complex 2.8a was isolated as dark-red square plates (80 mg, 74%) by crystallization of the dried final product mixture from 1:1 pentane/HMDS in two crops. 2.8a IR (cm -1 ) v(NO) 1596 (s). 1 HNMR (400 MHz, C6D6): 5 —3.17 (dd, 241x = 10.8 Hz, 5JHF = 6.2 Hz, 1H, C1-49,,H), 1.22 (s, 9H, CMe3), 1.57 (s, 15H, C5Me5), 5.66 (d, 2 JHH = 10.8 Hz, 1H, CHannH), 6.44 (m, 2H, Ar H), 7.88 (m, 1H, Ar H). 19F{ 1 1-1} NMR (282 MHz, C6D6) 5 —33.3, —62.1. MS (LREI, m/z, probe temperature 100 °C) 533 [Mt], 476 [M+—CMe3]. Anal. Calcd for C21H29F2NOW: C 47.29, H 5.48, N 2.63. Found: C 47.44, H 5.80, N 2.67. 58 2.8b: 'H NMR (400 MHz, C6D6) 8 —2.46 (d, %u= 10.8 Hz, 1H, Clisyn1-1), 1.46 (s, 15H, C5Me5), 4.77 (d, 2JHH = 11.0 Hz, 1H, CHantill), 7.22 (m, 1H, Ar H), 7.65 (m, 1H, Ar H). The neopentyl methyl proton signal and one aryl proton signal were probably obscured by the signals of 2.8a. 2.4.10 Preparation^of^Cp*W(NO)(CH2CMe3)(C6113-2,3-C12)^(2.9a)^and Cp*W(NO)(CH2CMe3)(C6H3-3,4-C12) (2.9b) Complexes 2.9a and 2.9b were prepared via thermolysis of 2.1 (91.0 mg, 0.185 mmol) in o-dichlorobenzene. At the end of the 40-h reaction period, the vessel was wrapped in aluminum foil, and o-dichlorobenzene (b. p. 180 °C) was removed in vacuo at 60 °C. The dried product mixture was redissolved in a minimum of pentane, and the pentane solution was transferred to the top of a neutral activated alumina I column (1 x 3 cm) made up in pentane and supported on a medium-porosity fit. The column was eluted with 1:1 ether/pentane whereupon a red band developed. The band was eluted and collected, and the solvent was removed from the eluate to obtain a red microcrystalline powder. Compound 9a was obtained as red plates (65 mg, 62%, 2 crops) by recrystallization of this powder from pentane. 2.9a: IR (cm -1 ) v(NO) 1580 (s). 'H NMR (400 MHz, C6D6) 8 —2.46 (d, ZJHH = 11.1 Hz, 1H, CHsy,,H), 1.32 (s, 9H, CMe3), 1.62 (s, 15H, C5Me5), 5.52 (d, 2JHH = 11.1 Hz, 1H, CHant,H), 6.77 (t, 1H, 3JHH = 7.9 Hz, Ar H), 7.06 (dd, 3JHH = 7.9Hz, 4JHH = 1.0 Hz, 1H, Ar H), 8.04 (dd, 3JHH = 7.9 Hz, 4JHH = 1.0 Hz, 1H, Ar H). 13C { I fI} NMR (100 MHz, 59 C6D6) 6 9.9 (C5Me5), 33.5 (CH2CMe3), 42.4 (CH2CMe3), 111.2 (C5Me5), 129.1 (Ar C), 130.8 (Ar C), 132.7 (Ar C), 133.4 (CH2CMe3), 139.9 (Ar C), 181.0 (WC ips0). Other aryl carbon signals were not observed. MS (LREI, m/z, probe temperature 100 °C) 565 [Mt], 508 [Mt—CMe3]. Anal Calcd for C21H29C12NOW: C 44.54, H 5.16, N 2.47. Found: C 44.32, H 5.07, N 2.43. 2.9b: 1 H NMR (400 MHz, C6D6) 6 —2.54 (d, 2JHH= 11.1 Hz, 1H, Clisy„H), 1.29 (s, 9H, CMe3), 1.51 (s, 15H, C5Me5), 4.98 (d, 2JHH= 11.1 Hz, 1H, CHantiH), 6.95 (m, 1H, Ar H), 7.38 (m, 1H, Ar H), 7.80 (d, 1H, Ar H). 2.4.11 Preparation^of Cp*W(N0)(CH2CMe3)(C6H3-2,4-F2)^(2.10a)^and Cp*W(N0)(CH2CMe3)(C6H3-2,6-F2) (2.10c) Complexes 2.10a and 2.10c were prepared via thermolysis of 2.1 (101 mg, 0.206 mmol) in m-difluorobenzene. The final dried product mixture was dissolved in a minimum of pentane, and the pentane solution was loaded onto a neutral activated alumina I column (2 x 7cm) made up in pentane and supported on a medium-porosity frit. Elution of the column with 1:4 ether/pentane developed two resolvable bands, a red one containing 2.10a that eluted ahead of the red-purple band containing 2.10c. Once the resolution of the two bands was complete, the eluant composition was changed to 2:1 ether/pentane. The two bands were then eluted and collected separately, and the solvents were removed from the collected eluates in vacuo. The desired compounds were isolated by recrystallization of the residues from pentane/HMDS and HMDS, respectively, to 60 obtain red irregularly-shaped crystals of 2.10a (64 mg, 59%) and dark-red rods of 2.10c (6 mg, 5%, 2 crops). 2.10a: IR (cm -1 ) v(NO) 1595 (s). 1 H NMR (400 MHz, C6D6): 8 —3.03 (dd, 2JHH 11.2 Hz, 5JHF = 5.5 Hz, 1H, C1-153,,,H), 1.25 (s, 9H, CMe3), 1.58 (s, 15H, C5Me5), 5.43 (d, 2JHFI = 11.2 Hz, 1H, CHantiH), 6.57 (m, 1H, Ar H), 6.67 (m, 1H, Ar H), 8.14 (m, 1H, Ar H). 19F { 1 11} NMR (282 MHz, C6D6): 8 —2.7, —34.2. MS (LREI, m/z, probe temperature 100 °C) 533 [Mt], 476 [Mt—CMe3], 462 [Mt—CH2CMe3]. Anal. Calcd for C21H29F2NOW: C 47.29, H 5.48, N 2.63. Found: C 47.14, H 5.26, N 2.37. 2.10c: IR (cm -1 ) v(NO) 1609 (s). 1 H NMR (400 MHz, C6D6): 8 —2.97 (dt, 2JHH = 10.9 Hz, 5JHF = 3.7 Hz, CHsynH), 1.27 (s, 15H, C 5Me5), 1.64 (s, 15H, C5Me5), 5.76 (d, 2,11-11-1 = 10.9 Hz, 1H, CHantjH), 6.65 (m, 1H, Ar H), 6.76 (m, 2H, Ar H). 19F { 1 H} NMR (282 MHz, C6D6): 8 —2.1. MS (LREI, m/z, probe temperature 100 °C) 533 [Mt], 476 [Mt—CMe3], 462 [Mt—CH2CMe3]. 2.4.12 Preparation^of Cp*W(N0)(CH2CMe3)(C6H3-2,4-C12)^(2.11a)^and Cp*W(N0)(CH2CMe3)(C6113-3,5-C12) (2.11b) This reaction involving m-dichlorobenzene was performed and worked up in a manner identical to that described above for the thermolysis of 2.1 in o-dichlorobenzene. Complex 2.11a was isolated as red needles (67 mg, 54%, 2 crops) by crystallization of the chromatographed product from pentane. 61 2.11a: IR (cm') v(NO) 1580 (s). NMR (400 MHz, C6D6) 8 —2.63 (d, 2Jfin = 10.9 Hz, 1H, CH$3,,,H), 1.27 (s, 9H, CMe3), 1.56 (s, 15H, C 5Me5), 5.47 (d, 2JHH= 10.9 Hz, 1H, CHantiH), 6.96 (dd, 1H, 3JHH = 8.0 Hz, 4JHH = 1.0 Hz, Ar H), 7.30 (d, 4JHH = 1.0 Hz, 1H, Ar H), 8.02 (d, 3JHH = 8.0 Hz, 1H, Ar H). 13C NMR (100 MHz, C6D6) 6 9.9 (C5Me5), 33.5 (CH2CMe3), 42.4 (CH2CMe3), 111.1 (C5Me5), 126.6 (Ar C), 128.5 (Ar C), 134.2 (CH2CMe3), 138.0 (Ar C), 139.8 (Ar C), 142.8 (Ar C), 176.3 (WC,p,o). MS (LREI, m/z, probe temperature 100 °C) 565 [M+], 508 [M+—CMe3]. Anal. Calcd. for C211-129C12NOW: C 44.54, H 5.16, N 2.47. Found: C 44.19, H 5.00, N 2.68. 2.11b: 1 H NMR (400 MHz, C6D6): 8 —2.73 (d, 2JHH= 11.1 Hz, 1H, CI-4,X), 1.19 (s, 9H, CMe3), 1.42 (s, 15H, C5Me5), 5.08 (d, 2JHH= 11.1 Hz, 1H, CHanttH), 7.08 (t, 1H, Ar H), 7.65 (s, 2H, Ar H). 2.4.13 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2-F-5-C1) (2.12a) and Cp*W(N0)(CH2CMe3)(C6113-2-C1-5-F) (2.12b) Complexes 2.12a and 2.12b were formed by the thermolysis of I (95.0 mg, 0.194 mmol) inp-chlorofluorobenzene. Complex 2.12a (48 mg, 45%) was isolated analytically pure by crystallization of the crude product mixture from pentane in three crops. No attempts were made to isolate 2.12b. 62 2.12a: IR (cm -1 ) v(NO) 1599 (s). 'H NMR (400 MHz, C6D6) 8 —3.18 (dd, 2JHH = 10.6 Hz, 5JHF = 6.0 Hz, 1H, CI-1,),„11), 1.22 (s, 9H, CMe3), 1.55 (s, 15H, C 5Me5), 5.63 (d, 2JHH = 10.6 Hz, 1H, CHantif1), 6.59 (m, 1H, Ar H), 6.92 (m, 1H, Ar H), 8.30 (m, 1H, Ar H). 19F NMR (282 MHz, C6D6) 8 —9.3. MS (LREI, m/z, probe temperature 100 °C) 549 [Mt], 492 [Mt—CMe3], 478 [Mt—CH2CMe3]. Anal. Calcd for C21H29C1FNOW: C 45.88, H 5.32, N 2.55. Found: C 46.04, H 5.11, N 2.29. 2.12b: 1 H NMR (400 MHz, C6D6) 8 —2.61 (d, 2./HH = 10.8 Hz, 1H, ClisynE1), 1.26 (s, 15H, C5Me5), 1.55 (s, 15H, C5Me5), 5.54 (d, 2JHH = 10.6 Hz, 1H, CHant,H), 6.51 (m, 1H, Ar H), 7.02 (m, 1H, Ar H), 8.05 (m, 1H, Ar H). 19F{ 1 1-1} NMR (282 MHz, C6D6): 8 — 41.5. 2.4.14 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2-F-5-0Me) (2.13a) and Cp*W(N0)(CH2CMe3)(C6H3-2-0Me-5-F) (2.13b) Complexes 2.13a and 2.13b resulted from the thermolysis of 2.1 (95.0 mg, 0.194 mmol) in p-fluoroanisole. The final dried product mixture was dissolved in a minimum of pentane, and the pentane solution was transferred to the top of a neutral activated alumina I column (2 x 7cm) made up in pentane and supported on a medium-porosity frit. The column was eluted with 1:4 ether/pentane, whereupon 2.13b (purple) eluted ahead of 2.13a (red). Once the two bands had completely resolved, the eluant was changed to diethyl ether and the two bands were eluted and collected separately. Compounds 2.13a and 2.13b were recrystallized from 1:1 pentane/HMDS and 1:1 ether/HMDS, 63 respectively, to obtain red irregularly shaped crystals (25 mg, 23%) of the former and purple diamond-shaped crystals (15 mg, 14%) of the latter. 2.13a: 1R (cm -1 ) v(NO) 1597 (s). 1 HNMR (400 MHz, C6D6) 6 —2.93 (dd, 11.9 Hz, 5JHF = 6.1 Hz, 1H, Clisynfl), 1.26 (s, 9H, CMe3), 1.63 (s, 15H, C 5Me5), 3.44 (s, 3H, OMe), 5.48 (d, 2JHH = 11.9 Hz, 1H, CHantiH), 6.63 (m, 1H, Ar H), 6.83 (m, 1H, Ar H), 7.91 (m, 1H, Ar H). 19F{ 1 F1} NMR (282 MHz, C6D6) S —17.0. MS (LREI, m/z, probe temperature 100 °C) 545 [Mt], 488 [Mt—CMe3]. Anal. Calcd for C22H32FNO2W: C 48.45, H 5.91, N 2.57. Found: C 48.70, H 6.22, N 2.81. 2.13b: IR (cm -1 ) v(NO) 1561 (s). 1 H NMR (400 MHz, C6D6) 6 —2.79 (d, 2411-1= 11.6 Hz, 1H, CHsynH), 1.30 (s, 9H, CMe3), 1.62 (s, 15H, C5Me5), 3.05 (s, 3H, OMe), 5.04 (d, 2JHH = 11.9 Hz, 1H, CHant,H), 6.30 (m, 1H, Ar H), 6.80 (m, 1H, Ar H), 8.25 (m, 1H, Ar H). 19F { 1 El} NMR (282 MHz, C6D6) 6 —48.0. MS (LREI, m/z, probe temperature 100 °C) 545 [Mt], 488 [Mt—CMe3]. Anal. Calcd for C22H32FNO2W: C 48.45, H 5.91, N 2.57. Found: C 48.65, H 5.84, N 2.38. 2.4.15 Preparation of Cp*W(N0)(CH2CMe3)(C6H3-2-OMe-5-C1) (2.14a) and Cp*W(N0)(CH2CMe3)(C6H3-2-C1-5-OMe) (2.14b) Complexes 2.14a and 2.14b were formed by the thermolysis of 2.1 (87.0 mg, 0.177 mmol) in p-chloroanisole. At the end of the 40-h reaction period, the reaction vessel was wrapped in aluminum foil, and p-chloroanisole (b.p. 200 °C) was removed in 64 vacuo at 70°C. The dried product mixture was dissolved in a minimum of pentane, and the pentane solution was transferred to the top of a neutral activated alumina I column (2 x 7cm) made up in pentane and supported on a medium-porosity frit. Elution of the column with 1:3 ether/pentane resulted in the development of two well-resolved bands as 2.14a (purple) eluted ahead of 2.14b (red). At this point, the eluant was changed to diethyl ether, and the two bands were eluted and collected separately. Compounds 2.14a and 2.14b were recrystallized from 1:1 ether/HMDS and HMDS to obtain purple plates (55 mg, 55%) and red plates (9 mg, 9%), respectively. 2.14a: IR (cm-1) v(NO) 1584 (s). 1 H NMR (400 MHz, C6D6) 8 —2.86 (d, 2JHH = 11.0 Hz, 1H, CHsynH), 1.30 (s, 9H, CMe3), 1.54 (s, 15H, C5Me5), 3.07 (s, 3H, OMe), 5.07 (d, 2JHH = 11.0 Hz, 1H, CHantjH), 6.28 (d, 3JHH = 8.0 Hz, 1H, Ar H), 7.12 (dd, 3JHH = 8.0 Hz, 4JHH = 1.2 Hz, 1H, Ar H), 8.45 (d, 4JHH = 1.2 Hz, 1H, Ar H). 13C NMR (100 MHz, C6D6) 8 9.9 (C5Me5), 33.8 (CH2CMe3), 41.4 (CH2CMe3), 54.5 (OMe), 110.4 (Ar C) 110.7 (C5Me5), 127.2 (Ar C), 128.6 (Ar C), 131.2 (CH2CMe3), 139.9 (Ar C), 158.5 (Ar C), 170.2 (WC,p,0). MS (LREI, m/z, probe temperature 100 °C) 561 [Mt], 504 [Mt -CMe3]. Anal. Calcd for C22H32C1NO2W: C 47.03, H 5.74, N 2.49. Found: C 46.85, H 6.08, N 2.88. 2.14b: IR (cm -1 ) v(NO) 1567 (s). 1 H NMR (400 MHz, C6D6) 8 —2.42 (d, 2JHH = 11.0 Hz, 1H, CHsyn1-1), 1.30 (s, 9H, CMe 3), 1.63 (s, 15H, C 5Me5), 3.43 (s, 3H, OMe), 5.44 (d, 2JHH = 11.0 Hz, 1H, CHantill), 6.57 (d, 3JHH = 8.0 Hz, 1H, Ar H), 7.21 (dd, 3JHH = 8.0 65 Hz, 4JHH = 1.6 Hz, 1H, Ar H), 7.93 (d, 4.4{H = 1.6 Hz, 1H, Ar H). MS (LREI, m/z, probe temperature 100 °C) 561 [Mt], 504 [M+—CMe3]. 2.4.16 Attempted Thermolysis of 2.1 in Iodobenzene, Trifluoromethoxybenzene and Acetophenone The thermolysis of 2.1 was performed in each of the 3 aforementioned reagents in the usual manner. In all 3 cases a brown solution was obtained. Analysis of the crude product by 1 H NMR indicated the formation of multiple organometallic products as evidenced by a myriad of peaks in the Cp* Me region of the corresponding spectrum. Attempts to isolate any new products by fractional crystallization from pentane were unsuccessful. Attempts to isolate products by Alumina chromatography led to the eventual decomposition of these products on the column 2.4.17 Preparation^of^[Et4N]+[Cp*W(N0)(CH2CMe3)(CN)(0-C6114F)] (fEt4Nr[2.15] -) A 4-dram vial was charged with 2.2a (103 mg, 0.200 mmol), Et 4NCN (31.1 mg, 0.199 mmol), MeNO2 (5mL) and a small magnetic stir bar. The mixture was stirred for 5 min at room temperature whereupon it rapidly turned yellow. The solvent was then removed in vacuo, and the yellow waxy residue was washed with pentane (2 x 5 mL). The remaining solid was redissolved in a minimum amount of THF, and diethyl ether was carefully layered on top of the solution. Storage of this mixture at —30 °C overnight 66 resulted in the deposition of yellow irregularly shaped crystals of [Et4N]12.151- (90 mg, 67%). [Et4N] + [2.15] -: IR (cm -1 ) v(CN) 2103 (s), v(NO) 1530 (s). 'H NMR (400 MHz, acetone-d6) 8 0.69, 1.42 (d, 2JHH= 11.1 Hz, 2H, CH2CMe3), 1.15 (s, 9H, CMe3), 1.34, (tt, 12H, CH3CH2), 1.63 (s, 15H, C 5Me5), 3.29 (q, 8H, CH3CH2), 6.66 (m, 1H, Ar H), 6.73 (m, 1H, Ar H), 6.86 (m, 1H, Ar H), 8.04 (m, 1H, Ar H). 19F {'H} (282 MHz, C6D6): 8 — 1.2. MS (LSIM): m/z 541 [Mi. Anal. Calcd for C301150FN3OW: C 53.65, H 7.50, N 6.26. Found: C 53.61, H 7.37, N 6.39. 2.4.18 Preparation of Cp*W(N0)(1 2-C(=0)CH2CMe3)(o-C 6H4F) (2.16) A Schlenk tube was charged with 2.2a (50.0 mg, 0.101 mmol), and hexanes (10 mL) were added via a syringe to obtain a red solution. CO (1 atm) was bubbled through this solution for 5 min, whereupon it turned yellow and a yellow precipitate deposited. The solvent was removed in vacuo, and the residue was washed with cold pentane (2 x 3 mL). The solid was then redissolved in a minimum of diethyl ether, and pentane was carefully layered on top. The mixture was stored at —30 °C overnight to induce the deposition of yellow feathery crystals of 2.16 (40 mg, 76%). 2.16: IR (cm -1 ): 1584 (s), 1566 (s). 'H NMR (400 MHz, C6D6) 8 0.92 (s, 9H, CMe3), 1.66 (s, 15H, C5Me5), 2.67 (d, 2JHH = 13.2 Hz, 1H, CH2CMe3), 2.98 (d, 2JHH = 13.2 Hz, 1H, CH2CMe3), 7.07-7.14 (m, 3H, Ar H), 8.20 (m, 1H, Ar H). 19F { 1 1-1} (282 67 MHz, C6D6) 6 —12.0. MS (LREI, m/z, probe temperature 100 °C) 543 [Mt], 486 [Mt -CMe3]. Anal. Calcd for C22H30FNO2W: C 48.63, H 5.57, N 2.58. Found: C 48.99, H 5.77, N 2.60. 2.4.19 X-Ray Crystallography Data collection for each compound was carried out at —100 ±1 °C on either a Rigaku AFC7/ADSC CCD diffractometer or a Bruker X8 APEX diffractometer, using graphite-monochromated Mo Ka radiation. Data for 2.2a were collected to a maximum 20 value of 55.8 ° in 0.5 ° oscillations with 8.0 s exposures. The structure was solved by direct methods 22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms HO7A and HO7B were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4883 observed reflections and 243 variable parameters. Data for 2.5a were collected to a maximum 20 value of 55.8 ° in 0.5 ° oscillations with 35.0 s exposures. The structure was solved by direct methods22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms HO8A and HO8B were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4666 observed reflections and 252 variable parameters. 68 Data for 2.6a were collected to a maximum 20 value of 55.6 ° in 0.5 ° oscillations with 10.0 s exposures. The structure was solved by direct methods 22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms H15A and H15B were refined isotropically with fixed bond distances, and all other hydrogen atoms were included in fixed positions. The final cycle of full- matrix least-squares analysis was based on 5848 observed reflections and 305 variable parameters. Data for 2.7 were collected to a maximum 20 value of 55.7 ° in 0.5 ° oscillations with 20.0 s exposures. The structure was solved by direct methods. 23 All hydrogen atoms were included in calculated positions but not refined, except H11, which was found in a difference map and refined isotropically. The final cycle of full-matrix least- squares analysis was based on 5404 reflections and 287 variable parameters. Data for 2.10c were collected to a maximum 20 value of 56.0 ° in 0.5 ° oscillations with 6.0 s exposures. The structure was solved by direct methods 22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms H7A and H7B were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4972 observed reflections and 251 variable parameters. 69 Data for 2.16 were collected to a maximum 20 value of 55.5 ° in 0.5 ° oscillations with 10.0 s exposures. The structure was solved by direct methods. 23 The fluorobenzyl ligand was disordered in two orientations. Restraints were used to maintain both reasonable geometries for both benzyl fragments and both C-F distances . The carbon atoms of the minor disordered fragment were refined with isotropic thermal parameters, all other non-hydrogen atoms were refined anisotropically. All hydrogen atoms were included in calculated positions but not refined. The final cycle of full- matrix least-squares refinement on F 2 was based on 5031 reflections and 262 variable parameters. For each structure neutral-atom scattering factors were taken from Cromer and Waber. 24 Anomalous dispersion effects were included in Fealc; 25 the values for Of and Af" were those of Creagh and McAuley. 26 The values for mass attenuation coefficients are those of Creagh and Hubbe11. 27 All calculations were performed using the CrystalClear software package of Rigaku/MSC,28 or Shelxl-97. 29 X-ray crystallographic data for all six structures are presented in Table 1, and full details of all crystallographic analyses are provided in the Supporting Information. 70 2.5^References and Notes (1) Selected recent examples of ortho-C-H activation: (a) Ben-Ari, E.; Gandelman, M.; Rozenberg, H.; Shimon, 1. J. W. and Milstein, D. Organometallics. 2006, 25, 3190-3210 and references therein. (b) Zhang, X.; Kanzelberger, M.; Emge, T. J. and Goldman, A. S. I Am. Chem. Soc. 2004, 126, 13192-13193. (c) Zhang, F.; Kirby, C. W.; Hairshine, D. W.; Jennings, M. C. and Puddephatt, R. J. I Am. Chem. Soc. 2005, 127, 14196-14197. (d) Renkema, K. B.; Bosque, R.; Streib, W. E.; Maseras, F.; Eisenstein, 0. and Caulton, K. G. J. Am. Chem. Soc. 1999, 121, 10895-10907. (e) Hill, A. F.; Schultz, M. and Willis, A. C. Organometallics 2004, 23, 5729-5736 and references therein. (f) Eguillor, B.; Esteruelas, M. A.; Olivan, M.; and Onate, E. Organometallics 2004, 23, 6015-6024. (g) Kiyooka, S. and Takeshita, Y. Tetrahedron Let. 2005, 46, 4279-4282. (2) For recent examples of a metal complex capable of both C-H and C-X (X = halogen) activation, see (a) Fan, L.; Parkin, S.; and Ozerov, 0. V. I Am. Chem. Soc. 2005, 127, 16772-16773. (b) We, F.; Dash, A. K. and Jordan, R. F. J. Am. Chem. Soc. 2004, 126, 15360-15361. (c) Barrio, P.; Castarlenas, R.; Esteruelas, M. A.; Lledos, A.; Maseras, F.; Onate, E.; Tomas, J. Organometallics 2001, 20, 442- 452. (3) Kakiuchi, F. and Murai, S. Acc. Chem. Res. 2002, 35, 826-834. (4) Matsubara, T.; Koga, N.; Musaev, D. G. and Morokuma, K. I Am. Chem. Soc. 1998, 120, 12692-12693. (5) Adams, C. S.; Legzdins, P. and Tran, E. I Am. Chem. Soc. 2001, 123, 612-624. (6) Adams, C. S.; Legzdins, P. and Tran, E. Organometallics 2002, 21, 1474-1486. 71 (7) To the best of our knowledge, coupling between two alkyne molecules and a metal-alkylidene linkage has not been reported previously, although the closely- related W=N and Mo=N linkages have been shown to be able to react with ring- strained alkyne such as cyclooctyne in a similar manner. See: Lokare, K. S.; Ciszewski, J. T.; and Odom, A. L. Organometallics 2005, 23, 5386-5388. (8) Bau, R.; Mason, S. A.; Patrick, B. 0.; Adams, C. S.; Sharp, W. B; Legzdins, P. Organometallics 2001, 20, 4492-4501. (9) Kraft, B. M.; Lachicotte, R. J.; Jones, W. D. Organometallics 2002, 21, 727-731. (10) Hughes, R. P.; Laritchev, R. B.; Williamson, A.; Incarvito, C. D.; Zakharov, L. N.; Rheingold, A. L. Organometallics 2003, 22, 2134-2141. (11) Crespo, M.; Font-Bardia, M. and Solans, X. Polyhedron 2002, 21, 105-114. (12) Bursten, B. E.; Cayton, R. H. Organometallics 1987, 6, 2004-2005. (13) A search of the Cambridge Structural Database reveals that W-F distances range from 1.657 to 2.189 A with a mean distance of 1.924(0.110) A and that W-0 distances range from 1.689 to 2.400 A with a mean distance of 1.973(0.108) A. (14) For examples of fluorobenzene complexes, see: (a) Bouwkamp, M. W.; Budzelaar, P. H. M.; Gercama, J.; Del Hierro Morales, I.; de Wolf, J.; Meetsma, A.; Troyanov, S. I.; Teuben, J. H.; Hessen, B. J. Am. Chem. Soc. 2005, 127, 14310- 14319 and references therein. (b) Basuli, F.; Aneetha, H.; Huffman, J. C.; Mindiola, D. J. I Am. Chem. Soc. 2005, 127, 17992-17993. (15) Previous work in our group has shown that Cp*W(N0)(CH2CMe3)(o-toly1) isomerizes in C6D6 at 70 °C over 2 days to a thermodynamic mixture having an o:m:p ratio of 1:59:40, identical to the aryl C-H activation product ratio resulting 72 from the thermolysis of 2.1 in toluene. See: Adams, C. S. C-H Activation of Hydrocarbons by Tungsten Alkylidene and Related Complexes. Ph. D. Thesis, University of British Columbia, Vancouver, BC, October 2001. (16) Selmeczy, A. D.; Jones, W. D.; Partridge, M. G. and Perutz, R. N. Organometallics 1994, 13, 522-532. (17) Clot E.; Besora, M.; Maseras, F.; Megret, C.; Eisenstein, O.; Oelckers, B. and Perutz, R. N. Chem. Comm. 2003, 490-491 (18) Aballay, A.; Clot, E.; Eisenstein, 0.; Garland, M. T.; Godoy, F.; Klahn, A. H.; Munoz, J. C. and Oelckers, B. New J. Chem. 2005, 29, 226-231. (19) Dryden, N. H.; Legzdins, P.; Lundmark, P. J.; Riesen, A. and Einstein, F. W. B. Organometallics 1993, 12, 2085-2093. (20) Debad, J. D.; Legzdins, P.; Batchelor, R. J. and Einstein, F. W. B. Organometallics 1993, 12, 2094-2102. (21) Legzdins, P.; Rettig, S. J.; Ross, K. J.; Batchelor, R. J.; Einstein, F. W. B. Organometallics, 1995, 14, 5579. (22) S1R92: Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A. J AppL Crystallogr. 1993, 26, 343. (23) S1R97: Altomare, A.; Burla, M. C.; Cammalli, G.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, A. I Appl. Crystallogr. 1999, 32, 115. (24) Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, 1974, Vol. IV. (25) Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781. 73 (26) Creagh, D. C.; McAuley, W. J. International Tables for X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (27) Creagh, D. C.; Hubbell, J. H. International Tables for X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (28) CrystalClear: Version 1.3.5b20; Molecular Structure Corp.: The Woodlands, TX, 2002. (29) SHELXL97; Sheldrick, G. M. University of Gottingen, Germany, 1997. 74 CHAPTER 3 Synthesis and Characterization of New Cp*W(NO)(CH2CMe3)(allyl) Complexes and Their Reactivity with Cyclic Amines 3.1^Introduction* Transition metal-allyls are an important class of organometallic complexes. Structurally, the allyl ligand can exhibit multiple binding modes (T) l and r1 3) and isomers (Figure 3.1). 1 Chemically, transition metal-allyl complexes often represent key intermediates during homogenous catalysis. 2 L  MLn R mLn antiexo syn Figure 3.1. (a) Conformational isomerism (endo vs. exo) in Cp'-containing transition metal allyl complexes, and (b) stereochemical isomerism regarding substituents on the allyl ligand (syn vs. anti with respect to the meso hydrogen). The investigation into the chemistry of Cp*W(N0)(CH2CMe3)(ally1) complexes is a relatively recent development in the Legzdins laboratories. The work was initiated by Dr. Craig S. Adams, a former group member who was intrigued by the result of the • Portions of this Chapter have been published as a communication. Tsang, J. Y. K.; Fujita-Takayama, C.; Buschhaus, M. S. A.; Patrick, B. 0.; Legzdins, P. Concurrent N-H and a-C-H Bond Activations of Pyrrolidine and Piperidine under Ambient Conditions by 18e Tungsten Allyl Nitrosyl Complexes. J. Am. Chem. Soc. 2006, 128, 14762-14763. olefin coupling -CMe4 'ON ''''''' ' w 75 following transformation (Scheme 3.1) — the formation of a metallacyclic allyl-alkyl species resulting from the reaction of Cp*W(NO)(CH2CMe 3)2 with 2-methyl-2-butene: 3 Scheme 3.1 70 °C, -CMe4 ON.. ''''''''' ^ <^ ON.......W +other products Adams proposed the following mechanism (Scheme 3.2) which involves the initial formation of an allyl-neopentyl species via C-H activation of 2-methyl-2-butene. Adams then proposed that this allyl-neopentyl species reacts further under thermal conditions leading to the formation of the isolated compound among multiple other products. Scheme 3.2 ONE W - —^— / < ' WON '''''' 76 To test his hypothesis, Adams attempted to synthesize and isolate Cp*W(N0)(CH2CMe3)(11 3-CH2CHCMe2) (3.1) via metathesis, and he was successful in this regard. After Adams departed from the group with his Ph.D. degree, Steve H. K. Ng and Dr. Chikako Fujita-Takayama, both former group members, carried on investigating the characteristic reactivity of 3.1. The research has been productive (Scheme 3.3). 4 The intermediates generated during the thermolysis of 3.1 have been demonstrated to perform C-H activation on hydrocarbon solvent molecules. Trapping experiments suggest that there exist two such intermediate species, one of them being a 16e allene complex, Cp*W(NO)(r1 2-CH2=C=CMe2) (A), which has been isolated as a trimethylphosphine adduct, Cp*W(N0)(11 2-CH2=C—CMe2)(PMe3) (3.2) — the only identifiable organometallic species formed during the reaction between 3.1 and PMe 3 at 50 °C. The other intermediate species are believed to be i 2-diene complexes, their identities having been inferred by 1) hydrocarbon labeling studies, since deuterium is observed to be incorporated onto the terminal methyl carbons in addition to the middle allyl carbon, and 2) the reaction between 3.1 and cyclohexene which forms Cp*W(N0)(11 3 ,ii 1 - CH2CHCHCH2C01-1(C4H8)C,,H) (3.3), resulting from the olefin coupling followed by isomerization, as one of two principal organometallic species, the other one being Cp*W(NO)(r1 3-CH2C(3-cyclohexyl)CMe2)(H) (3.4), attributable to the trapping of the allene intermediate. 3.3 3.4 ON'''' ' W- PMe3 *.4C7PMe3 C6D650 °C, -CMe4 ON- W ON.... W-co 54.< CH2D ON W3.1 ON, W'H 77 Scheme 3.3 Surprisingly, complex 3.1 is also able to perform C-H activations even without losing neopentane and going through an olefin intermediate. 5 Specifically, when complex 3.1 is dissolved in pyrrolidine for 17 h, Cp*W(N0)(CH2CMe3)(NC4117-2-Me2C3H3) (3.12) is formed quantitatively as judged by 1 1-1 NMR spectroscopy. Complex 3.12 is apparently formed by the concurrent N-H and ICC-H activation of pyrrolidine, with the concomitant loss of two hydrogen atoms, the migration of the metal-bound allyl onto the 2-position of the pyrrolidyl, and the formation of a W-N amido linkage (Scheme 3.4). To our knowledge, this type of transformation has not been observed previously.6 Therefore, more insights about this chemistry have been sought, particularly details concerning possible mechanisms for the reaction and whether this type of transformation is general for various systems. ( ^/ NH OW- W 4_( 3.1 0 n=1,3.12 n=2,3.13 20 °C 17 h (n=1) or 7 d (n=2) Scheme 3.4 78 To address these unanswered questions arising from both projects, the syntheses of complexes bearing allyl ligands containing different substituents have been attempted. All new complexes have been subjected to conventional spectroscopic and, if necessary, X-ray structural studies, in order to establish their identities. The thermal chemistry of these new complexes has then been investigated in hopes of confirming the identity of the elusive 11 2-diene intermediate by a Lewis-base trapping experiment. It was anticipated that complexes bearing an allyl ligand that contains a meso-hydrogen or a terminal methyl group would be thermally active. Finally, all new complexes have been treated with various amines in order to establish the generality of the concurrent N-H and K-C-H activation reactions. In this chapter we present some of the results of these investigations. Four new allyl-neopentyl complexes and one allyl-CH2SiMe3 complex have been synthesized by conventional metathesis reactions with magnesium reagents and have been studied spectroscopically. As far as the thermal chemistry is concerned, two of the newly synthesized complexes, namely, Cp*W(N0)(CH2CMe3)(i 3 -CH2CHCHMe) (3.7) and 79 Cp*W(N0)(CH2CMe3)(1) 3 -CH2CHCHPh) (3.8), form C-H activating intermediates under thermal conditions, while Cp*W(N0)(CH2SiMe3)(T1 3-CH2CHCHMe) (3.9) also loses tetramethylsilane at elevated temperatures. The thermal reactivity of 3.7 and 3.8 is documented in chapters 4 and 5 of this thesis, respectively. The concurrent N-H and KC- H activation reaction is general for four of the new complexes, but the scope of organic substrates for the reaction is limited to cyclic amines. 3.2^Results and Discussion 3.2.1 Synthesis and Spectroscopic Properties of New Compounds The five new compounds 3.5-3.9 can all be synthesized via metathesis with magnesium reagents, and they are all isolable as yellow to orange solids (Scheme 3.5) in moderate yields. These compounds are formally 18e entities; hence it is not surprising that they are somewhat stable towards oxygen and moisture in the crystalline state. For example, crystals of 3.5, 3.6 and 3.8 all maintain their lustre for at least three months while being exposed to air. 80 Scheme 3.5 1/2 Mg(CH2EMe3)2 . x(dioxane)^1/2 C– ^ g(ally1)2 x(dioxane) , .W—_, )̂11 ON......W C1 ON""^—E— / CI^ CI^I , Complex E R R' Color Yield (%) 3.5 C H H Yellow 62 3.6 C Me H Pale yellow 62 3.7 C H Me Yellow-orange 43 3.8 C H Ph Orange 58 3.9 Si H Me Yellow-orange 65 The solid-state molecular structures of compounds 3.5, 3.7, 3.8 and 3.9 have all been established by X-ray crystallographic analyses, and these structures are shown in Figures 3.2 to 3.6, respectively. All four complexes feature allyl ligands that are in the endo conformation (middle carbon pointing down and away from Cp* ring). It is well established by DFT calculations that the two different allyl conformations in group 6 half-sandwich compounds Cp'MLIL2(ally1) are very close in energy, with the endo form being slightly more stable. 7 In complex 3.7 where the asymmetric 1-methylally1 ligand is present, the methyl substituent occupies a syn position of the allyl ligand and is cis to the smaller nitrosyl ligand, not to the bulkier neopentyl or CH2SiMe3 ligand. Complex 3.8 also crystallizes as a discrete isomer that features the phenyl substituent cis to the nitrosyl ligand. Interestingly, complex 3.9 crystallizes as two isomers. The major isomer, present as a ca. 2:1 majority, has a structure that is totally analogous to that of 3.7. The minor isomer features the methyl substituent of the 1-methylally1 ligand on the opposite end, cis C14^ C15 C16 C13 C17 81 to the CH2SiMe3 ligand. As expected, the ally' ligand of each of the complexes exhibits a—TC distortion (C-C trans to nitrosyl bearing a higher multiple-bond character than C-C cis to nitrosyl), a manifestation of electronic asymmetry at the metal centre. 8-12 Figure 3.2.^Solid-state molecular structure of 3.5 with 50 % probability thennal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.416(6), W(1)-C(2) = 2.339(6), W(1)-C(3) = 2.252(6), W(1)-C(5) = 2.267(6), W(1)-N(1) = 1.770(5), N(1)-0(1) = 1.236(7), C(1)-C(2) = 1.361(10), C(2)-C(3) = 1.425(10), C(1)- C(2)-C(3) = 118.3(7), W(1)-C(5)-C(6) = 124.3(4), W(1)-N(1)-0(1) = 171.2(5). Figure 3.3.^Solid-state molecular structure of 3.7 with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.401(3), W(1)-C(2) = 2.346(3), W(1)-C(3) = 2.282(3), W(1)-C(5) = 2.257(3), W(1)-N(1) = 1.764(2), N(1)-0(1) = 1.221(3), C(1)-C(2) = 1.372(5), C(2)-C(3) = 1.425(4), C(3)-C(4) = 1.509(4), C(1)-C(2)-C(3) = 119.3(3), C(2)-C(3)-C(4) = 120.4(3), W(1)-C(5)-C(6) = 123.4(2), W(1)-N(1)-0(1) = 170.5(2). 82 83 Figure 3.4.^Solid-state molecular structure of 3.8 with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.397(3), W(1)-C(2) = 2.345(3), W(1)-C(3) = 2.304(3), W(1)-C(10) = 2.265(3), W(1)-N(1) = 1.772(3), N(1)-0(1) = 1.223(4), C(1)-C(2) = 1.365(5), C(2)-C(3) = 1.437(5), C(3)-C(4) = 1.494(4), C(1)-C(2)-C(3) = 120.9(3), C(2)-C(3)-C(4) = 121.0(3), W(1)-C(10)-C(11) = 123.6(2), W(1)-N(1)-0(1) = 169.7(2). 84 Figure 3.5.^Solid-state molecular structure of 3.9, major isomer, with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(la) = 2.44(1), W(1)-C(2a) = 2.339(10), W(1)-C(3a) = 2.278(8), W(1)-C(5) = 2.212(6), W(1)- N(1a) = 1.690(8), N(la)-O(la) = 1.210(11), C(la)-C(2a) = 1.392(16), C(2a)-C(3a) = 1.415(16), C(3a)-C(4a) = 1.504(14), C(1a)-C(2a)-C(3a) = 118.0(11), C(2a)-C(3a)-C(4a) = 119.3(10), W(1)-C(5)-Si(1) = 119.4(4), W(1)-N(1a)-0(1a) = 167.5(10). 85 Figure 3.6.^Solid-state molecular structure of 3.9, minor isomer, with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(lb) -- 2.35(3), W(1)-C(2b) = 2.39(2), W(1)-C(3b) = 2.41(3), W(1)-C(5) = 2.212(6), W(1)-N(110) = 1.863(15), N(1)-0(1b) = 1.275(17), C(lb)-C(2b) = 1.40(2), C(2b)-C(3b) = 1.41(2), C(3b)-C(4b) = 1.50(2), C(lb)-C(2b)-C(3b) = 118(3), C(2b)-C(3b)-C(4b) = 120(3), W(1)- C(5)-Si(1) = 119.4(4), W(1)-N(1b)-0(1b) = 171(2). 86 The 1 14 NMR data for all the above complexes are very similar. The data indicate that the solid-state molecular structures persist in solution, and signals attributable to the protons on the allyl ligand are typical for organometallic allyl complexes in general. In retrospect, the solution structure 13 of 3.1 (dimethyl allyl terminal cis to neopentyl) is somewhat surprising, simply because of the steric congestion between the neopentyl and ally' methyl groups. For complexes 3.7 and 3.9, a second set of proton signals, attributable to the respective minor isomers, are observable, and these signals are listed in the experimental section. The minor isomer of compound 3.7 apparently does not co- crystallize with the observed major isomer. Complex 3.8 does not exhibit stereoisomerism, most likely because the ally! phenyl substituent is too bulky to be placed cis to the even bulkier neopentyl ligand. Not surprisingly, the 13C NMR data support the fact that allyl 6-TC distortion persists in solution. Specifically, the chemical shifts for the a-terminal ally! carbon (ca. 40 ppm when unsubstituted) is some 35 ppm upfield from the 7r-terminal allyl carbon (ca. 75 ppm when unsubstituted). The middle carbon signal appears in the vicinity of 110 ppm when the carbon is unsubstituted. In order to investigate structural isomerism, the ill NMR spectra of selected compounds have been acquired at both low and high temperatures. The spectral results indicate that the solution structures are essentially static, endo-exo isomerism is not observable, and isomers featuring the asymmetric ally! ligand CH2CHCHMe do not interconvert on an NMR timescale. For example, the 'H NMR spectrum of complex 3.5 in acetone-d6 remains essentially unchanged during the temperature range from RT to — 75 °C. The 1 H NMR spectrum of the same compound at 70 °C in C6D6 is identical to the 87 RT spectrum. Similarly, in a series of low-temperature II-1 NMR spectra of complex 3.9 in CDC13 , the ally! signals due to the minor isomer begin to sharpen as the temperature falls near —15 °C, but there is no observable peak shifting or coalescing. 3.2.2 Thermal Stabilities of New Compounds The new compounds have been heated in various organic solvents in order to investigate their thermal properties. As stated before, it was anticipated that the presence of a meso-hydrogen or a terminal methyl group would lead to thermal reactivity of the metal complex. Thermolysis reactions prove that this expectation is true for the most part, except for complex 3.5 which appears to be stable at 70 °C in both C6D6 and PMe3 for 16 h (overnight). The reason for this thermal stability is unclear at this point. Complex 3.6, which has neither a meso proton nor a terminal methyl group, also remains unchanged after being heated at 70 °C for 16 h in C6D6. On the other hand, complex 3.7 proves to be unstable even at room temperature, decomposing in the solid state into a brown intractable solid over 64 h. In solution it decomposes completely during 1 d at RT. Crystals of complex 3.8 are stable at RT for at least a few months (vide infra), but in solution at 75 °C it is consumed within 1 d. Complex 3.9 is also stable at RT, but loses SiMe4 in solution at 70 °C also over the course of 1 d. 88 3.2.3 Reactions of New Complexes with Pyrrolidine and Piperidine In order to acquire more insight about the reaction depicted in Scheme 3.4, each of the new compounds has been treated with pyrrolidine. Current results indicate that the concurrent N-H and a-C-H activation reaction appears to be general for complexes 3.6- 3.9, but the scope of the reaction is limited to cyclic amines. 3.2.3.1 Reactions Between Cyclic Amines and 3.5 When^complex^3.5^is^treated^with^pyrrolidine^at^RT, Cp*W(NO)(NC4H8)(CHMeCH2NC4H8) (3.10) is formed as the only organometallic product along with an unidentifiable white solid. The reaction is deemed to be complete within 5 h. Prolonged reaction times lead to reduced yields — this has been further confirmed by the loss of the orange color of complex 3.10 and the formation of a white insoluble solid when it is redissolved in pyrrolidine for a few days. Complex 3.10 is not amenable to chromatography on alumina, but extraction with pentane, filtering through Celite, and subsequent crystallization are adequate procedures for the isolation of an analytically pure sample of the compound. Crystallization from pentane affords fibrous needles that are too thin for X-ray diffraction studies. Therefore an alternative solvent has to be used, and Et20 proves to be effective in this regard. The solid-state molecular structure of 3.10 is shown in Figure 3.7. Two equivalents of pyrrolidine have been incorporated, the neopentyl ligand has been lost, and what used to be the allyl ligand has now become a pyrrolidylisopropyl entity. Figure 3.7.^Solid-state molecular structure of 3.10 with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(2) = 2.198(6), W(1)-N(2) = 1.926(4), W(1)-N(3) = 1.749(5), N(3)-0(1) = 1.246(5), C(1)-C(2) =- 1.537(7), C(2)-C(3) = 1.544(6), C(3)-N(1) = 1.462(7), C(1)-C(2)-C(3) = 110.0(4), C(2)- C(3)-N(1) = 114.3(5), C(3)-N(1)-C(4) = 114.0(4), C(3)-N(1)-C(7) = 112.9(5), W(1)- N(2)-C(8) = 128.7(3), W(1)-N(2)-C(11) = 125.1(3), W(1)-N(3)-0(1) = 168.8(4). 89 90 The overall transformation is the well-known la,7,12,14 nucleophilic attack (by pyrrolide) on a metal-bound allyl, protonation on the opposite terminal of the allyl, and the replacement of the neopentyl by a pyrrolidyl. It is unclear at present why complex 3.5 does not react with pyrrolidine in the same way as do the other complexes bearing other allyl ligands. In any event, a plausible mechanism can be proposed (Scheme 3.6). Firstly, the allyl ligand is attacked on the ally! terminal trans to the nitrosyl by a pyrrolide nucleophile, which should be present in equilibrium with pyrrolidinium and pyrrolidine. 15 It has been well established long ago that nucleophilic attack on bound allyls in group-6 half-sandwich compounds of this type occurs trans to the better r<-acceptor (i.e. the NO ligand) when the ally! is in the endo conformation. 7 ' 16 Next, the neopentyl group is liberated by protonation, and a neutral, coordinatively unsaturated metal centre is formed. Finally, a second molecule of pyrrolidine coordinates to the metal centre and yields 3.10 after proton migration. Similarly, piperidine reacts with 3.5 at RT to form Cp*W(NO)(NC5H10)(CHMeCH2NC 5H10) (3.11). The reaction time required is much longer (2 d), and consequently a considerable amount of 3.11 decomposes before 3.5 is completely consumed, hence accounting for the lower yield of the reaction. Meanwhile, complex 3.5 remains unchanged when it is dissolved in aniline, cyclohexylamine, diethylamine or tert-butylamine for 1 d at RT. OW—W-1 3.5 ON......W^H2NC41-18+ -CMe4-C NH ON....... w zit__ N0 3.10 t H migration ON,.....W, N/\ H ON"— w Scheme 3.6 91 3.2.3.2 Reactions Between Cyclic Amines and 3.6-3.9 After the initial discovery of concurrent N-H and a-C-H activation effected by 3.1, more examples of the same transformation have been sought. Treatment of complex 3.6 with pyrrolidine at RT for 64 h leads to the formation of two new species, one of which is Cp*W(N0)(CH2CMe3)(NC4H7-2-CH2CMe=a12) (3.14). The reaction is sluggish and does not go to completion before significant product degradation occurs. Complex 3.14 can be obtained in low yields by fractional crystallization after extraction from the less soluble unreacted starting material following 92 initial chromatography of the crude product on alumina. The solid-state molecular structure of 3.14 is shown in Figure 3.8, and its metrical parameters closely resemble those of 3.12. Specifically, the atoms W 1, N2, C6 and C9 are essentially coplanar, as evidenced by the sum of the angles around N2 (ca. 358 0). This indicates that the nitrogen atom is behaving as a 3-electron donor to the W centre. The bond distance between W1 and N2 is 1.938(2) A, which is longer than typical W-N double bonds' 7 , and probably reflects steric crowdedness around the W centre. A second product is formed in a ca. 1:2 ratio vs 3.14 according to the integration of their respective 1 1-1 NMR Cp* methyl peaks. However, this product has not yet been identified since it appears to decompose upon chromatography. As a result it cannot be ruled out that the second product is the analogue of 3.10 which also decomposes on alumina. Complex 3.7 also reacts with pyrrolidine to form the concurrent N-H and a-C-H activation product, Cp*W(N0)(CH2CMe3)(NC4H7-2-CHMeCH=CH2) (3.15). As in the case of complex 3.6, the reaction is not clean. This feature may well reflect the fact that complex 3.7 also possesses thermal pathways that could, for example, lead to the simple C-H activation on the pyrrolidine CH 2 backbone. These pathways are discussed in the next chapter. Nevertheless, complex 3.15 can be isolated as the sole organometallic product after chromatography on alumina. Not surprisingly, complexes 3.8 and 3.9, which are thermally stable at RT, produce the most facile reactions. Both compounds Cp*W(N0)(CH2CMe3)(NC4F17-2- CHPhCH=CH2) (3.16) and Cp*W(N0)(CH2SiMe3)(NC4H7-2-CHMeCH=CH2) (3.17) are C7 C8 010 C11 93 formed quantitatively in 16 h and 4 d, respectively, at ambient temperatures as judged by 'H NMR spectroscopy. Figure 3.8.^Solid-state molecular structure of 3.14 with 50 % probability thermal ellipsoids. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.184(3), W(1)-N(2) = 1.938(2), W(1)-N(1) = 1.763(2), N(1)-0(1) = 1.239(3), C(11)-C(12) = 1.324(5), C(10)-C(11)-C(12) = 121.6(4), W(1)-N(2)-C(9) = 127.17(18), W(1)-N(2)-C(6) = 124.65(18), C(6)-N(2)-C(9) = 106.14(18), W(1)-N(1)-0(1) = 168.7(2). 94 Unfortunately, the concurrent N-H and a-C-H activation transformation has a very limited range of substrates. Piperidine also reacts with complex 3.1 to form the concurrent N-H and a-C-H activation product, namely, Cp*W(N0)(CH2CMe 3)(NC 5H9 - 2-Me2CCH=CH2) (3.13). However, other amines, such as aniline, cyclohexylamine, diethylamine and tert-butylamine, are all unreactive in this regard. Furthermore, replacing the neopentyl with a smaller alkyl ligand, such as n-penty1, 18 also renders the complex unreactive towards pyrrolidine. 3.2.3.3 Mechanistic Insights on the Concurrent N-H and a-C-H Activation Process The reaction between 3.6 and pyrrolidine has been monitored by NMR spectroscopy in order to gain some mechanistic insights concerning the general reaction. Unfortunately, no organometallic intermediates are observable. Interestingly, the 1 I-1 NMR spectrum of the volatiles from the reaction contains a small singlet at 4.80 ppm, indicative of the production of H2 during the course of the reaction. This chemical shift has been confirmed by recording the 1 I-1 NMR spectrum of a separately prepared sample of H2 in pyrrolidine in a J-Young NMR tube equipped with a C6D6 capillary. Since all the product complexes are formed at room temperature, it is unlikely that the allyl reactants convert to an olefin intermediate 4 or that the pyrrolidine is dehydrogenated to pyrroline prior to reacting. 19 Nevertheless, a number of possible mechanisms can be envisaged for these conversions, and more studies will be required to evaluate the various possibilities. A possible reaction mechanism, involving the allyl r13- (NH 95 •rl isomerization, coordination of pyrrolidine, followed by a pericyclic-type arrangement, is proposed in Scheme 3.7. Scheme 3.7 3.3^Conclusion During the investigations of these new allyl complexes, we have discovered that the presence of a meso-hydrogen on the ally! alone does not lead to thermal reactivity. Other factors, such as steric factors, can render the loss of neopentane more facile, as in the cases of complexes 3.5 vs 3.8. On the other hand, the presence of a methyl group does lead to thermal reactivity of the compounds, presumably because of the possibility of p-hydrogen elimination by a 16e complex as it undergoes allyl r1 3 -ri 1 isomerization. 96 The reactivity with cyclic amines also depends on the sterics of the allyl ligand — apparently concurrent N-H and a-C-H activation happens readily when the allyl ligand is sterically demanding, as in the cases of complex 3.7-3.9. In the intermediate case of complex 3.6 concurrent N-H and a-C-H activation is sluggish, and for 3.5, the complex with the smallest allyl ligand, only traditional nucleophilic attack by cyclic amines occurs. 3.4^Experimental Procedures 3.4.1 General Considerations All reactions and subsequent manipulations involving organometallic reagents were performed under anaerobic and anhydrous conditions either under high vacuum or an inert atmosphere of prepurified dinitrogen. Purification of inert gases was achieved by passing them first through a column containing MnO and then a column of activated 4 A molecular sieves. Conventional glovebox and vacuum-line Schlenk techniques were utilized throughout. The gloveboxes utilized were Innovative Technologies LabMaster 100 and MS-130 BG dual-station models equipped with freezers maintained at —30 °C. Most of the reactions were performed in thick-walled glass vessels possessing Kontes greaseless stopcocks and side-arm inlets for vacuum-line attachment. Small-scale reactions and NMR spectroscopic analyses were conducted in J. Young NMR tubes which were also equipped with Kontes greaseless stopcocks. All solvents were dried with appropriate drying agents under a dinitrogen atmosphere and were distilled prior to 97 use, or they were transferred directly under vacuum from the appropriate drying agent. Hydrocarbon solvents, diethyl ether, and tetrahydrofuran were dried and distilled from sodium benzophenone ketyl. Commercially available (C 3H5)MgC1 (Aldrich, 1.0 M in THF), (CH2CMeCH2)MgC1 (Aldrich, 0.5 M in THF) and (CH2CHCHMe)MgC1 (Aldrich, 0.5 M in THF) were transformed into the corresponding diallylmagnesium reagents in the usual manner.2° '21 Cp*W(N0)(CH2CMe3 )C12° and Cp*W(N0)(CH2CMe3)(r1 3 - CH2CHCMe 2) (3.1)4 were prepared according to published procedures. The synthesis of (CH2CHCHPh)MgCI from cinnamyl chloride (Aldrich) and magnesium (Strem) was carried out in a manner similar to that described previously for the synthesis of other allylmagnesium reagents, 4 and it was converted into the bis(allyl)magnesium reagent in the usual manner. 20 The progress of most reactions was monitored by NMR spectroscopy, and the isolated yields of all new complexes have not been optimized. All IR samples were prepared as Nujol mulls, and their spectra were recorded on a Thermo Nicolet 4700 FT-IR spectrometer. NMR spectra were recorded at room temperature on Bruker AV-300, AV-400 or AMX-500 spectrometers. All chemical shifts are reported in ppm, and all coupling constants are reported in Hz. 1 H NMR spectra are referenced to the residual protio isotopomer present in a particular solvent, and 13C NMR spectra are referenced to the natural-abundance carbon signal of the solvent employed. Where necessary, 1 H- 1 H COSY, 1 H- 1 H NOEDS, 1 H- 13C HMQC, 1 H- 13C HMBC, and 13C APT experiments were carried out to correlate and assign 1 H and 13 C NMR signals. Low-resolution mass spectra (EI, 70 eV) were recorded by the staff of the UBC mass 98 spectrometry facility using a Kratos MS-50 spectrometer. Elemental analyses were performed by Mr. Minaz Lakha of the UBC microanalytical facility. 3.4.2 Preparation of Cp *W(N0)(CH2CMe3)(113-012CHCH2) (3.5) Complexes 3.5, 3.6, 3.7 and 3.8 were synthesized and isolated in a similar manner, and the preparation of complex 3.5 is described here as a representative example. In a glovebox a medium (ca. 250-mL) Schlenk tube was charged with a magnetic stir bar and Cp*W(N0)(CH2CMe 3)C1 (2.50 g, 5.50 mmol). A second medium Schlenk tube was charged with a magnetic stir bar and (C3H5)2Mg x(dioxane) (titre = 98.0 g / mol R, 0.538 g, 0.5 equiv). On a vacuum line, Et20 (approx. 150 mL and 20 mL) was vacuum- transferred onto the Cp*W(NO)(CH2CMe3)Cl and the diallylmagnesium reagents, respectively. The Et20 above the Cp*W(NO)(CH 2CMe3)Cl was allowed to melt while the Schlenk tube was placed in a dry ice/acetone bath. The mixture was stirred to ensure complete dissolution of the Cp*W(N0)(CH2CMe3)C1 reagent. The Schlenk glass stoppers were replaced by Suba septa. The second Schlenk tube containing the magnesium reagent was maintained in a liquid N2 bath, and the purple Cp*W(NO)(CH2CMe3)Cl solution was added dropwise via a cannula The rate of addition was slow enough to allow the added solution to freeze upon contact with the frozen Et20. Additional cold Et20 (2 x 10 mL) was used to ensure quantitative transfer of the Cp*W(NO)(CH2CMe3)Cl reactant. After the addition of the Cp*W(NO)(CH2CMe3)Cl solution was complete, the mixture was stirred for a further 45 min while maintained in the dry ice/acetone bath. The solution gradually turned brown, 99 with the concomitant formation of a brown suspension of Mg salts. The dry ice/acetone bath was then removed, and the solvent was evaporated from the final mixture in vacuo. The residue was extracted with hexanes (4 x 100 mL), and the combined extracts were transferred to the top of a neutral activated alumina (I) column (2 x 8 cm) made up in hexanes and supported on a medium or high porosity fit. The column was eluted with 1:1 hexanes/Et20, and the resulting yellow band was collected. Solvents were removed from the eluate in vacuo to obtain a yellow microcrystalline powder which was recrystallized from 3:1 pentane/Et20 at —30 °C. Fluffy, bright yellow needles of 3.5 were obtained in multiple crops. The crystals were washed with small amounts of cold pentane (-30 °C, 2 x 5 mL) and dried in vacuo. Yield 1.70 g (62%). Characterization data for 3.5: IR (cm 1 )1597 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 0.49 (br s, 1H, allyl CH2), 0.92 (d, 2JHH = 12.4, 1H, CH2CMe 3), 1.30 (s, 9H, CMe3), 1.49 (s, 15H, C5Me5), 1.67 (d, 2JHH = 12.4, 1H, CH2CMe3), 1.89 (br s, 1H, ally! CH 2), 2.29 (br s, 1H, ally' CH2), 3.78 (br s, 1H, allyl CH2), 5.12 (m, ally! CH). 13C{ I I-1} NMR (100 MHz, C6D6) 8 9.8 (C5Me5), 26.7 (CH2CMe3), 34.5 (CH2CMe3) 39.1 (CH204e3), 40.0 (allyl CH2), 78.9 (allyl CH2), 106.1 (C 5Me5), 111.8 (allyl CMe). MS (LREI), m/z, probe temperature 120 °C) 461 [Mt]. Anal. Calcd. for C18H3INOW: C, 46.87; H, 6.77; N, 3.03. Found: C, 46.95; H, 7.10; N, 3.07. 100 3.4.3 Preparation of Cp*W(N0)(CH2CMe3)(71 3-CH2CMeCH2) (3.6) Complex 3.6 was synthesized from the reaction between Cp*W(N0)(CH2CMe3)C1 (2.00g, 4.40 mmol) and (CH2CMeCH2)2Mg x(dioxane) (titre = 113.0 g / mol R, 0.501g, 0.5 equiv). Complex 3.6 was worked up in a manner identical to that of 3.5 and was isolated as long pale-yellow needles (0.65 g, 62%). Characterization data for 3.6: IR (cm-1 ) 1563 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 0.56 (br d, 2^= 2.7, 1H, allyl CH2), 1.06 (d, 2JHH = 13.0, 1H, CH2CMe3), 1.35 (s, 9H, CMe3), 1.50 (s, 15H, C 5Me5), 1.73 (d, 2JHH= 13.0, 1H, CH2CMe3), 1.79 (br s, 11-1, allyl CH2), 2.02 (dd, 2JHH= 2.7, 4JHH= 4.2, 1H, allyl CH2), 2.28 (s, 3H, allyl Me), 3.52 (br d, 4JHH = 4.2, 1H, allyl CH2). 13 C{ 1 11} NMR (100 MHz, C6D6) 8 9.9 (C5Me5), 21.8 (allyl Me), 27.4 (CH2CMe3), 35.0 (CH2CMe 3) 37.4 (CH2CMe3), 43.5 (allyl CH2), 74.5 (allyl CH2), 106.5 (C5Me5), 129.5 (allyl CMe). MS (LREI, m/z, probe temperature 120 °C) 475 [Mt]. Anal. Calcd. for C19H33NOW: C, 48.01; H, 7.00; N, 2.95. Found: C, 48.13; H, 7.12; N, 3.17. 3.4.4 Preparation of Cp*W(N0)(CH2CMe3)(r13-CH2CHCHMe) (3.7) Complex 3.7 was synthesized from the reaction between Cp* W(NO)(CH2CMe3)Cl (3.20g, 7.03 mmol) and (CH2CHCHMe)2Mg x(dioxane) (titre = 112.5 g / mol R, 0.791g, 0.5 equiv). Since complex 3.7 is thermally unstable, cold solvents (-30 °C) had to be employed throughout its extraction and subsequent 101 chromatography in order to minimize its decomposition. The residue from the chromatographic eluate was redissolved and crystallized from pentane at —30 °C overnight to obtain 3.7 as orange-yellow crystalline, irregularly-shaped clusters in multiple crops. The solids were washed with small amounts of cold pentane (-30 °C, 2 x 5 mL) and then dried in vacuo. Yield 2.22 g (43%). Characterization data for 3.7: IR (cm 1 )1594 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 (major isomer) 0.89 (d, 2JHH = 13.2, 1H, CH2CMe3), 1.01 (m, 1H, allyl CHMe), 1.32 (s, 9H, CMe3), 1.48 (s, 15H, C 5Me5), 1.56 (d, 3JHH= 14.0, 1H, ally' CH2), 1.59 (d, 2AH= 13.2, 1H, CH2CMe3), 1.89 (d, 3JHH = 6.0, 3H, allyl Me), 3.67 (d, 3 JHH = 7.2 1H, allyl CH2), 4.97 (ddd, 3JHH= 7.2, 3 JHH = 9.4, 3 JF11-1 = 14.0, 1H, allyl CH). 8 (minor isomer) selected signals 0.51 (m, 1H, ally' CH2), 1.35 (s, 9H, CMe3), 2.30 (m, 1H, ally! CH2), 2.67 (m, 1H, allyl CH), 4.47 (m, 1H, allyl CH). 13 C{ 1 H} NMR (100 MHz, C6D6) 8 9.5 (C5Me5), 16.9 (ally! Me), 27.9 (CH2CMe3), 34.6 (CH2CMe3), 39.3 (CH2CMe3), 52.4 (ally! CHMe), 74.3 (allyl CH2), 106.0 (C5Me5), 114.6 (allyl CH). MS (LREI, m/z, probe temperature 120 °C) 475 [M+]. Anal. Calcd. for C I9H3 3NOW: C, 48.01; H, 7.00; N, 2.95. Found: C, 47.88; H, 7.32; N, 3.24. 3.4.5 Preparation of Cp*W(N0)(CH2CMe3)(n 3-CH2CHCHPh) (3.8) Complex 3.8 was synthesized from Cp*W(NO)(CH 2CMe3 )Cl (0.50g, 1.10 mmol) and (CH2CHCHPh)2Mg x(dioxane) (titre = 187.0 g / mol R, 0.205g, 0.5 equiv) and worked up in a manner similar to that described for 3.5 above. The orange eluate was 102 collected, the solvent was removed in vacuo, and the residue was crystallized from pentane at —30 °C overnight to obtain 3.8 as orange rods. The crystals were washed with small amounts of cold pentane (-30 °C, 2 x 2 mL) and then dried in vacuo. Yield 0.34 g (58%). Characterization data for 3.8: IR (cm -1 ) 1588 (s, vN0). I FI NMR (400 MHz, C6D6) 8 0.93 (br s, 1H, CH2CMe3), 1.24 (obscured, 1H, ally! H), 1.32 (br s, 9H, CMe 3), 1.43 (br s, 15H, C5Me5), 1.60 (br s, 1H, CH2CMe3), 2.11 (br s, 1H, ally' H), 3.74 (br s, 1H, allyl H), 5.53 (br s, 1H, allyl CH), 7.07-7.36 (br m, 5H, aryl H). 13 C{ 1 1-1} NMR (100 MHz, C6D6) 8 9.5 (C5Me5), 29.1 (CH2CMe3), 34.8 (CH2CMe3), 39.0 (CH2CMe3), 61.1 (ally! CHPh), 72.0 (ally! CH2), 106.3 (C5Me5), 109.1 (allyl CH), 126.4 (aryl C), 127.2 (aryl C), 128.7 (aryl C), 137.4 (ipso C). MS (LREI, m/z, probe temperature 120 °C) 537 [M +]. Anal. Calcd. for Ci9H 33NOW: C, 53.64; H, 6.56; N, 2.61. Found: C, 53.58; H, 6.32; N, 2.64. 3.4.6 Preparation of Cp*W(N0)(CH2SiMe3)(13-CH2CHCHMe) (3.9) Complex 3.9 was synthesized from the reaction between Cp*W(NO)(CH2SiMe3)Cl (1.93g, 4.40 mmol) and (CH2CHCHMe) 2Mg x(dioxane) (titre --= 112.5 g / mol R, 0.501g, 0.5 equiv). Complex 3.9 was worked up in a manner identical to that described for 3.5. Complex 3.9 was crystallized as yellow-orange prisms (1.10 g, 65%). 103 Characterization data for 3.9: IR (cm -1 ) 1593 (s, vN0). 1 H NMR (300 MHz, C6D6) two isomers are present in an approx. 3:1 ratio. 8 (major isomer) -0.62 (d, 2JHH = 13.2, 1H, CH2SiMe3), -0.09 (d, 2JHH = 13.2, 1H, CH2SiMe3), 0.37 (s, 9H, SiMe3), 1.01 (m, 1H, allyl CHMe), 1.48 (s, 15H, C 5Me5), 1.58 (d, 3JHH= 13.8, 1H, allyl CH 2), 1.88 (d, 3JHH = 5.8, 3H, ally! Me), 3.36 (d, 3JHH = 7.0 1H, allyl CH2), 5.10 (ddd, 3JHH = 13.8, 3JHH = 9.4, 3JHH = 7.0, 1H, allyl CH). 8 (minor isomer) selected signals —0.76 (d, 2JHH = 13.2, 1H, CH2SiMe3), -0.48 (d, 2JHH = 13.2, 1H, CH2SiMe3). 0.40 (s, 9H, SiMe3), 1.34 (d, 3JHH = 5.8, 3H, allyl Me), 1.49 (s, 15H, C 5Me5), 2.12 (m, 1H, ally! CH2), 2.24 (m, 1H, ally! CH), 4.61 (m, 1H, ally! CH). 13C{ 1 11} NMR (75 MHz, C6D6) 8 -6.2 (CH2 SiMe3), 4.1 (CH2SiMe3), 10.3 (C5Me5), 17.1 (ally! Me), 53.3 (ally! CHMe), 74.5 (ally! CH2), 106.5 (C5Me5), 114.2 (ally! CH). MS (LREI, in/z, probe temperature 100 °C) 491 [Ml. Anal. Calcd. for C18H33NOW: C, 44.00; H, 6.77; N, 2.85. Found: C, 44.04; H, 6.90; N, 2.85. 3.4.7 Preparation of Cp*W(N0)(NC4H8)(CHMeCH2NC4H8) (3.10) In a 4-dram vial inside a glove box complex 3.5 (46 mg, 0.10 mmol) was dissolved in excess pyrrolidine (2 mL). The mixture was allowed to stand for 5 h, after which pyrrolidine was removed in vacuo. The orange-brown residue was redissolved in pentane, and the solution was filtered through Celite. Subsequent concentration and cooling to —30 °C overnight yielded thin orange needles of Cp*W(N0)(NC4F18)(CHMeCH2NC4H8). X-Ray quality crystals were obtained when Et20 was employed as the crystallization solvent. Yield 21mg (40%). 104 Characterization data for 3.10: IR: 1553 (s, vN0). 1 H NMR (400MHz, C6D6): 8 selected signals 1.18-1.46 (m, 5H, pyrrolidyl CH2), 1.54 (d, 3JHH = 7.2, 3H, WCHMe), 1.72 (s, 15H, C5Me5 and m, 1H, WCHMe), 2.51 (m, 2H, CNCH2), 2.76 (m, 2H, CNCH2), 2.83 (m, 1H, WNCH2), 3.11 (m, 1H, WNCH2), 3.43 (dd, 2JHH = 12.0, 3JHH = 3.9, 1H, WCHMeCH2), 3.60 (t, 2JHH = 12.0, 3JHH = 12.0, WCHMeCH2), 4.03 (m, 1H, WNCH2), 4.34 (m, 1H, WNCH2). 13C{ I H} NMR (100 MHz, C6D6) 8 9.5 (C5Me5), 21.1 (WCHMe), 24.1, 26.3, 26.5 (pyrrolidyl CH2), 42.9 (WCHMe), 53.8 (pyrrolidyl CNCH2), 58.0, 67.5 (WNCH2), 68.2 (WCHMeCH2), 109.9 (C5Me5). MS (LREI, m/z, probe temperature 100 °C) 531 [M+]. Anal. Calcd. for C211-137N30W: C, 47.47; H, 7.02; N, 7.91. Found: C, 47.34; H, 6.96; N, 7.85. 3.4.8 Preparation of Cp*W(N0)(NC51110)(CHMeCH2NC5H10) (3.11) In a 4-dram vial inside a glove box complex 3.5 (92 mg, 0.200 mmol) was dissolved in excess piperidine (2 mL). The mixture was allowed to stand for 2 d, after which piperidine was removed in vacuo. The orange-brown residue was extracted with pentane, leaving behind an off-white unidentifiable residue. The solution was filtered through Celite. Subsequent concentration and cooling of the filtrate to —30 °C overnight afforded 3.11 as orange needles. Yield 22 mg (21%). Characterization data for 3.11: IR: 1561 (s, vN0). 1 11 NMR (400MHz, C6D6): 8 selected signals 1.20-1.50 (m, pyrrolidyl CH2), 1.64 (d, 3JHH = 7.2, 3H, WCHMe), 1.71 (s, 15H, C5Me5), 2.39 (m, 2H, CNCH2), 2.77 (m, 2H, CNCH2), 3.05 (m, 1H, WNCH2), 3.17 105 (m, 1H, WNCH2), 3.38 (t, 2JHH = 12.0, 3JHH = 12.0, WCHMeCH2), 3.54 (dd, 2JHH = 12.0, 3JHH = 3.9, 1H, WCHMeCH2), 3.90 (m, 1H, WNCH2), 4.64 (m, 1H, WNCH2). "COM NMR (100 MHz, C6D6) 6 9.6 (C5Me 5), 21.1 (WCHMe), 24.3, 25.6, 26.9, 28.2, 29.0 (piperidyl CH2), 41.3 (WCHMe), 54.8 (pyrrolidyl CNCH2), 60.7, 70.3 (WNCH2), 71.7 (WCHMeCH2), 109.9 (C5Me5). MS (LREI, m/z, probe temperature 100 °C) 559 [M+]. Anal. Calcd. for C23H4INOW: C, 49.36; H, 7.39; N, 7.51. Found: C, 49.24; H, 7.26; N, 7.47. 3.4.9 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-Me2CCH=CH2) (3.12) Revisited In a 4-dram vial inside the glove box, complex 3.1 (97.1 mg, 0.199 mmol) was dissolved in pyrrolidine (2 mL) for 17 h at room temperature. The final reaction mixture was taken to dryness in vacuo, and the residue was dissolved in a minimum of pentane. The pentane solution was chromatographed on a column of alumina (1 x 3 cm) with pentane as eluant to develop a single orange band that was eluted and collected. Concentration of the eluate under reduced pressure and cooling at -30 °C overnight resulted in the deposition of 3.12 as an orange crystalline solid (58 mg, 52% yield). Characterization data for 3.12: IR (cm -1 ) 1561 (s, vN0). 1 1-1 NMR (500 MHz, C6D6) 6 0.67 (d, 2JHH = 14.09, 1H, CH2CMe3), 1.06 (s, 3H, Me2C), 1.17 (s, 3H, Me2C), 1.18 (d, 2JHH = 14.09, 1H, CH2CMe3), 1.36 (s, 9H, CMe3), 1.48-1.61 (m, 3H, pyrrolidine H), 1.67 (s, 15H, C5Me 5), 1.80-1.89 (m, 1H, pyrrolidine H), 3.00 (m, 1H, pyrrolidine NCH2), 3.20 106 (m, 1H, pyrrolidine NCH2), 4.89-5.00 (m, 3H, pyrrolidine NCH and H 2C=CH). 5.81 (dd, 3JHH = 17.5, 341H = 10, 1H, H2C=CH). 13 C { I FI} NMR (125 MHz, C6D6) 6 10.0 (C5Me 5 ), 23.6 (Me2C) 23.8 (pyrrolidine CH2), 24.0 (Me2C) 24.5 (Me2C), 28.0 (pyrrolidine CH2), 34.4 (CH2CMe3), 37.1 (CH2CMe3), 54.4 (CH2CMe3), 58.9 (pyrrolidine NCH 2), 85.0 (pyrrolidine NCH), 110.2 (C5Me5), 111.8 (CH2=CH), 146.4 (CH2=CH). MS (LREI, m/z, probe temperature 120 °C) 558 [Mt], 489 [M-allyr]. Anal. Calcd. for C24H42N20W: C, 51.62; H, 7.58; N, 5.02. Found: C, 51.93; H, 7.90; N, 5.01. 3.4.10 Preparation of Cp*W(N0)(CH2CMe3)(NC5H9-2-Me2CCH=CH2) (3.13) Revisited In a 4-dram vial inside a glove box a sample of compound 3.1 (90.3 mg, 0.185 mmol) was dissolved in piperidine (2 mL), and the solution was set aside for 1 week at room temperature. The final reaction mixture was taken to dryness, and the residue was dissolved in a minimum amount of pentane. This solution was then chromatographed on a column of alumina (1 x 3 cm) with pentane as eluant to obtain an orange eluate that was collected. Concentration of the eluate under reduced pressure and cooling to -30 °C overnight resulted in the deposition of 3.13 as an orange microcrystalline material. Characterization data for 3.13: IR (cm -1 ) 1564 (s, vNo). 'H NMR (500 MHz, C6D6) 6 1.10 (s, 3H, Me2C), 1.20 (m, 1H, piperidine H), 1.23 (s, 3H, Me2C), 1.29 (d, 2JHH = 5.92, 1H, CH2CMe3), 1.36 (m, 1H, piperidine H), 1.41 (s, 9H, CMe3), 1.50 (m, 1H, piperidine H), 1.69 (d, 2JHH = 5.92, 1H, CH2CMe3), 1.69 (s, 15H, C 5Me5), 1.72-1.75 (m, 2H, 107 piperidine H), 2.03-2.05 (m, 1H, piperidine H), 3.01 (br d, 1H, piperidine NCH 2), 3.63 (td, 3JHH = 12, 4JHH = 3.2, 1H, piperidine NCH2), 4.91 (d, 3JHH = 10.7, 1H, H2C=CH), 4.96 (d, 3JHH = 17.4, 1H, H2C=CH) 5.09-5.11 (br ,1H, piperidine NCH). 6.05 (dd, 3JHH = 17.46, 3JHH= 10.7, 1H, CH2=CH). 13 C{ 1 1-1} NMR (125 MHz, C6D6) 6 10.0 (C 5Me5), 20.4 (piperidine CH2), 23.5 (Me2C), 26.4 (piperidine CH2), 26.6 (Me2C), 27.6 (piperidine CH2), 34.6 (CH2CMe 3), 37.0 (CH2CMe3), 49.4 (CH2CMe3), 56.0 (piperidine NCH 2), 81.4 (piperidine NCH), 110.3 (C 5Me5), 110.8 (CH2=CH), 148.9 (CH2=CH). The signal for CH2=CH-CMe2 is probably obscured. MS (LREI, m/z, probe temperature 120 °C) 572 [M1, 503 [M-allyll. Anal. Calcd. for C25H4N2OW: C,52.45; H, 7.75; N, 4.89. Found: C, 52.18; H, 7.74; N, 5.29. 3.4.11 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-CH2CMe=CH2) (3.14) In a small Schlenk tube complex 3.6 (95.0 mg, 0.200 mmol) was dissolved in pyrrolidine (2 mL), and the mixture was stirred under a gentle flow of N2 for 64 h, after which time the volatiles were removed in vacuo. The orange-yellow residue was redissolved in a minimum of pentane and chromatographed on alumina using 3:1 pentane/Et20 as eluant. The orange band that developed was eluted from the column and collected, and the solvent was removed in vacuo. NMR spectroscopy revealed that the residue was an approx. 60:40 mixture of 3.6 (starting material) and 3.14. The yellow- orange solid was extracted with cold pentane (-30 °C, 2 x 3 mL), leaving behind mostly 3.6 which is the less soluble of the two species. The extracts were combined and reduced 108 in volume. Complex 3.14 was fractionally crystallized as fine yellow-orange rods (18 mg, 16%). Longer reaction times led to the decomposition of 3.14 into an off-white solid. Characterization data for 3.14: IR (cm-1 ) 1563 (s, vN0). 1 H NMR (400 MHz, C6D6) 6 0.79 (d, 2JHH= 14.0, 1H, CH2CMe 3), 0.97 (d, 2JHH = 14.0, 1H, CH2CMe3), 1.39 (s, 9H, CH2CMe3), 1.47 (m, 1H, pyrrolidine CH2), 1.65 (s, 15H, C 5Me5), 1.70 (m, 1H, pyrrolidine CH2), 1.95 (t, 3JHH = 11.6, 1H, H2C=CMe—CH2), 1.96 (s, 3H, H2C=CMe), 2.74 (dd, 3JHH= 4.0, 3JHH= 11.6, 1H, H2C=CMe—CH2), 3.03 (m, 2H, pyrrolidine NCH2), 4.80-4.83 (overlapping br s, 2H, H2C=CMe), 5.14 (m, 1H, pyrrolidine NCH). Other pyrrolidine CH2 signals are obscured. 13C{ 1 H} NMR (100 MHz, C6D6) 6 9.6 (C5Me5), 22.2 (H2C=CMe), 26.0 (pyrrolidine CH2), 31.0 (pyrrolidine CH2), 34.6 (CH2CMe3), 37.3 (CH2CMe3), 50.1 (H2C=CMe—CH2), 57.9 (pyrrolidine NCH2), 58.4 (CH2CMe3), 75.0 (pyrrolidine NCH), 109.7 (C5Me 5), 112.2 (H2C=CMe), 144.5 (H2C=CMe). MS (LREI, m/z, probe temperature 120 °C) 544 [Mt], 489 [M-allylt]. Anal. Calcd. for C23H40N20W: C, 50.74; H, 7.41; N, 5.15. Found: C, 50.63; H, 7.38; N, 5.03. The reaction was also performed in a sealed vessel in order to detect the H2 being evolved. A 250-mL bomb was charged with complex 3.6 (approx 35.0 mg) and a small stir bar. Pyrrolidine (approx. 5 mL) was added via vacuum transfer, and the contents were stirred for 1 d. The volatiles, including an appropriate amount of pyrrolidine (approx. 0.75 mL), were then vacuum-transferred into a J-Young NMR tube equipped with a C6D6 capillary. The presence of H2 was indicated by a singlet at 4.79 ppm in the 1 FI NMR spectrum. This chemical shift was confirmed by recording the i t1 NMR 109 spectrum of a separately prepared sample of H2 in pyrrolidine in a J-Young NMR tube equipped with a C6D6 capillary. 3.4.12 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-CHMeCH=CH 2) (3.15) Complex 3.15 was synthesized in a manner similar to that described above for the preparation of complex 3.12. The 1 H NMR spectrum of the product mixture in C6D6 indicated the formation of at least two new organometallic species, with compound 3.15 being the major product. The orange-brown crude product residue was redissolved in a minimum of pentane and chromatographed on alumina using 3:1 pentane/Et20 as eluant. The orange band that developed was eluted from the column and collected. Solvent was removed in vacuo, resulting in the recovery of 3.15. The minor products appeared to have decomposed on the column. Complex 3.15 was recrystallized from pentane at -30 °C overnight to yield an orange-yellow microcrystalline solid (18 mg, 22%). Characterization data for 3.15: IR (cm-1 ) 1563 (s, vNo). I ET NMR (400 MHz, C6D6) 8 0.72 (d, 2JHH = 14.4, 1H, CH2CMe3), 0.88 (d, 3JHH = 6.8, 3H, H2C=CH—CHMe), 1.10 (d, 2JHH = 14.4, 1H, CH2CMe3), 1.35 (obscured, 2H, pyrrolidine CH2), 1.37 (s, 9H, CMe3), 1.48 (m, 1H, pyrrolidine CH2), 1.67 (s, 15H, C 5Me5), 1.70 (obscured, 1H, pyrrolidine CH2), 2.79 (m, 1H, H2C=CH—CHMe), 3.02 (m, 2H, pyrrolidine NCH2), 5.01-5.03 (m, 2H, pyrrolidine NCH and H2C=CH), 5.16 (d, 3JHH = 17.2, 1 H, H2C=CH), 5.99 (ddd, 3JHH = 7.2, 3JHH = 10.4, 3JHH = 17.2,1H, H2C=CH). 13 C{ I H} NMR (100 MHz, C6D6) 8 9.8 (C5Me5), 14.6 (H2C=CH—CI-1Me), 25.5 (pyrrolidine CH 2), 28.7 (pyrrolidine CH 2), 34.5 110 (CH2CMe3), 37.1 (CH2CMe3), 45.6 (H2C=CH—CHMe), 55.1 (CH2CMe3), 58.6 (pyrrolidine NCH2), 80.6 (pyrrolidine NCH), 109.9 (C5Me5), 114.1 (H2C–CH), 142.9 (H2C=CH). MS (LREI, m/z, probe temperature 120 °C) 544 [M+], 489 [M-allyn. Anal. Calcd. for C23H40N20W: C, 50.74; H, 7.41; N, 5.15. Found: C, 51.03; H, 7.50; N, 4.94. 3.4.13 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-CHPhCH=CH 2) (3.16) Complex 3.16 was synthesized from 3.8 (30 mg, 0.558 mmol) and pyrrolidine (2 mL) in a manner identical to that described above for the preparation of complex 3.12. The I FI NMR spectrum of the crude product in C6D6 revealed the quantitative conversion of 3.8 into 3.16. Complex 3.16 was worked up in a manner identical to that described above for complex 3.12. Complex 3.16 was crystallized from pentane at -30 °C overnight as an orange-yellow microcrystalline solid (24 mg, 71%). Characterization data for 3.16: IR (cm-1 ) 1562 (s, vN0). 1H NMR (400 MHz, C6D6) 8 0.86 (d, 2JHH = 14.0, 1H, CH2CMe3), 1.07 (d, 2JHH= 14.0, 1H, CH2CMe3), 1.39 (s, 9H, CMe3), 1.71 (s, 15H, C5Me5), 3.00-3.15 (m, 3H, PhCH and pyrrolidine NCH2), 4.89 (dd, 2JHH = 1.4, 3JHH = 16.9, 1H, H2C=CH), 5.02 (dd, 2JHH – 1.4, 3JHH – 10.0, 1H, H2C=CH), 5.59 (m, 1H, pyrrolidine NCH), 6.78 (dt, 3JHH = 10.0, 3JHH= 16.9, 1H, H2C=CH), 7.01 (m, 1H para CH), 7.11 (m, 2H, meta CH), 7.32 (m, 2H, ortho CH). Other pyrrolidine CH2 signals are obscured. 13C{ I H} NMR (100 MHz, C6D6) 6 10.0 (C5Me5), 23.3 (pyrrolidine CH2), 29.2 (pyrrolidine CH2), 34.5 (CH2CMe3), 37.0 (CH2CMe3), 53.2 (CII2CMe3), 55.8 (pyrrolidine NCH 2), 56.1 (CHPh), 82.8 (pyrrolidine NCH), 110.3 (C5Me5), 115.2 111 (H2C=CH), 126.6 (Ar C), 128.5 (Ar C), 129.1 (Ar C), 143.0 (H2C=CH), 144.3 (Ar ipso C). MS (LREI, m/z, probe temperature 120 °C) 606 [Mt]. Anal. Calcd. for C28H42N2OW: C, 55.44; H, 6.98; N, 4.62. Found: C, 55.23; H, 7.20; N, 4.77. 3.4.14 Preparation of Cp*W(N0)(CH2CMe3)(NC4H7-2-CHPhCH=CH2) (3.17) Complex 3.17 was synthesized by dissolving 3.9 (30 mg, 0.558 mmol) in pyrrolidine (2 mL) for 4 d. The 1H NMR spectrum of the crude product in C6D6 revealed the quantitative conversion of 3.9 into 3.17. Curiously, multiple attempts to obtain 3.17 as a tractable solid was unsuccessful. Characterization data for 3.17: IR (cm-1 ) 1561 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 -0.50 (overlapping d, 2H, CH2SiMe3), 0.38 (s, 9H, CMe3), 1.67 (s, 15H, C5Me 5), 2.90- 3.08 (m, 3H, PhCH and pyrrolidine NCH2), 4.97-5.03 (m, 2H, pyrrolidine NCH and H2C=CH), 5.17 (d, 3./Flii = 17.2, 1H, H2C=CH), 5.98 (ddd, 3JHH = 7.2, 3JHH = 10.4, 3JHH = 17.2,1H, H2C=CH).. Other pyrrolidine CH2 signals are obscured. 13C{ 1 1-1} NMR (100 MHz, C6D6) 8 -7.0 (CH2SiMe3), 3.3 (CH2SiMe3), 9.9 (C 5Me5), 14.5 (H2C=CH—CI-IMe), 25.8 (pyrrolidine CH2), 27.5 (pyrrolidine CH2), 45.3 (H2C=CH—CHMe), 58.6 (pyrrolidine NCH2), 80.9 (pyrrolidine NCH), 109.0 (C5Me5), 114.1 (H2C=CH), 142.8 (H2C=CH). MS (LREI, m/z, probe temperature 120 °C) 560 [Mi. 112 3.4.15 X-Ray Crystallography Data for 3.5 were collected at a temperature of -100.0 + 0.1 0C to a maximum 2 0 value of 56.1° in 0.5 ° oscillations. The structure was solved by direct methods22 using non-overlapped data from the major twin component. Subsequent refinements were carried out using an HKLF 5 format data set containing complete data from the major twin component and overlapped reflections of the second, minor component. All non- hydrogen atoms were refined anisotropically. All allyl hydrogens were located in difference maps and refined isotropically. All other hydrogen atoms were included in calculated positions but not refined. The batch scale refinement showed a roughly 82:18 ratio between the major and minor twin components. The final cycle of full-matrix least- squares refinement on F2 was based on 31125 reflections from both twin components and 219 variable parameters. X-ray crystallographic data for the structure are presented in Table A.8. Data for 3.7 were collected to a maximum 20 value of 55.8 ° in 0.5 ° oscillations. The structure was solved by direct methods22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms Hla, Hlb, H2, H3, H5a and H5b were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4599 observed reflections and 232 variable parameters. X-ray crystallographic data for the structure are presented in Table A.3. 113 Data for 3.8 were collected to a maximum 20 value of 55.8 ° in 0.5 ° oscillations. The structure was solved by direct methods 22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms Hla, H 1 b, H2 and H3 were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 5262 observed reflections and 268 variable parameters. X-ray crystallographic data for the structure are presented in Table A.8. Data for 3.9 were collected to a maximum 29 value of 60.8 ° in 0.5 ° oscillations. The structure was solved by direct methods 22 and expanded using Fourier techniques. The two isomers co-crystallized such that Wl, C5, Sil and the Cp* ligand were crystallographically equivalent in both compounds. The rest of the solution was modeled as two disordered parts, Part A (major isomer) and Part B (minor isomer), present in a 0.67 to 0.33 ratio. All non-hydrogen atoms were refined anisotropically, except for Nlb, C6b and C3b which were refined isotropically. All hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 5957 observed reflections and 278 variable parameters. X-ray crystallographic data for the structure are presented in Table A.7. Data for 3.10 were collected to a maximum 29 value of 47.0 ° in 0.5 ° oscillations. The structure was solved by direct methods22 and expanded using Fourier techniques. The crystal was twinned, and the crystallographic solution contained two molecules of 3.10. In the second molecule, atom ClOA was disordered in two positions in 114 a 0.65 to 0.35 ratio and was modeled isotropically. All other non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 11672 observed reflections and 481 variable parameters. X-ray crystallographic data for the structure are presented in Table A.9. Data for 3.14 were collected to a maximum 20 value of 55.0 ° in 0.5 ° oscillations. The structure was solved by direct methods22 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 5392 observed reflections and 248 variable parameters. X-ray crystallographic data for the structure are presented in Table A.9. For each structure neutral-atom scattering factors were taken from Cromer and Waber. 23 Anomalous dispersion effects were included in Fcalc;24 the values for Of and Ar were those of Creagh and McAuley. 25 The values for mass attenuation coefficients are those of Creagh and Hubbe11. 26 All calculations were performed using SHELXL- 97 . 2 7 115 3.5^References and Notes (1) For examples on studies on isomerisms on transition metal-ally1 complexes, see: (a) Faller, J. W.; Rosan, A, M. J. Am. Chem. Soc. 1976, 98, 3388. (b) Bi, S.; Ariafard, A.; G, Jia.; Lin, Z. Organometallics 2005, 24, 680. (2) Selected reviews in this topic: (a) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257. (b) Trost, B. M.; Van Vranken, D. L. Chem. Rev., 1996, 96, 395. (3) Tran, E. Development of Tungsten Alkylidene Complexes for Activation of Hydrocarbons: Synthesis, Selectivities and Mechanisms. Ph. D. Thesis, University of British Columbia, Vancouver, BC, December 2001. (4) Ng, S.H.K.; Adams, C. S.; Hayton, T. W.; Legzdins, P.; Patrick, B. 0. , J. Am. Chem. Soc. 2003, 125 , 15210. (5) I hereby thank Dr. Chikako Fujita-Takayama for her preliminary work — the reactions between 3.1 and pyrrolidine and piperidine. (6) A related example of this reaction is the N-H / C-H exchange of secondary amines catalyzed at high temperatures by homoleptic transition-metal dimethylamidos M(NMe2),,. See: Nugent, W. A.; Ovenall, D. W.; Holmes, S. J. Organometallics 1983, 2, 161. (7) Schilling, B. E. R.; Hoffmann, R.; Faller, J. W.J. Am. Chem. Soc. 1979, 101, 592. (8) Bent, H. A. Chem. Rev. 1961, 61, 275. (9) Ipaktschi, J.; Mirzaei, F.; Demuth-Eberle, G. J.; Beck, J.; Serafin, M. Organometallics 1997, 16, 3965. (10) Frohnapfel, D. S.; White, P. S.; Templeton, J. Organometallics 1997, 16, 3737. 116 (11) Villanueva, L. A.; Ward, Y. D.; Lachicotte, R.; Liebeskind, L. S. Organometallics 1996, 15, 4190. (12) Adams, R. D.; Chodosh, D. F.; Faller, J. W.; Rosan, A. M. . J Am. Chem. Soc. 1979, 101, 2570. (13) Multiple attempts to study the solid-state structure of 3.1 have been unsuccessful. The solution structure of 3.1 has been deduced by 1) 1 H NOE experiments — irradiation of the Cp* Me signal leads to enhancement of the ally! anti Me signal, thereby suggesting that the allyl is in an endo configuration. 2) 13C NMR and HETCORR experiments — the chemical shift of CMe2 (101.2 ppm) suggests that it resembles a sp2 carbon more so than the CH2 carbon (chemical shift 37.6 ppm), and therefore is more likely to be trans to the NO ligand / cis to the neopentyl ligand. See: Adams, C. S. C-H Activation of Hydrocarbons by Tungsten Alkylidene and Related Complexes. Ph. D. Thesis, University of British Columbia, Vancouver, BC, October 2001. (14) Nucleophilic attack on a metal-bound ally! is a very common reaction type for these complexes. The nucleophilc attack on the related Cp'MoL2(ally1) type complexes have been well documented. In addition to the aforementioned references see: (a) Vanarsdale, W. E.; Winter, R. E. K.; Kochi, J. K. Organometallics 1986, 5, 645. (b) Faller, J. W.; Murray, H. H.; White, D. L.; Chao, K. H. Organometallics 1983, 2, 400. (c) Pearson, A. J.; Khan, Md. N. I.; Clardy, J. C.; Cunheng, H. J Am. Chem. Soc. 1985, 107, 2748. (15) For a recent example of this step of the transformation, see: Amatore, C.; Genin, E.; Jutand, A.; Mensah, A. Organometallics 2007, 26, 1875. 117 (16) If the reverse is true (i.e. nucleophilic attack on the ally' terminal cis to the NO) we would then expect the formation of a diastereomer — inverted stereochemistry at C2 in Figure 3.7 — of complex 3.10. (17) A search of the Cambridge Structural Database (October 2007) reveals that typical W=N distances fall between 1.70 and 1.80 A. (18) Spefically, the neopentyl ligand of 3.7 can be replaced by an n-pentyl ligand by simply dissolving 3.7 in pentane at RT for 1 d. For details regarding the transformation, refer to section 4.2.1 of this thesis. (19) For a review of methods for the synthesis of z\'-pyrrolines, see: Shvekhgeimer, M.-G. A. Chem. Heterocycl. Comp. 2003, 39, 405. (20) Debad, J. D.; Legzdins, P.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1993, 12, 2094. There were instances where the isolation of the bis(allyl)magnesium reagent was unsuccessful, as removal of solvent left behind an intractable oily material. In such cases the oily residue was rediluted with Et20, and the solution was used as such after the concentration of the allylating reagent was determined by an HCl titration. The solution was stored in a resealable glass bomb. (21) Dryden, N. H.; Legzdins, P.; Einstein, F. W. B.; Jones, R. H. Can. J. Chem. 1988, 66, 2100. (22) SIR92: Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A. J. Appl. Cryst. 1993, 26, 343. (23) Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, 1974; Vol. IV. (24) Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 1 7, 781. (25) Creagh, D. C.; McAuley, W. J. International Tables of X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (26) Creagh, D. C.; Hubbell, J. H. International Tables for X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (27) SHELXL97: Sheldrick, G. M. University of Gottingen, Germany, 1997. 118 119 CHAPTER 4 Facile Aliphatic C-H Bond Activation Initiated by Cp*W(N0)(CH2CMe3)(1 3-CH2CHCHMe) 4.1^Introduction * Alkanes are major components of natural gas and petroleum, but are difficult to convert directly to more valuable chemicals since they possess strong C-C and C-H bonds and lack Lewis acidic or Lewis basic sites of reactivity. Alkanes do react with highly reactive species such as free radicals, carbenes, and super acids, but these transformations are generally not selective and do not tolerate other functionalities. Consequently, a goal of researchers in this area of chemistry has been the selective conversion of alkanes to functionalized molecules at low temperatures. While striving for this goal, investigators have expended considerable efforts in recent years to develop transition-metal complexes for the activation and functionalization of alkane C-H bonds, and they have achieved some notable successes.' Particularly noteworthy in this latter regard is the selective oxidation of alkanes in aqueous solution in the presence of platinum salts first reported by Shilov and co-workers Ic and the catalytic, regioselective functionalization of alkanes with borane reagents recently developed by Hartwig and coworkers. le As described in chapter 3, the complex Cp*W(N0)(CH2CMe3)(1) 3 - CH2CHCHMe) (3.7) was originally studied to further understand the general thermal • Portions of this Chapter have been published as a communication. Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P. Selective Activation and Functionalization of Linear Alkanes Initiated under Ambient Conditions by a Tungsten Allyl Nitrosyl Complex. J. Am. Chem. Soc. 2007, 129, 5372 —5373. 120 behaviour of Cp*W(NO)(alkyl)(allyl) complexes. Complex 3.7 was targeted because of its structural resemblance to the well studied Cp*W(N0)(CH2CMe 3)(1 3 -CH2CHCMe2) (3.1)2 and also because of the commercial availability of the Grignard reagent (CH2CHCHMe)MgC1 (Aldrich), the precursor for the diallylmagnesium reagent (CH2CHCHMe)2Mgx(dioxane) required to introduce the ally! ligand onto the W centre. Not long after its synthesis was achieved, it was discovered that complex 3.7 is also a precursor for a C-H activating intermediate. Interestingly, and unlike 3.1, complex 3.7 is unstable even at room temperature. Because of the mild temperature at which the C-H activation process is initiated, many C-H activations that are difficult to perform by traditional transition-metal complexes have become a reality. This chapter summarizes the investigations into the C-H activation of a variety of hydrocarbon substrates initiated by complex 3.7. The intermediate species responsible for the C-H activation step is the elusive r1 2-diene complex, Cp*W(NO)01 2- CH2=CHCH=CH2) (A), which has been trapped as the PMe3 adduct. When dissolved in aliphatic hydrocarbons, complex 3.7 effects facile C-H activations exclusively at terminal positions. Complex 3.7 can tolerate amines, halides, and ethers, but not unsaturations since coupling reactions occur between the ri g-diene intermediate and the unsaturated substrate. Gaseous substrates such as methane and ethane can also be activated under moderate pressures. Finally, the activated hydrocarbyl fragment can be released from the metal centre as an iodoalkane by treatment with 12 at low temperatures. 121 4.2^Results and Discussion 4.2.1 Thermal Instability of Cp*W(N0)(CH2CMe3)(1 3-CH2CHCHMe) (3.7) The synthesis of complex 3.7 has been described in section 3.2 of this Thesis. As stated before, complex 3.7 is thermally sensitive, especially in solution, and has to be kept cold during its preparation and isolation. As a solid, complex 3.7 can be kept for months at -30 °C without significant signs of decomposition. In solution at the same temperature, 3.7 is stable for a few weeks. However, at RT crystals of 3.7 decompose into an intractable brown solid over the course of 2 d. 4.2.2 C-H Activation of n-Pentane -- a Serendipitous Discovery Early on during the investigation of the thermal chemistry of 3.7, a vial of a pentane solution of the complex was mistakenly left at RT outside the freezer inside the glove box. When the sample was next examined two days later, the yellow colour had slightly, but noticeably, darkened. Surprisingly, the 1 H NMR spectrum of the sample redissolved in C6D6 revealed a single Cp* Me resonance, the absence of the neopentyl Me peak, and the appearance of allyl proton signals at slightly different chemical shifts than those of the starting material. Several new broad featureless signals were also visible between 1.30 to 2.00 ppm. This new complex can be chromatographed on alumina and then crystallized from pentane to obtain yellow-orange rods. An X-ray crystallographic analysis reveals the identity of the complex to be Cp*W(N0)(n- 122 C51-111)(11 3-CH2CHCHMe) (4.1). The ORTEP diagram of 4.1 is shown in Figure 4.1. Complex 4.1 is structurally similar to 3.7, apart from the fact that the neopentyl ligand has been replaced by an n-pentyl ligand which apparently is formed by the single C-H activation of n-pentane. The ability of complex 3.7 to perform clean aliphatic C-H bond activation is a fascinating phenomenon. Effecting such transformations for linear alkanes is particularly challenging since the activation of aliphatic C-H bonds at transition-metal centres often requires generation of the active species by high-energy thermal or photochemical means. 3 Secondly, the activations frequently result in the formation of initial organometallic products that are unstable under the experimental conditions employed and undergo decomposition via processes such as 13-hydrogen elimination, which can occur even at low temperatures on the newly formed alkyl ligand, to form a metal ri 2- olefin-hydrido species.4 Such is the case for the Cp*Mo(NO)(alkylidene) system which also operates at room temperature, but does not effect single aliphatic C-H activation unless [3-hydrogens are absent. 5 At even slightly elevated temperatures, which is the usual condition during which the initial single C-H activation product is formed, other decomposition pathways such as a-hydrogen abstraction or reductive elimination are also available. 6 Thirdly, the activations can be non-regioselective since several types of C-H activation sites are usually present on most hydrocarbons.7 123 Figure 4.1. Solid-state molecular structure of Cp*W(N0)(n-05Hi i)( 11 3-CH2CHCHMe) (4.1) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.333(4), W(1)-C(2) = 2.313(3), W(1)-C(3) = 2.294(3), W(1)-C(5) = 2.242(3), W(1)-N(1) = 1.788(3), N(1)-O(1) = 1.216(3), C(1)-C(2) -- 1.363(5), C(2)-C(3) = 1.414(5), C(3)-C(4) = 1.501(5), C(1)-C(2)-C(3) = 118.8(3), C(2)- C(3)-C(4) = 120.6(3), W(1)-C(5)-C(6) = 116.5(2), W(1)-N(1)-0(1) = 174.9(2). Complex 3.7 experiences none of the aforementioned problems. Specifically, the initial C-H activation product 4.1 is an 18e species; therefore it does not readily 124 hydrogen eliminate despite possessing 0-hydrogen atoms on the newly-attached n-pentyl ligand. Furthermore, the transformation occurs at RT, a temperature at which the 18e allyl-pentyl species happens to be stable. For comparison, the reaction between n-pentane and complex 3.1 at 50 °C, the temperature required to generate the reactive Cp*W(N0)(r1 2-olefin) intermediates, only leads to a mixture of organometallic products that are poorly characterized. 8a Also, the thermal reaction of n-pentane initiated by the alkyl-vinyl complex Cp*W(N0)(CH2SiMe3)(11 2-CPhCH2)8b leads to the double C-H activation of n-pentane as well as coupling with the vinyl ligand. Finally, the C-H activation by 3.7 is 100% selective for the terminal positions of pentane, presumably due to a variety of reasons such as steric considerations. 4.2.3 Investigations into the Reactive Intermediate — Trapping and Labelling Studies In order to trap the intermediate species responsible for the C-H activation of n- pentane, compound 3.7 has been dissolved in PMe3 for 1 d whereupon the mixture lightens in color. The 1 1-1 NMR spectrum of the crude product reveals the presence of a new organometallic species — a new Cp* Me signal at 1.65 ppm among a few other peaks in the 1.25 - 2.00 ppm region that have yet to be assigned. The final mixture is not amenable to chromatography on alumina, and therefore the sole organometallic product has to be extracted from a mixture of pale-coloured insoluble solids with multiple portions of cold pentane. Concentrating the extracts and subsequent crystallization yields pale-yellow square plates, and an X-ray crystallographic analysis reveals the identity of 125 this compound to be the PMe3-trapped fl 2-diene complex, Cp*W(N0)(r1 2- CH2=CHCH=CH2)(PMe3) (4.2). The solid-state molecular structure of complex 4.2 is shown in Figure 4.2. Complex 4.2 possesses a three-legged piano-stool type geometry. The diene fragment is 1 2-coordinated, with the metrical parameters clearly indicating the differences between the bound and free olefin units. NMR spectroscopic data indicate that the solid-state molecular structure of complex 4.2 is maintained in solution. The 1 H NMR spectrum of complex 4.2 in C6D6 contains three diagnostic downfield resonances between 4.70 to 6.07 ppm for the protons on the uncoordinated H2C=CH unit and three upfield resonances from 0.32 to 2.04 ppm for the protons on the bound H2C=CH unit. Similarly, in the 13 C { i El} NMR spectrum of 4.2 in the same solvent, the chemical shifts of the signals due to the unbound C=C linkage are much more downfield (149.7 and 102.5 for CH= and CH2=, respectively) than are the chemical shifts for the signals attributable to the bound C=C group (42.7 and 31.4 for CH= and CH2=, respectively). In the IR spectrum of complex 4.2, the NO stretching frequency occurs at 1634 cm -1 , the highest among all the new compounds reported in this Thesis. This high wavenumber is probably a reflection of the competition for metal electron density by three strong n-accepting ligands. 126 Figure 4.2. Solid-state molecular structure of Cp*W(NO)(r12- CH2=CHCH=CH2)(PMe3) (4.2) with 50% probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.221(4), W(1)-C(2) = 2.218(3), W(1)-P(1) = 2.4335(8), W(1)-N(1) = 1.774(3), N(1)-0(1) = 1.230(4), C(1)-C(2) = 1.453(5), C(2)-C(3) = 1.456(5), C(3)-C(4) = 1.306(5), C(1)-C(2)-C(3) = 121.4(3), C(2)- C(3)-C(4) = 126.7(4), W(1)-N(1)-0(1) = 170.1(3). The isolation of complex 4.2 unambiguously establishes that the ri 2 -diene intermediate Cp*W(N0)(T1 2-CH2=CHCH=CH2) (A) is responsible for the C-H activation chemistry initiated by 3.7, although it is unclear why it does so in such a facile manner. It 127 might have been expected that loss of a hydrogen from the ally! terminal methyl group in 3.7, 9 and its metal-mediated transfer to the neopentyl ligand resulting in the loss of CMe4, could lead to the formation of the 18e i 4-trans-diene complex Cp*W(NO)(r14- CH2=CHCH=CH2), which is a thermally stable yellow compound that has been prepared previously in the Legzdins group by treating diethyl ether solutions of Cp*W(NO)(CH2SiMe3)2 at -78 °C with H2 in the presence of 1,3-butadiene. I° It is unlikely that this complex is formed during the C-H activation chemistry initiated by 3.7 since it has also been established previously that such i 4-trans-diene complexes are relatively kinetically inert to substitution by PMe3, 11 a process that would be required for the formation of 4.2. Furthermore, it is highly unlikely that in the presence of n-pentane, Cp*W(N0)(i 4-CH2=CH-C11-- CH2), with its favored 18e configuration at the metal, would open up the coordination position at the tungsten centre required for C-H activation by spontaneously converting to the 16e intermediate A. Hence, we believe that it is A that is formed initially by loss of CMe4 from 3.7. Before the coordinated alkene can rotate about the alkene—metal bond, allowing the uncoordinated diene to approach the metal centre, the reactive intermediate A comes into contact with a solvent molecule and activates a C-H bond, possibly via an oxidative addition pathway, 12 after which the hydrido and the metal-bonded olefin combine to regenerate the 11 3 -ally1 ligand. I3 The isolation of complex 4.2 also leads us to revisit the reaction between PMe 3 and complex 3.1. 2 Since compound 4.2 does not survive chromatography on alumina, and since Steve Ng attempted to purify the crude product from the reaction between 3.1 and PMe3 by the same technique, it is entirely possible that the 11 2-diene-PMe3 adduct from W•....NO Me3P' ,  \ „,W NO 50 °C PMe3 3.1 -CMe4 ,W ....NO Me3 13^\ 128 that reaction was lost during the work-up process and was therefore never identified (Scheme 4.1). Sure enough, by reinspecting the less crowded regions of the 1 H NMR spectrum from the crude product of this latter reaction and by comparing to the spectroscopic data of 4.2, we have identified a multiplet at 0.00 ppm that could very well correspond to a proton on the metal-bound diene double bond. Similarly, two broad singlets at 4.69 and 5.07 ppm, respectively, could correspond to terminal CH2= protons on the free diene double bond which is substituted with a methyl group. Scheme 4.1 w NO not isolated At the same time, the question arises why the 1 2-allene-PMe3 adduct, the only fully characterized product in the case of 3.1, is not isolated in this case. To address this question, a labelling reaction has been conducted. Complex 4.1-d12 has been synthesized by dissolving complex 3.7 in n -05D12 for 1 d, and the result suggests that exactly one n-05Di 2 d11 W NO CH2D 4. 1 -d12 20 °C w ....... ..NO -CMe4 3.7 .1NO  A 129 deuterium is incorporated into the terminal allyl methyl substituent (Scheme 4.2) as indicated by a conspicuous 1:1:1 triplet at 17.5 ppm in the 13 C { 1 1-1} NMR spectrum. This also suggests that the initial C-D activation of n-pentane-d12 occurs exclusively at the terminal position, and not at a CD2 position, since subsequent isomerization of 1- methylbutyl (CD(C 3D7)(CD3)) or 1-ethylpropyl (CD(C2D 5)2) to the observed n-pentyl ligand by a chain-walking type mechanism 14 could very well result in the incorporation of more than one deuterium atom on the methyl group. At the same time, the allyl middle carbon signal in complex 4.1-d12 remains a singlet. This feature indicates that the allene intermediate is not formed at all, otherwise deuterium incorporation onto the allyl middle carbon would have been observed. 2 A possible explanation for this phenomenon is that the loss of the middle allyl hydrogen requires heating, which is not applied during the reaction with 3.7. Scheme 4.2 130 4.2.4 Aliphatic C-H Activation -- Scope of Substrates To investigate the functional group tolerance associated with the C-H activation processes, complex 3.7 has been reacted with a variety of organic substrates. 4.2.4.1 C-H Activation of Linear and Branched Hydrocarbons Treatment of 3.7 with n-heptane leads to the formation of Cp*W(N0)(n- C7H15)(1 3-CH2CHCHMe) (4.3). As in the case of n-pentane, C-H activation occurs exclusively at the terminal positions. Treatment of 3.7 with methylcyclohexane also leads to the exclusive formation of the terminal C-H activation product Cp*W(N0)(CH2(cyclohexyl))(1 3 -CH2CHCHMe) (4.4). For comparison, the reaction between methylcyclohexane and 3.1 at 50 °C leads to the triple C-H activation of the substrate and the formation of a exocyclic allyl-hydrido species, after the methylallyl ligand is eliminated from initial C-H activation product. 2 This difference in reactivity illustrates the importance of effecting the initial C-H activation under mild conditions. Finally, treatment of 3.7 with cyclohexane only leads to an intractable mixture of organometallic products. 15 This indicates that the scope of C-H activation of aliphatic hydrocarbons is limited to primary C-H bonds. With a judicious choice of solvents, C-H activation of gaseous hydrocarbons can also be effected under moderately elevated pressures: 6 Cp*W(N0)(CH2CH2CH3)(r1 3 - CH2CHCHMe) (4.5) is formed in moderate yields by stirring a C6F6 17 solution of 3.7 131 under an atmosphere of propane (ca. 150 psi) 18 for 1 d. Cp*W(NO)(CH2CH3)(11 3 - CH2CHCHMe) (4.6) and Cp*W(N0)(CH3)(r1 3 -CH2CHCHMe) (4.7) can be obtained in moderate yields by pressurizing a 1.5 mL solution of 3.7 (ca. 50 mg) in C6F6 and cyclohexane, respectively, with ethane (400 psi) and methane (1000 psi) in a stainless steel pressure reactor for the same amount of time. The solid-state molecular structure of complex 4.6 is shown in Figure 4.3 as a representative example of these products. 19 4.2.4.2 C-H Activation of Heteroatom-Containing Saturated Substrates Treatment of 3.7 with tetramethylsilane (SiMe 4) leads to the expected formation of Cp*W(N0)(CH2SiMe3)(r1 2-CH2CHCHMe) (3.9), which can also be obtained via a metathetical route as described in Chapter 3 of this Thesis. Treatment of 3.7 with 1- chloropentane, 2° diethyl ether, and triethylamine all leads to exclusive formation of the terminal C-H activation products, namely, Cp*W(NO)((CH2) 4C1)(r1 2 -CH2CHCHMe) (4.8), Cp*W(N0)(CH2CH2OCH2CH3)(112-CH2CHCHMe) (4.9) and Cp*W(N0)(CH2CH2N(CH2CH3)2)(r1 2-CH2CHCHIVIe) (4.10), respectively. Particularly notable in the case of the triethylamine reaction is the fact that the 18e r1 2-diene-amine adduct is not observed. 132 Figure 4.3. Solid-state molecular structure of Cp*W(N0)(CH2CH3)(r1 3 -CH2CHCHMe) (4.6) with 35 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1a) = 2.368(14), W(1)-C(2a) = 2.285(8), W(1)-C(3a) -- 2.174(12), W(1)-C(5a) = 2.332(11), W(1)-N(1) = 1.772(3), N(1)-0(1) = 1.218(4), C(la)- C(2a) = 1.320(17), C(2a)-C(3a) = 1.398(12), C(3a)-C(4a) = 1.556(16), C(5a)-C(6a) = 1.099(16), C(la)-C(2a)-C(3a) = 117.4(11), C(2a)-C(3a)-C(4a) = 93.8(9), W(1)-C(5a)- C(6a) = 133.6(11), W(1)-N(1)-0(1) = 169.3(3). W NO A ally! W- NO^isomerization W - NO 4.11 133 4.2.4.3 Attempted C-H Activation of Unsaturated Substrates Treatment of 3.7 with cyclohexene leads to the exclusive formation of Cp*W(N0)(r1 3 ,r1 1 -CH2CHCHCH2C01-1(C4H8)C,,H) (4.11). Complex 4.11 is analogous to Cp*W(N0)(11 3 ,i 1 -CH2CHCMeCH2C011(C4H8)C aH) (3.4), which is formed between cyclohexene and the then-putative r1 2-diene intermediate generated from 3.1. 2 The proposed mechanism for the formation of 4.11 involves 1) the coordination of cyclohexene to the metal centre, 2) the coupling between the two coordinated olefins, and 3) the ri 1 -1 3 isomerization of the allylic portion of the organic fragment (Scheme 4.3). The solid-state molecular structure of 4.11 is shown in Figure 4.4. Scheme 4.3 134 Treatment of 3.7 with acetone, 3-pentanone, and 2-butyne all leads to the same type of coupling product that results from the reaction between 3.7 and cyclohexene. Cp*W(NO)(r1 3 ,ri 1 -CH2CHCHCH2C(CH3)20) (4.12) is formed as the principal organometallic product, while Cp*W(NO)(r1 3 ,11 1 -CH2CHCHCH2C(CH2CH3)20) (4.13) and Cp*W(NO)(r1 3 ,ri l -CH2CHCHCH2CCH3=CCH3) (4.14) are formed exclusively. These organometallic species can all be purified by chromatography on alumina. This type of coupling reaction has been reported previously to occur between Cp'Mo(NO)(r1 4- diene) complexes (Cp' = Cp or Cp*) and acetone. 21 The solid-state molecular structures of 4.13 and 4.14 have been established by X-ray crystallographic analyses and are shown in Figures 4.5 and 4.6, respectively. 135 Figure 4.4.^Solid-state molecular structure of Cp*W(NO)(r1 3 ,r1 1 - CH2CHCHCH2CpH(C4H8)C,H) (4.11) with 50 % probability thetmal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.267(19), W(1)-C(2) =- 2.301(19), W(1)-C(3) = 2.44(2), W(1)-C(6) = 2.22(2), W(1)-N(1) = 1.78(2), N(1)-O(1) =- 1.19(3), C(1)-C(2) = 1.43(3), C(2)-C(3) = 1.39(3), C(3)-C(4) = 1.49(3), C(4)-C(5) = 1.54(3), C(5)-C(6) = 1.46(3), C(1)-C(2)-C(3) = 120(2), C(2)-C(3)-C(4) = 127(2), C(3)- C(4)-C(5) = 104.3(19), C(4)-C(5)-C(6) = 110(2), W(1)-C(6)-C(5) = 115.9(16), W(1)- N(1)-O(1) = 170.6(17). 136 Figure 43. Solid-state molecular structure of Cp*W(N0)(n 3 ,n I -CH2CHCHCH2C(CH2CH3)20) (4.13) with 50 % probability thermal ellipsoid shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.227(4), W(1)-C(2) = 2.336(3), W(1)-C(3) = 2.437(4), W(1)-0(2) = 2.012(3), W(1)-N(1) = 1.763(3), N(1)-O(1) = 1.230(4), C(1)-C(2) = 1.447(6), C(2)-C(3) = 1.363(6), C(3)-C(4) = 1.488(5), C(4)-C(5) = 1.565(5), C(5)-O(2) = 1.413(4), C(1)-C(2)-C(3) = 117.9(4), C(2)-C(3)-C(4) = 124.3(4), C(3)-C(4)-C(5) = 109.0(3), C(4)-C(5)-O(2) = 107.8(3), W(1)-O(2)-C(5) = 122.6(2), W(1)-N(1)-O(1) = 171.4(3). 137 Figure 4.6.^Solid-state molecular structure of Cp*W(N0)(11 3 01 1 - CH2CHCHCH2CCH3=CCH3) (4.14) with 50 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.228(3), W(1)-C(2) 2.299(3), W(1)-C(3) = 2.360(3), W(1)-C(6) = 2.191(3), W(1)-N(1) = 1.766(3), N(1)-O(1) = 1.212(4), C(1)-C(2) = 1.410(5), C(2)-C(3) = 1.381(5), C(3)-C(4) = 1.488(4), C(4)-C(5) = 1.503(4), C(5)-C(6) = 1.325(4), C(1)-C(2)-C(3) = 117.3(3), C(2)-C(3)-C(4) = 125.0(3), C(3)-C(4)-C(5) = 108.9(2), C(4)-C(5)-C(6) = 119.4(3), W(1)-C(6)-C(5) = 123.5(2), W(1)-N(1)-0(1) = 169.8(2). 138 When the site of unsaturation is sufficiently sterically hindered, as in the case of 2,3-dimethyl-2-butene, C-H activation again becomes dominant, and so the C-H activation product, Cp*W(N0)(i 1 -CH2C(CH3)C(CH3)2)(r1 3-CH2CHCHMe) (4.15), is formed exclusively from 3.7. 20 The solid-state molecular structure of 4.15 is shown in Figure 4.7. In complex 4.15 the newly-formed 2,3-dimethyl-2-butenyl ligand exhibits an il l -binding mode, while the original 1-methylally1 ligand remains 11 3 -bonded to the metal centre.22 4.2.5 Attempted Aryl C-H Activation of Aromatic Substrates During C-H activations by transition-metal complexes, benzene usually yields the cleanest reactions, because 1) benzene possesses one type of C-H bond, and 2) the resulting metal-aryl-carbon bond is more thermodynamically stable than a metal- aliphatic-carbon bond. 23 Curiously, the same does not apply in the case of complex 3.7. Treatment of complex 3.7 with benzene under ambient conditions only affords a brown solution that consists of a mixture of as yet unidentified organometallic compounds. Treatment of complex 3.7 with toluene also produces a mixture of possibly aryl- and alkyl-C-H activation products, 16 as evidenced by four allyl meso-proton signals in the NMR spectrum. Attempts to separate these complex by chromatography on alumina led to the isolation of the benzyl allyl complex Cp*W(N0)(CH2C6115)(11 3 -CH2CHCHMe) (4.16) (Figure 4.7), as evidenced by its characteristic signals in the 1 H NMR spectrum. 139 Figure 4.7.^Solid-state molecular structure of Cp*W(N0)(ri I - CH2C(CH3)C(CH3)2)(i 3-CH2CHCHMe) (4.15) with 50 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.361(6), W(1)- C(2) = 2.302(6), W(1)-C(3) = 2.290(6), W(1)-C(5) = 2.261(5), W(1)-N(1) = 1.761(6), N(1)-O(1) = 1.224(7), C(1)-C(2) = 1.357(9), C(2)-C(3) = 1.417(8), C(3)-C(4) = 1.485(10), C(5)-C(6) = 1.485(8), C(6)-C(7) = 1.350(8), C(1)-C(2)-C(3) = 120.4(7), C(2)- C(3)-C(4) = 120.6(7), W(1)-C(5)-C(6) = 121.6(4), C(5)-C(6)-C(7) = 123.7(6), C(6)- C(7)-C(8) = 124.3(6), W(1)-N(1)-0(1) = 170.9(5). 140 Presumably, the aryl C-H activation products are unstable, as in the case of product(s) from the benzene C-H activation reaction, and readily decompose on alumina. Regarding the solid-state molecular structure of 4.16, the metrical parameters for the allyl ligand are typical, and the benzyl ligand adopts an ri 1 -binding motif to the metal centre. This feature contrasts with those in related Cp*W(NO)(benzyl)(alkyl) complexes in which the benzyl ligand is r1 2-coordinated to the meta1. 24 Complex 4.16 has been formed in 23% NMR yield according to the integration of the meso-proton signals of the various allyl- containing species. This benzyl regioselectivity is similar to what has been observed during the C-H activation of toluene effected by 3.1.2 141 Figure 4.8. Solid-state molecular structure of Cp *W(N0)(CH2C6Hs)(71 3 - CH2CHCHMe) (4.16) with 50 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.410(7), W(1)-C(2) = 2.311(6), W(1)-C(3) = 2.299(6), W(1)-C(5) = 2.216(7), W(1)-N(1) = 1.770(5), N(1)-O(1) = 1.190(6), C(1)-C(2) = 1.395(9), C(2)-C(3) = 1.436(9), C(3)-C(4) = 1.458(10), C(1)-C(2)- C(3) = 120.5(6), C(2)-C(3)-C(4) = 120.5(6), W(1)-C(5)-C(6) = 117.8(4), W(1)-N(1)-O(1) = 170.2(5). 142 4.2.6 Attempted Functionalization of C-H Activated Fragments To complete the transformation of an alkane into a functionalized species, the representative complex 4.1 has been treated with a variety of reagents. Treatment of a CDC13 solution of 4.1 with solid 12 (2 equivalents) at RT leads to a large number of organic and organometallic products, as evidenced by a myriad of peaks in various regions of the 1 1-1 NMR spectrum of the final mixture. A triplet at 3.20 ppm could very well be the signal for the a-protons of n-pentyl iodide, as supported by the 1 1-1 NMR spectrum of an authentic sample of the organic compound in the same solvent. However, the NMR yield is only ca. 10% according to integration against HMDS, which has been added as the internal standard. By lowering the reaction temperature to —60 °C and adding the 12 as a CDC1 3 solution in a dropwise manner, the NMR yield can be improved to ca. 70%. 25 In addition, signals due to the known compound Cp*W(NO)I2 can be detected in both the 1 1-1 NMR and IR spectra of the solid residue after vacuum transfer of the volatiles, which are analyzed separately. An ELMS analysis of the volatiles supports the presence of n-pentyl iodide, and indicates that at least one isomer of methylallyl iodide is also formed. However, the exact identity of these isomer(s) is not decipherable from the 1 1-1 NMR data. Unfortunately, attempts to release the n-pentyl fragment by a variety of other chemical methods lead either to no reaction or no identifiable products. It should be noted that the use of heat during these functionalizations is not feasible, because complex 143 4.1 loses n-pentane and re-forms the 11 2-diene intermediate. This fact has been confirmed by the formation of 4.2 when 4.1 is heated in PMe3 at 35 °C for 5 d. No reaction occurs when oxygen gas is bubbled through a C6D6 solution of 4.1 for 16 h. Treatment of 4.1 with benzoyl peroxide or cumene hydroperoxide also leads to no reaction. Treatment of 4.1 with a suspension of AgBF4 in NMR solvents (C6D 6 or CDC13) leads to the deposition of a silver mirror, but the 1 H NMR spectrum of the resulting solution is devoid of decipherable signals. Treatment of 4.1 with PC1 5 leads to no tractable organic or organometallic products. Treatment of 4.1 with pivaloyl chloride leads to no discernible organometallic product and at least two new organic species, one of which possesses a 1-methyl-2-propenyl substituent, resulting from the liberation of the methylallyl ligand from the metal centre, according to 1 E1 NMR spectroscopic analyses. Finally, treatment of 4.1 with pyrrolidine for 16 h results in no reaction — this result has been described in Chapter 3 of this Thesis. 4.3^Conclusion In summary, we have discovered a unique tungsten ally! nitrosyl complex (3.7) that selectively activates the terminal C-H bonds of n-alkanes under ambient conditions and forms thermally stable n-alkyl complexes that may be isolated and fully characterized. In addition, we have found that the n-alkyl ligands can be released from these complexes in a derivatized form with the functional group at the terminal position. 3.7 can initiate similar C-H bond activations on saturated organic molecules even in the -CMe4 base -HX Overall transformation HR + EX^HX +ER E = electrophile (e.g. H+ , RC=0+ , Ph3C + ) ER ^EX X = counteranion (e.g.^SO3CF3 - ) W....NO 144 presence of functional groups containing heteroatoms such as nitrogen, oxygen and chlorine. Further efforts will include investigations on the optimal conditions to selectively release the activated hydrocarbyl fragment, and the potential development of a catalytic cycle, such as the one shown in Scheme 4.5, which invokes the electrophilic funtionalization of the newly formed hydrocarbyl fragment. Scheme 4.5 With the initiation and step 1 of the catalytic cycle established, the next challenges are as follows: 1) the discovery of electrophiles that will preferentially attack 145 the new hydrocarbyl fragment over the methylallyl ligand, and 2) the search for a suitable non-coordinating base that can facilitate the loss of HX from Cp*W(N0)(r1 3 - CH2CHCHMe)X. Studies on individual steps of this catalytic cycle are currently in progress in the Legzdins group. 4.4^Experimental Procedures 4.4.1 General Considerations All reactions and subsequent manipulations involving organometallic reagents were performed under anaerobic and anhydrous conditions either under high vacuum or an inert atmosphere of pre-purified dinitrogen. Purification of inert gases was achieved by passing them first through a column containing MnO and then a column of activated 4 A molecular sieves. Conventional glove box and vacuum-line Schlenk techniques were utilized throughout. The glove boxes utilized were Innovative Technologies LabMaster 100 and MS-130 BG dual-station models equipped with freezers maintained at — 30 °C. Most of the reactions were performed in thick-walled glass vessels possessing Kontes greaseless stopcocks and side-arm inlets for vacuum-line attachment. All solvents were dried with appropriate drying agents under a dinitrogen atmosphere and were distilled prior to use, or they were transferred directly under vacuum from the appropriate drying agent. Hexamethyldisiloxane (HMDS), hydrocarbon solvents, diethyl ether, and tetrahydrofuran were dried and distilled from sodium benzophenone ketyl. Commercially available (CH2CHCHMe)MgC1 (Aldrich, 0.5 M in THF) was transformed into the 146 corresponding diallylmagnesium reagents in the usual manner. 26 Cp*W(NO)(CH2CMe3)Cl was prepared according to published procedures. 27 The synthesis of Cp*W(N0)(CH 2CMe3)(r1 3-CH2CHCHMe) (3.7) has been described in Chapter 3 of this Thesis. All other chemicals are used as received. The progress of most reactions was monitored by NMR spectroscopy, and the isolated yields of all new complexes have not been optimized. All IR samples were prepared as Nujol mulls, and their spectra were recorded on a Thermo Nicolet 4700 FT-IR spectrometer. NMR spectra were recorded at room temperature on Bruker AV-300 or AV-400 spectrometers. All chemical shifts are reported in ppm, and all coupling constants are reported in Hz. 1 H NMR spectra are referenced to the residual protio isotopomer present in a particular solvent, and 13C NMR spectra are referenced to the natural-abundance carbon signal of the solvent employed. Where necessary, 1 H- 1 H COSY, 1 H- 13C HMQC, 1 H- 13C HMBC, and 13C APT experiments were carried out to correlate and assign 1 H and 13 C NMR signals. Low- resolution mass spectra (EI, 70 eV) were recorded by the staff of the UBC mass spectrometry facility using a Kratos MS-50 spectrometer. Elemental analyses were performed by Mr. Minaz Lakha of the UBC microanalytical facility. 4.4.2 Preparation of Cp*W(N0)(n-05H0(T1 3-CH2CHCHMe) (4.1) In a glove box a sample of 3.7 (60.0 mg, 1.26 mmol) was dissolved in pentane in a 4-dram vial, and the solution was set aside. After 20 h, the solution, which had 147 darkened slightly in color, was transferred to the top of an alumina I column (0.5 x 5 cm) supported by glass wool in a Pasteur pipette. The column was eluted with 3:1 pentane/Et20, and the yellow band that developed was eluted and collected. The solvent was removed from the eluate in vacuo, and the oily residue was redissolved in pentane (2 mL). The solution was stored at -30 °C overnight to induce to deposition of orange rods of 4.1 (48 mg, 81 %). Characterization data for 4.1: IR (cm -1 ) 1597 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 1.04 (t, 3./HH= 7.3, 3H, n-pentyl Me), 1.07 (overlapping m, 1H, n-pentyl CH2), 1.11 (overlapping m, 1H, ally' CHMe), 1.40 (m, 2H, n-pentyl CH 2), 1.49 (obscured, 3H, n- pentyl CH2), 1.50 (s, 15H, C5Me5), 1.51 (obscured, 1H, ally! CH2), 1.59 (m, 1H, n-pentyl CH2), 1.93 (d, 3JHH = 5.8, 3H, ally! Me), 2.08 (m, 1H, n-pentyl CH2), 3.23 (d, 3JHH= 7.2, 1H, ally! CH2), 4.89 (ddd, 3./11H = 7.2, 3./xx = 9.6, 3JHH = 13.6, 1H, ally! CH). 13 C { 1 H} NMR (100 MHz, C6D6) 8 9.4 (C5Me5), 14.7 (n-pentyl Me), 16.2 (n-pentyl CH2), 17.7 (allyl Me), 23.0 (n-pentyl CH2), 34.0 (n-pentyl CH2), 39.3 (n-pentyl CH2), 54.1 (allyl CHMe), 74.4 (ally! CH2), 105.5 (C5Me5), 109.5 (ally! CH). MS (LREI, m/z, probe temperature 120 °C) 475 [M+]. Anal. Calcd for Ci9H33NOW: C, 48.01; H, 7.00; N, 2.95. Found: C, 47.92; H, 6.91; N, 3.17. The compound Cp *W(N0)(n-05D11)(1 3-CH2CHCHCH2D) (4.1-d12) was similarly prepared from 3.7 and n-05D12. The 1 H NMR spectrum of 4.1-d12 displays similar features arising from the ally! ligand, with the exception that the methyl proton signal at 8 1.93 now appears as a multiplet. The 13 C { 1 H} NMR spectrum exhibits a 1:1:1 148 triplet at 17.5 ppm Om = 19 Hz), indicative of a deuterium atom having been incorporated in the ally! methyl group. 4.4.3 Preparation of Cp*W(N0)(1 2-CH2=CHCH=CH2)(PMe3) (4.2) In a glove box a sample of 3.7 (60.0 mg, 1.26 mmol) was added to a small resealable vessel. At a vacuum line, an excess of PMe3 (2 mL) was vacuum-transferred onto the solid, and the resulting yellow-orange solution was set aside. After 20 h, the solution had lightened in color. The volatiles were then removed in vacuo, and the remaining solid was extracted with cold pentane (-30 °C, 5 x 5 mL), leaving behind an unidentified white residue. The combined extracts were filtered through Celite supported on glass wool in a Pasteur pipette, and the filtrate was reduced in volume in vacuo. Storage of the sample at -30 °C overnight led to the deposition of 4.2 as a yellow microcrystalline solid (25 mg, 41%). Characterization data for 4.2: IR (cm-1 ) 1634 (s, vN0). I I-I NMR (400 MHz, C6D6) 8 0.32 (m, 1H, metal-bound H2C=CH), 1.14 (d, 2JHP = 8.4, 9H, PMe3), 1.59 (m, 1H, metal-bound H2C=CH), 1.65 (s, 15H, C5Me5), 2.04 (m, 1H, metal-bound H2C=CH), 4.70 (dd, 2JHH = 2.0, 3JHH = 10.0, 1H, uncoordinated H2C=CH), 5.15 (dd, 2JHH = 2.0, 3A-a4 =- 16.4, 1H, uncoordinated H2C=CH), 6.07 (dt, 3JHH = 10.0, 3JHH = 16.4, 1H, uncoordinated H2C=CH). 13C { 1 11} NMR (100 MHz, C6D6) 8 10.1 (C5Me5), 16.3 (d, 1 Jcp --- 32.0, PMe3), 31.4 (d, 2Jcp = 12.0, metal-bound H2C=CH), 42.7 (metal-bound H2C=CH), 102.5 (uncoordinated H2C=CH), 103.1 (C5Me5), 149.7 (uncoordinated H2C=CH). MS (LREI, 149 m/z, probe temperature 120 °C) 479 [M+]. Anal. Calcd. for C,7H30NOPW: C, 42.61; H, 6.31; N, 2.92. Found: C, 42.67; H, 6.50; N, 2.72. 4.4.4 Preparation of Cp*W(N0)(n-C71-115)(1 3-CH2CHCHMe) (4.3) Complex 4.3 was prepared from 3.7 (47.5 mg, 0.100 mmol) and n-heptane (2 mL) and purified in manners identical to those described above for the isolation of complex 4.1. Complex 4.3 was isolated as orange irregularly-shaped crystals (21 mg, 42%). Characterization data for 4.3: IR (cm-1 ) 1593 (s, vNo). 1 H NMR (400 MHz, C6D6) 6 0.92 (t, 3JHH = 7.2, 3H, n-heptyl Me), 1.08 (overlapping m, 2H, n-heptyl CH2), 1.10 (overlapping m, 1H, allyl CHMe), 1.30 (m, 1H, n-heptyl CH2), 1.36 (br m, 4H, n-heptyl CH2), 1.49 (obscured, 4H, n-heptyl CH2), 1.51 (s, 15H, C5Me5), 1.52 (obscured, 1H, allyl CH2), 1.93 (d, 3JHH ---  5.6, 31-1, allyl Me), 2.08 (m, 1H, n-pentyl CH2), 3.24 (d, 3./HH--- 7.2, 1H, allyl CH2), 4.90 (ddd, 3JHH = 7.2, 3JHH= 9.2, 3JHH = 13.6, 1H, allyl CH). 13C{ 1 H} NMR (100 MHz, C6D6) 5 9.4 (C5Me5), 14.4 (n-heptyl Me), 16.4 (n-heptyl CH2), 17.7 (allyl Me), 23.3, 29.8, 32.7, 34.4, 38.0 (n-heptyl CH2), 54.1 (allyl CHMe), 74.4 (allyl CH2), 105.5 (C5Me5), 109.5 (allyl CH). MS (LREI, m/z, probe temperature 120 °C) 503 [Mt]. Anal. Calcd. for C211137NOW: C, 50.09; H, 7.41; N, 2.78. Found: C, 49.97; H, 7.40; N, 2.70. 150 4.4.5 Preparation of Cp*W(N0)(CH2(cyclohexyl))(r1 3-CH2CHCHMe) (4.4) Compound 4.4 was prepared from compound 3.7 (45 mg, 0.094 mmol) and methylcyclohexane in a manner identical to that described above for the synthesis of compound 4.1 from 3.7 and n-pentane. Compound 4.4 was isolated as orange irregularly-shaped crystals (20 mg, 42%). Characterization data for 4.4: lR (cm -1 ): 1591 (s, vN0). I HNMR (400 MHz, C6D6), selected signals 8 1.00-1.40 (m, cyclohexylmethyl CH2), 1.49 (s, 15H, C 5Me5), 1.69-1.79 (m, cyclohexylmethyl CH2), 1.89 (d, 3JHH = 6.0, 3H, ally! Me), 2.62 (br d, cyclohexyl CH), 3.38 (d, 3JHH = 7.2, 1H, ally! CH2), 4.94 (ddd, 3JHH = 13.6, 3JHH = 9.2, 3JHH = 7.2, 1H, allyl CH). 13 C { 1 ll} (100 MHz, C 6D6): 8 9.4 (C5Me5), 17.1 (ally! Me), 24.1, 27.4, 27.7, 37.1, 42.1 (cyclohexylmethyl CH2), 44.5 (cyclohexylmethyl CH), 54.4 (ally! CHMe), 73.9 (ally! CH2), 105.6, (C5Me5), 110.3 (ally! CH). MS (LREI, probe temp. 100 °C) m/z 501 [M+]. Anal. Calcd. for for C211-135NOW: C, 50.29; H, 7.04; N, 2.79. Found: C, 50.47; H, 7.28; N, 2.78. 4.4.6 Preparation of Cp*W(N0)(CH2CH2CH3)(9 3-CH2CHCHMe) (4.5) In a glove box a sample of 3.7 (47.5 mg, 0.100 mmol) was dissolved in C6F6 (2 mL) in a ca. 50 mL glass reaction bomb charged with a magnetic stir bar. At a vacuum- N2 dual manifold, propane (ca. 2 mL) was condensed into the reaction bomb under a gentle flow of N2 with the help of a liquid N2 bath. The bomb was sealed and placed 151 above a stir plate located against a wall behind a blast shield, and the content was stirred for 20 h., after which the volatiles were removed in vacuo. Complex 4.5 was worked up in a manner identical to that for complex 4.1. Complex 4.5 was isolated as orange crystalline clusters. Yield 30 mg (65%). Characterization data for 4.5: ER (cm-1 ): 1599 (s, vN0). I li NMR (400 MHz, C6D6) selected signals 8 1.00 (m, 1H, allyl CHMe), 1.28 (t, 3JHH = 7.2, 3H, propyl CH3), 1.50 (s, 15H, C5Me5), 1.94 (d, 3JHH = 6.0, 3H, allyl Me), 2.08 (m, 1H, propyl WCH2), 3.18 (d, 3JHH = 7.6, 1H, ally! CH2), 4.78 (ddd, 3JHH = 13.6, 3JHH = 9.8, 3JHH = 7.6, 1H, allyl CH). 13C { 1 11} (100 MHz, C6D6): 8 9.4 (C5Me5), 17.6 (allyl Me), 19.4 (propyl CH2), 22.5 (propyl CH3), 27. 5 (propyl CH2), 54.1 (allyl CHMe), 74.3 (allyl CH2), 105.4, (C5Me5), 109.5 (allyl CH). MS (LREI, probe temp. 100 °C) m/z 447 [Mt]. Anal. Calcd. for Ci7H29NOW: C 45.65, H 6.53, N 3.13. Found: C 45.80, H 6.81, N 3.22. 4.4.7 Preparation of Cp*W(N0)(CH2CH3)(1 3-CH2CHCHMe) (4.6) In a glove box a sample of 3.7 (34 mg, 0.072 mmol) was dissolved in C6F6 (1 mL) in a 4-dram vial to obtain a light orange solution. The solution was placed in a stainless steel pressure reactor, removed from the glove box, and purged with C2H6 (99.9%) for 10 min. The reactor was pressurized with C2H6 (400 psig) and allowed to warm to room temperature. After 20 h, the pressure was released and the solution transferred to the top of an alumina I column (0.5 x 4 cm). The column was eluted with 4:1 pentane/Et20 and the light yellow band that developed was collected. The solvent was removed from the 152 eluate in vacuo, and the residue was taken into a minimum amount of pentane. The solution was stored overnight at -30 °C to induce deposition of 4.6 as flaky orange crystals (20 mg, 59%). Characterization data for 4.6: IR (cm -1 ) 1600 (s, vN0). 1 11 NMR (400 MHz, C6D6) 6 1.15-1.28 (m, 3H, ally! CHMe and ethyl CH2Me, overlapping), 1.48 (s, 15H, C 5Me5), 1.49 (obs, 1H, allyl CH2), 1.76 (t, 3JHH = 7.3, 3H, ethyl CH 3), 1.93 (d, 3JHH = 5.6, 3H, ally! Me), 3.22 (d, 3JHH = 7.0, 1H, allyl CH2), 4.90 (ddd, 3JHH = 13.7, 3JHH = 9.4, 3JHH = 7.0, 1H, ally! CH). 13 C { 1 11} NMR (100 MHz, C6D6) 8 8.4 (ethyl CH2), 9.8 (C5Me5), 18.1 (ally! Me or ethyl CH 3), 18.5 (ally! Me or ethyl CH 3), 54.7 (allyl CHCH 3), 74.7 (allyl CH2), 105.9 (C5Me5), 109.5 (allyl CH). MS (LREI, m/z, probe temperature 120 °C) 433 [Mt]. Anal. Calcd for C 16H27NOW: C, 44.36; H, 6.28; N, 3.23. Found: C, 44.10; H, 6.26; N, 3.17. 4.4.8 Preparation of Cp*W(N0)(CH3)(1 3-CH2CHCHMe) (4.7) In a glove box a sample of 3.7 (40 mg, 0.084 mmol) was dissolved in C61112 (1.5 mL) in a 4-dram vial to obtain an orange solution. The solution was placed in a stainless steel pressure reactor, removed from the glove box, and purged with CH4 (99.99%) for 10 min. The reactor was pressurized with CH 4 (1025 psig) and allowed to warm to room temperature. After 20 h, the pressure was released and the solution transferred to the top of an alumina I column (0.5 x 6 cm). The column was eluted with 2:1 pentane/Et20 and the light yellow band that developed was collected. The solvent was removed from the 153 eluate in vacuo, and the oily orange residue was recrystallized from pentane layered onto Et20. The solution was stored overnight at -30 °C to induce deposition of 4.7 as needle- like orange crystals (25 mg, 63%). Characterization data for 4.7: IR (cm') 1600 (s, vN0). 'H NMR (300 MHz, C6D6) 6 0.14 (s, 3H, WCH3), 1.45 (obs, 1H, allyl CH2), 1.51 (s, 15H, C 5Me5), 1.95 (d, 3.4u4= 5.8, 3H, allyl Me), 3.02 (d, 34m = 7.2, 1H, ally! CH2), 4.60 (ddd, 3JHH = 13.7, 8.7, 7.8, 1H, ally! CH). 13 C {'H} NMR (100 MHz, C6D6) 8 3.2 (WCH3), 10.1 (C5Me5), 16.1 (ally! Me), 54.5 (ally! CHMe), 74.7 (ally! CH2), 105.8 (C5Me5), 107.9 (ally! CH) MS (LREI, m/z, probe temperature 100 °C) 419 [Mt]. 4.4.9 Preparation of Cp*W(N0)(CH2SiMe3)(1) 3-CH2CHCHMe) (3.9) -- C-H Activation Route Complex 3.9 was prepared from 3.7 (47.5 mg, 0.100 mmol) and tetramethylsilane (3 mL) and purified in a manner identical to that described above for the synthesis of complex 4.1. Complex 3.9 was isolated as yellow-orange irregularly-shaped crystals. Yield 37 mg (75%). 4.4.10 Preparation of Cp*W(N0)((012)5C1)(1 3-CH2CHCHMe) (4.8) Complex 4.8 was prepared from 3.7 (47.5 mg, 0.100 mmol) and 1-chloropentane (2 mL) in a manner identical to that described above for the synthesis of complex 4.1. 154 Complex 4.8 was not amenable to chromatographic purification, and was obtained as an orange-yellow analytically-pure solid by crystallization of the crude product from pentane in multiple crops. Yield 20 mg (40%). Characterization data for 4.8: 1R (cm 1 ): 1598 (s, vivo). I FINMR (400 MHz, C6D6), selected signals: 8 1.10 (m, 1H, allyl CHCH3), 1.49 (s, 15H, C5Me5), 1.93 (d, 3JHH = 6.0, 3H, allyl Me), 3.14 (d, 3JHH = 7.2, 1H, ally! CH2), 3.29 (m, 2H, CH2C!), 4.87 (ddd, 3JHH = 13.6, 3JHH = 9.6, 3JHH = 7.2, 1H, allyl CH). 13C { 1 H} (100 MHz, C6D6): 8 9.4 (C5Me5), 15.6 (WCH2), 17.6 (allyl Me), 32.9, 33.5, 34.7 (chloropentyl CH2), 45.5 (CH2C!), 54.3 (ally! CHMe), 74.3 (ally! CH2), 105.5, (C5Me5), 109.6 (ally! CH). MS (LREI, probe temp. 100 °C) m/z 509 [Mt]. Anal. Calcd. for C19H32C1NOW: C 44.77, H 6.33, N 2.75. Found: C 44.66, H 6.49, N 2.69. 4.4.11 Preparation of Cp*W(N0)(CH2CH2OCH2CH3)(1 3-CH2CHCHMe) (4.9) Complex 4.9 was prepared from 3.7 (47.5 mg, 0.100 mmol) and Et20 (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.8. Complex 4.8 was obtained as a tan solid by crystallization of the crude product from pentane in multiple crops. Yield 16 mg (34%). Characterization data for 4.9: IR (cm-1 ): v(NO) 1595. I li NMR (400 MHz, C6D6): 8 1.00 (m, 1H, ally! CHCH3), 1.29 (t, 3JHH = 7.0, 3H, CH3CH2O), 1.47 (s, 15H, C 5Me5), 1.49 (obs, 1H, ally! CH2) 1.88 (d, 2JHH = 5.8, 3H, ally! Me), 3.34 (d, 3JHH = 7.2, 1H, ally! 155 CH2), 3.39 (m, 1H, OCH2), 3.56 (m, 2H, OCH2), 4.06 (m, 1H, OCH2) 4.81 (ddd, 3JHH = 13.6, 3JHH = 9.2, 3JHH = 7.2, 1H, ally! CH). 13 C MI (100 MHz, C6D6): 8 9.4 (C 5Me5), 14.0 (WCH2), 16.2 (CH3CH2O), 17.4 (ally! Me), 53.6 (ally! CHMe), 64.9 (OCH2), 73.8 (allyl CH2), 76.8 (OCH2) 105.8, (C5Me5), 110.5 (ally! CH). MS (LREI, probe temp. 100 °C) m/z 477 [Mt]. Anal. Calcd. for C18E131NO2W: C 45.30, H 6.55, N 2.93. Found: C 45.48, H 6.71, N 2.67. 4.4.12 Preparation of Cp*W(N0)(CH2CH2N(CH2CH3)2)(i3-CH2CHCHMe) (4.10) Complex 4.10 was prepared from 3.7 (47.5 mg, 0.100 mmol) and triethylamine (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.8. Attempts to crystallize complex 4.10 only led to the isolation of it as a yellow oily solid. Yield 20 mg (40%). Characterization data for 4.10: IR (cmd) 1596 (s, vN0). 1 H NMR (400 MHz, C6D6) selected signals 8 0.86 (dt, 3JHH = 6.9, 2JHH = 6.9, 1H, WCH2), 1.02 (m, 1H, ally! CHMe), 1.21 (t, 3JHH = 7.0, 6H, NCH2CH3), 1.49 (s, 15H, C5Me5), 1.89 (d, 3JHH = 5.9, 3H, allyl Me), 2.40 (dt, 3JHH = 6.9, 2JHH = 6.9, 1H, WCH2), 2.50 (m, 1H, WCH2CH2N), 2.73 (q, 3 JHH = 7.0, 4H, NCH2CH3), 3.19 (m, 1H, WCH2CH2N), 3.43 (d, 3JHH = 7.0, 1H, ally! CH2), 4.86 (ddd, 3JHH = 13.6, 3JHH = 9.4, 3J1-114 = 7.0, 1H, ally! CH). 13 C { 1 1-1} NMR (100 MHz, C6D6) 8 9.8 (C 5Me5), 11.4 (WCH2CH2N), 13.7 (NCH2CH3), 18.0 (allyl Me), 47.4 (NCH2CH3), 54.3 (allyl CHMe), 58.0 (NCH2CH2W), 73.7 (ally! CH2), 106.0 (C 5Me5), 110.4 (allyl CH). 156 4.4.13 Preparation of Cp*W(N0)(13 ,11 1 -CH2CHCHCH2Cp14(C4H8)C all) (4.11) Complex 4.11 was prepared from 3.7 (47.5 mg, 0.100 mmol) and cyclohexene (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.1. Complex 4.11 was obtained as yellow rods by crystallization of the chromatographically purified product from pentane in multiple crops. Yield 20 mg (41%). Characterization data for 4.11: ER (cm 1 )1588 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 0.37 (dd, 2JHH = 3.0, 3JHH = 9.6, 1H, ally! CH2), 1.35-1.45 (overlapping m, 2H, cyclohexyl CH2), 1.62 (s, 15H, C5Me5), 1.72 (dt, 1H, 3JHH = 12.8, 3JHH = 3.0, 1H, cyclohexyl WCH), 1.77 (m, 2H, cyclohexyl CH2), 1.90 (m, 1H, cyclohexyl CH2), 2.07 (m, 1H, WCH2CH=CHCH2), 2.11 (dd, 2JHH = 3.0, 3JHH = 6.4, 1H, ally! CH2), 2.39 (m, 1H, cyclohexyl CH), 2.48 (m, 1H, cyclohexyl CH2), 2.58 (m, 1H, WCH2CH=CHCH2), 2.74 (m, 1H, ally! CH), 5.26 (ddd, 3JHH= 12.8, 3JHH= 9.6, 3JHH = 6.4, 1H, allyl CH). 13C{ 1 11} NMR (100 MHz, C6D6) 8 9.8 (C5Me5), 22.5, 32.6, 32.8, 34.4 (cyclohexyl CH2), 34.2 (WCH2CH=CHCH2), 36.0 (ally! CH2), 39.7 (WCH), 62.3 (cyclohexyl CH), 102.4 (WCH2CH=CH), 105.4 (C5Me5), 109.8 (WCH2CH=CH). MS (LREI, m/z, probe temperature 120 °C) 485 [Ml. Anal. Calcd for C20H3INOW: C, 49.50; H, 6.44; N, 2.89. Found: C, 49.53; H, 6.31; N, 2.71. 157 4.4.14 Preparation of Cp*W(N0)(113,11-CH2CHCHCH2C(CH3)20)  (4.12) Complex 4.12 was prepared from 3.7 (47.5 mg, 0.100 mmol) and acetone (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.1. Complex 4.12 was obtained as orange irregularly-shaped crystals by storing a concentrated solution of the chromatographically purified product in pentane for -30 °C overnight. Yield 18 mg (39%). Characterization data for 4.12: IR (cm -1 ): v(NO) 1594 (s, vN0). 1 H NMR (400 MHz, C6D6): 8 0.76 (ddd, 2JHH = 3.0, 3JHH = 9.2, 4JHH = 1.2, 1H, allyl CH2), 1.35 (s, 3H, OCMe2), 1.40 (s, 3H, OCMe2), 1.52 (dd, 1H, 2JHH = 12.4, 3JHH = 7.6, WCH2CH=CHCH2), 1.64 (s, 15H, C 5Me5), 1.71 (dd, 2JHH = 3.0, 3JHH = 6.4, 1H, allyl CH2), 1.79 (dd, 2JHH 12.4, 3JHH = 7.6, 1H, WCH2CH=CHCH2), 3.98 (dtd, 3JHH = 12.4, 3JHH = 7.6, 4JHH = 1.2, 1H, allyl CH), 6.14 (ddd, 3JHH = 13.2, 3JHH 9.2, 3JHH = 6.4, 1H, allyl CH). 13C f ifIl (100 MHz, C6D6): 8 10.0 (C5Me5), 33.0, 35.8 (OCMe2), 40.8 (allyl CH2), 42.6 (WCH2CH=CHCH2), 83.5 (OCMe2), 104.7 (C5Me5), 111.5 (allyl CH), 118.7 (allyl CH). MS (LREI, probe temp. 100 °C) m/z 461 [M+]. Anal. Calcd. for Ci7H27NO2W: C, 44.27; H, 5.90; N, 3.04. Found: C, 44.40; H, 5.86; N, 3.05. 4.4.15 Preparation of Cp*W(N0)(11 301 1-CH2CHCHCH2C(CH2CH3)20) (4.13) Complex 4.13 was prepared from 3.7 (47.5 mg, 0.100 mmol) and 3-pentanone (2 mL) and worked up in a manner identical to that described above for the synthesis of 158 complex 4.1. Complex 4.13 was obtained as orange irregularly-shaped crystals by storing a concentrated solution of the chromatographically purified product in pentane for -30 °C overnight. Yield 33 mg (67%). Characterization data for 4.13: IR (cm 1 ): 1593 (s, vN0). 1 H NMR (400 MHz, C6D6) selected signals 8 0.77 (m, 1H, ally! CH2), 0.91 (t, 3JHH = 7.2, Ethyl CH3), 1.01 (t, 3 JHH = 7.2, Ethyl CH3), 1.66 (s, C5Me5), 1.80 (m, 2H, CH2-C(C(Et)2)-O), 3.98 (m, 1H, allyl CHCH2), 6.08 (ddd, 341H= 6.4, 3JHH = 8.8, 3JHH = 13.2, 1H, ally' CH2CH). 13 C { 1 H} (100 MHz, C6D6): 8 8.5, 10.3 (Ethyl CH3), 10.0 (C5Me5), 33.8, 36.9 (Ethyl CH2), 39.3 (allyl CH2), 40.8 (WCH2CH=CHCH2), 108.0 (C-0), 109.7 (C5Me5), 112.4 (allyl CH) , 119.3 (allyl CH). MS (LREI, probe temp. 100 °C) m/z 489 [M+]. Anal. Calcd. for C19H3INOW: C, 46.64; H, 6.39; N; 2.86. Found: C, 46.50; H, 6.27; N, 2.83. 4.4.16 Preparation of Cp*W(N0)(1139111-CH2CHCHCH2CCH3=CCH3) (4.14) Complex 4.14 was prepared from 3.7 (47.5 mg, 0.100 mmol) and 2-butyne (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.1. Complex 4.14 was obtained as orange rod-shaped crystals by storing a concentrated solution of the chromatographically purified product in pentane for -30 °C overnight. Yield 30 mg (66%). Characterization data for 4.14: IR (cm -1 ): 1609 (s, vN0). 1 H NMR (400 MHz, C6D6) selected signals 8 0.52 (dd, 2JHH = 2.4, 3JHH = 9.6, 1H, ally! CH2), 1.63 (s, 15H, 159 C5Me5), 1.71 (s, 3H, 2-buytne CH3), 2.17 (s, 3H, 2-buytne CH3), 2.42 (dd, 3JHH = 2.4, 3 JHH = 6.8, 1H, ally! CH2), 2.48 (dd, 3JHH = 6.8, 2JHH = 16, 1H, ally! CH2), 2.68 (dd, 3JHH = 3.6, 2JHH = 16, allyl CH2), 3.28 (m, 1H, ally! CH), 5.38 (ddd, 3JHH = 6.8, 3JHH 9.6, 3JHH = 13.2, ally! CH). 13 C { 1 H} (100 MHz, C6D6): 6 10.3 (C5Me5), 18.1, 26.4 (CH3), 38.8 (allyl CH2), 41.9 (WCH2CH=CHCH2), 101.9 (ally! CH), 106.8 (C5Me5), 111.9, (allyl CH), 154.5, 158.7 (C=C). MS (LREI, probe temp. 100 °C) m/z 457 [Mt]. Anal. Calcd. for C18H27NOW: C 47.28, H 5.95, N 3.06. Found: C 47.20, H 6.21, N 2.75. 4.4.17 Preparation of Cp*W(NO)Cr1 l-CH2C(CH3)C(C113)2)(11 3-CH2CHCHMe) (4.15) Complex 4.15 was prepared from 3.7 (47.5 mg, 0.100 mmol) and 2,3-dimethy1-2- butene (2 mL) and worked up in a manner identical to that described above for the synthesis of complex 4.1. Complex 4.15 was obtained as orange irregularly-shaped crystals by storing a concentrated solution of the chromatographically purified product in THF/HMDS for -30 °C overnight. Yield 24 mg (49%). Characterization data for 4.15: IR (cm -1 ): 1597 (s, vN0). 1 H NMR (400 MHz, C6D6) selected signals 6 1.30 (m, 1H, ally! CHCH3) 1.50 (s, 15H, C5Me 5), 1.88 (s, 3H, CH3), 1.93 (br s, 9H, CH3), 2.14 (d, 3JHH = 8.8, 1H, WCH2), 3.31 (d, 3JHH = 6.8, ally! CH2), 4.80 (ddd, 3JHH = 13.2, 3JHH = 8.8, 3JHH = 6.8, 1H, ally! CH) . 13 C { 1 H} (100 MHz, C6D6) 6 9.5 (C5Me5), 17.2 (methylallyl Me), 20.9 (WCH2), 21.0, 21.1, 21.9 (trimethylallyl Me), 55.9 (methylallyl CHMe), 77.0 (methylallyl CH2), 105.8, (C5Me5), 111.0 (methylallyl CH), 116.7, 140.7 (trimethylallyl olefinic C). MS (LREI, probe temp. 160 100 °C) m/z 487 [Mt]. Anal. Calcd. for C 201-133NOW: C 49.73, H 6.02, N 2.64. Found: C 49.68, H 6.03, N 2.71. 4.4.18 Preparation of Cp*W(N0)(CH2C6H5)(r1 3-CH2CHCHMe) (4.16) In a glove box a sample of 3.7 (33.0 mg, 0.069 mmol) was dissolved in toluene (1.2 mL) in a 4-dram vial to obtain an orange solution. The solution was left to sit in the glovebox. After 20 h, the orange solution was transferred to the top of an alumina I column (0.5 x 5 cm). The column was eluted with 4:1 pentane/Et20 and the yellow band that developed was collected. The solvent was removed from the eluate in vacuo, and the oily yellow residue was dissolved in benzene-d6 to obtain a yellow solution. The yellow solution was heated at 50 °C for 20 h to afford a brown solution. The brown solution was transferred to the top of an alumina I column (0.5 x 6 cm). The column was eluted with 2:1 pentane/Et20 and the light yellow band that developed was collected. The solvent was removed from the eluate in vacuo, and the oily yellow residue was re-crystallized from layered 1:1 pentane/Et20. The solution was stored overnight at -30 °C to induce deposition of 4.16 as orange crystals (22.0 mg, 67%). Characterization data for 4.16: IR (cm -1 ) 1603 (s, vN0). 1 H NMR (400 MHz, C6D6) 8 1.25 (m, 1H, allyl CHMe buried), 1.47 (s, 15H, C5Me5), 1.52 (d, 3JHH = 13.6, 1H, allyl CH2), 1.76 (d, 3JHH = 5.9, 3H, allyl Me), 1.95 (d, 3JHH = 9.1, 1H, benzyl CH2), 2.82 (d, 3JHH = 9.1, 1H, benzyl CH2), 3.43 (d, 3JHH = 7.4, 1H, allyl CH2), 4.43 (ddd, 3JHH = 13.6, 3JHH = 9.3, 3JHH = 7.4, 1H, allyl CH), 7.00 (d, 3JHH = 7.4, 1H, para CH), 7.29 (t, 3JHH = 161 7.4, 2H, meta CH), 7.51 (d, 3JHH = 7.4, 2H, ortho CH). 13 C { 1 H} NMR (100 MHz, C6D6) 9.8 (C,Me5), 17.5 (ally! Me), 21.1 (benzyl CH2), 56.5 (ally! CHCH3), 77.0 (ally! CH2), 110.4 (ally! CH), 123.5 (Ar C), 128.1 (Ar C), 129.1 (Ar C). MS (LREI, m/z, probe temperature 100 °C) 495 [Mt]. Anal. Calcd for C211-130NOW: C, 50.82; H, 6.09; N, 2.82. Found: C, 50.97; H, 5.97; N, 2.82. 4.4.19 Reaction Between 4.1 and 12 In a glove box, complex 4.1 (42.0 mg, 0.884 mmol) was dissolved in CDC13 (3 mL) in a medium Schlenk tube containing a small stir bar. HMDS (10 lit) was added via a microsyringe as an NMR integration standard. The 1 H NMR spectrum of a sample of the mixture was recorded, and the area under the doublet at 3.40 ppm (1H, ally! CH2CHCHCH3) was integrated against the singlet at 0.10 ppm (18H, HMDS). The NMR sample was recombined with the rest of the solution. At a vacuum line the Schlenk tube was attached to a vacuum line and maintained at -60 °C with a dry ice/acetone bath. A solution of I2 (45.0 mg, 2 equiv) in CDC13 (15 mL) was prepared in a second Schlenk tube, and the solution was added dropwise via a cannula to the first Schlenk tube maintained at -60 °C. The Schlenk tube was finally rinsed with a small amount of cold CDC1 3 (2 x 2 mL) to ensure quantitative transfer. The cold bath was removed after the addition of I2 was complete, and the reaction mixture was stirred for a further lh. Overall the reaction mixture changed color from yellow-orange to dark greenish yellow. A small amount of the reaction mixture was transferred into an NMR tube via a thin cannula. The sample was analyzed by 1 H NMR spectroscopy, and integration of the area under the 162 triplet at 3.20 ppm (2H, CH3CH2CH2CH2CH2I) against the HMDS signal revealed that 1- C 5H, l I had been formed in approximately 73% yield. The volatiles from the final reaction mixture were then vacuum-transferred into another Schlenk tube and were analyzed by 'H NMR spectroscopy. Signals at 3.20 ppm (t, 2H, CH3CH2CH2CH2CH2I), 1.84 ppm (m, 2H, CH3CH2CH2CH2CH2I), 1.38 ppm (m, 4H, CH3CH2CH2CH2CH2I and CH3CH2CH2CH2CH2I) and 0.91 ppm (t, 3H, CH3CH2CH2CH2CH2I) indicated the presence of 1-iodopentane, as confirmed by a'1-1 NMR spectrum of an authentic sample. The volatiles were also analyzed by ELMS. The presence of C5fl 1 I I, likely 1-iodopentane, was indicated by a signal at m/z =197.9 [P+}, while a signal at m/z = 181.9 indicated the presence of at least one isomer of methallyl iodide. The final organometallic residue was extracted with pentane (2 x 20 mL). The extracts were filtered through Celite supported on a medium-porosity frit. The pentane was removed from the filtrate in vacuo, and the green-yellow residue was analyzed by 'H NMR and IR spectroscopy. Spectroscopic data ['H NMR in CDC13 : 6 2.18 (C 5Me5); IR (Nujol mull): v 1630 cm' (vN0)] were consistent with the residue being principally the well known Cp*W(NO)I2.28 163 4.4.20 X-Ray Crystallography Data collection for each compound was carried out at —100 ±1 °C on either a Rigaku AFC7/ADSC CCD diffractometer or a Bruker X8 APEX diffractometer, using graphite-monochromated Mo Ka radiation. Data for 4.1 were collected to a maximum 20 value of 56.4 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. The crystal was a two-component twin. All non-hydrogen atoms were refined anisotropically; hydrogen atoms Hla, Hlb, H2 and H3 were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4679 observed reflections and 222 variable parameters. X-ray crystallographic data for the structure are presented in Table A.5. Data for 4.2 were collected to a maximum 20 value of 55.8 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms Hla, Hlb, H2, H3, H4a and H4b were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4503 observed reflections and 222 variable parameters. X-ray crystallographic data for the structure are presented in Table A.5. 164 Data for 4.6 were collected to a maximum 20 value of 55.4 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. The two [mirror-image] chiral isomers of the compound co-crystallized to produce a crystallographically averaged solution. This was modeled as two disordered components called Part A and Part B for the methyl-allyl ligand and the ethyl ligand. Each part had 50% occupancy. All non-hydrogen atoms were refined anisotropically. Related bond distances in the two parts were constrained to the same length within a standard deviation of 0.02 for the following pairs: Cla-C2a and Clb-C2b; C2a-C3a and C2b-C3b; C3a-C4a and C3b-C4b; C5a-C6a and C5b-C6b; W1 -05a and W1 -05b; Cla-C3a and Clb-C3b; and C2a-C4a and C2b-C4b. All hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 3767 observed reflections and 235 variable parameters. X-ray crystallographic data for the structure are presented in Table A.5. Data for 4.11 were collected to a maximum 20 value of 57.4 ° in 0.5 ° oscillations. The structure was solved by direct methods29 and expanded using Fourier techniques. The crystal was twinned and one component of the twin was used to generate the solution. The crystallographic solution contained two molecules of A16. Atoms C6, C7, C14, C26, C31 and C35 were refined isotropically and all other non-hydrogen atoms were refined anisotropically. All hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 8753 observed reflections and 396 variable parameters. The final solution was definite as to structure but unsuitable 165 for publication due to the effects of the twinning on the R values. X-ray crystallographic data for the structure are presented in Table A.6. Data for 4.13 were collected to a maximum 20 value of 56.0 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms Hla, Hlb, H2 and H3 were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4493 observed reflections and 231 variable parameters. X-ray crystallographic data for the structure are presented in Table A.6. Data for 4.14 were collected to a maximum 20 value of 55.2 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms H1 a, Hlb, H2 and H3 were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 3834 observed reflections and 213 variable parameters. X-ray crystallographic data for the structure are presented in Table A.6. Data for 4.15 were collected to a maximum 20 value of 56.0 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. In the crystal lattice 4.15 was solvated with THF in a 2:1 ratio. The disordered THF molecule was modeled with constrained, isotropic atoms. All other non- 166 hydrogen atoms were refined anisotropically, and all hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 5277 observed reflections and 237 variable parameters. X-ray crystallographic data for the structure are presented in Table A.7. Data for 4.16 were collected to a maximum 20 value of 56.0 ° in 0.5 ° oscillations. The structure was solved by direct methods 29 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically, and all hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 4538 observed reflections and 223 variable parameters. X-ray crystallographic data for the structure are presented in Table A.7. For each structure neutral-atom scattering factors were taken from Cromer and Waber.3° Anomalous dispersion effects were included in Fcaic;31 the values for Af and Of ' were those of Creagh and McAuley. 32 The values for mass attenuation coefficients are those of Creagh and Hubbe11. 33 All calculations were performed using SHELXL- 9 7 . 3 4 167 4.5^References and Notes (1) For recent books and reviews on the topic of C-H activation at transition-metal centers, see: (a) Activation and Functionalization of C-H Bonds; Goldberg, K. I., Goldman, A. S., Eds.; ACS Symposium Series 885; American Chemical Society: Washington, DC, 2004. (b) Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154. (c) Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879. (d) Labinger, J. A.; Bercaw, J. E. Nature, 2002, 417, 507. (e) Hartwig, J. F. In ref I a; Chapter 8. (2) Ng, S.H.K.; Adams, C. S.; Hayton, T. W.; Legzdins, P.; Patrick, B. 0. , J. Am. Chem. Soc. 2003, 125 , 15210. (3) (a) Jones, W. D.; Hessell, E. T. J. Am. Chem. Soc. 1993, 115, 554 and references cited therein. (b) Bhalla, G.; Liu, X. Y.; Oxgaard, J.; Goddard, W. A., III; Periana, R. A. I Am. Chem. Soc. 2005, 127, 11372 and references cited therein. (4) (a) Kostelansky, C. N.; MacDonald, M. G.; White, P. S.; Templeton, J. L. Organometallics 2006, 25, 2993 and references cited therein. (b) Vetter, A. J.; Jones, W. D. Polyhedron, 2004, 23, 413. (c) A successful example of clean aliphatic C-H activation is the Cp2Zr(t-butylimido) system, which activates n- pentane and n-hexane exclusively at the terminal positions at 75 °C to form 18e alkyl amido products. See: Hoyt, H. M.; Michael, F. E.; Bergman, R. G. I Am. Chem. Soc. 2004, 126, 1018. (5)^K. Wada, B. Craig, C. B. Pamplin, P. Legzdins, B. 0. Patrick, I. Tsyba, R. Bau. I Am. Chem. Soc. 2003, 125, 7035. 168 (6)^(a) Jones, W. D.; Feher, F. J. Organometallics 1983, 2, 562. (b) Periana, R. A.; Bergman, R. G. J. Am. Chem. Soc. 1986, 108, 7332. (c) Arndtsen, B. A.; Bergman, R. G. Science 1995, 270, 1970. (d) Debad, J. D.; Legzdins, P.; Lumb, S. A.; Rettig, S. J.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1999, 18, 3414 and references cited therein. (7)^(a) Flood, T. C.; Janak, K. E.; Iimura, M.; Zhen, H. I Am. Chem. Soc. 2000, 122, 6783 and references cited therein. (8) (a) Ng, S.H.K. Unpublished observations. (b) Debad, J. D.; Legzdins, P.; Lumb, S. A.; Batchelor, R. J.; Einstein, F. W. B. I Am. Chem. Soc. 1995, 117, 3288. (9) (a) Oshima, M.; Sakamoto, T.; Maruyama, Y.; Ozawa, F.; Shimizu, I.; Yamamoto, A. Bull Chem. Soc. Jap. 2000, 73, 453 (b) Chin, C. S.; Lee, H.; Noh, S. Park, H.; Kim, M. Organometallics 2003, 22, 2119. (10) Debad, J. D.; Legzdins, P.; Young, M. A.; Batchelor, R. J.; Einstein, F. W. B. J. Am. Chem. Soc. 1993, 115, 2051. (11) Christensen, N. J.; Hunter, A. D.; Legzdins, P. Organometallics 1989, 8, 930. (12) The Cp*W(NO)L fragment, where L is a 2e donor, is known to effect oxidative addition of C-H bonds. For a recent example of this transformation, see: Lee, K.; Legzdins, P.; Pamplin, C. B.; Patrick, B.O.; Wada, K. Organometallics 2005, 24, 638. (13) (a) Jun, C. H.; Bu, J. Bull. Of the Korean Chem. Soc. 1989, 10, 114. (b) Fryzuk, M. D.; Piers, W. E.; Rettig, S. J. Einstein, F. W. B.; Jones, T.; Albright, T. A. I Am. Chem. Soc. 1989; 111, 5709. (14) Vetter, A. J.; Flaschenriem, C.; Jones, W. D. J. Am. Chem. Soc. 127, 35, 12315 169 (15) In the case of complex 3.1, reaction with cyclohexane led to the isolation of the complex Cp*W(NO)(r1 3 -C6H9)(H), the result of a triple C-H activation on cyclohexane. See ref. 2. (16) I hereby thank Dr. Peter M. Graham and Mr. Scott P. Semproni for their intellectual and technical contributions to these part of the project. (17) Treatment of 3.7 with C6F6 alone leads to the formation of several new Cp*- containing organometallic species and a number of signals in the 19F NMR spectrum of the crude product. Unfortunately these new species have eluded characterization so far. (18) The vapour pressure for propane at 300 K is approximately 0.9990 Mpa (145 psi). Miyamoto, H.; Uematsu, M. Mt. I Thermophysics 2006, 27, 1052. (19) The two mirror-image chiral isomers of complex 4.6 were modeled as two disordered components called Part A and Part B for the methyl-allyl ligand and the ethyl ligand. Each part had 50% occupancy. Only part A is shown in Figure 4.3. (20) I hereby thank Mr. Simon Kim for his intellectual and technical contributions to these parts of the project. (21) Christensen, N.J.; Legzdins, P; Trotter, J.; Yee, V. C. Organometallics, 1991, 10, 4021. (22) For comparison, the reaction between 3.1 and 2,3-dimethylbutene yields the same type of compound, except that the original dimethylallyl ligand has adopted an 11 1 -coordination mode while the new 2,3,3-trimethylallyl ligand bas become the 1 3-bonded ligand. Fujita-Takayama, C. Unpublished observations. 170 (23) (a) The preferential generation of aryl-C-H activation products over that of benzylic is a trend commonly seen in many transition-metal-based C-H activating systems. The most prevalent rationalization for this selectivity is the thermodynamics of bond-breaking and bond-formation, as the resulting M-C(sp2) bond is stronger than M-C(sp 3) bonds. See: Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91 and references cited therein. (b) Exceptions arise when C-H(sp 3) activation leads to other stabilizing interactions, such as the favourable M-1 3 - benzyl structures arising from the C-H activation of methylbenzenes by a platinum complex. See: Heyduk, A. F.; Driver, T. G., Labinger, J. A.; Bercaw, J. E. I Am. Chem. Soc., 2004, 126, 15034. (24) Adams, C. S.; Legzdins, P.; Tran, E. Organometallics 2002, 21, 1474. (25) For comparison, it may be noted that direct iodinations of pentane either by tert- butyl hypoiodite or by HCI3 in the presence of solid NaOH are unselective and produce mixtures of iodopentanes. See: (a) Montoro, R.; Wirth, T. Synthesis 2005, 1473. (b) Schreiner, P. R.; Lauenstein, 0.; Butova, E. D.; Fokin, A. A. Angew. Chem., Mt. Ed. 1999, 38, 2786. (26) Dryden, N. H.; Legzdins, P.; Trotter, J.; Yee, V. C. Organometallics 1991, 10, 2857. (27) Debad, J. D.; Legzdins, P.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1993, 12, 2094. (28) Dryden, N. H.; Legzdins, P.; Einstein, F. W. B.; Jones, R. H. Can. I Chem. 1988, 66, 2100. (29) S1R92: Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A. I Appl. Cryst. 1993, 26, 343. (30) Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, 1974; Vol. IV. (31) Ibers, J. A.; Hamilton, W. C. Acta Crystallogr. 1964, 17, 781. (32) Creagh, D. C.; McAuley, W. J. International Tables of X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (33) Creagh, D. C.; Hubbell, J. H. International Tables for X-ray Crystallography; Kluwer Academic Publishers: Boston, 1992; Vol. C. (34) SHELXL97: Sheldrick, G. M. University of Gottingen, Germany, 1997. 171 172 CHAPTER 5 Preliminary Investigations on C-H Bond Activations Initiated by Cp*W(N0)(CH2CMe3)(1 3-CH2CHCHPh) 5.1^Introduction The complex Cp*W(N0)(CH2CMe3)(r1 3 -CH2CHCHPh) (3.8) is another member of the new series of allyl-alkyl complexes. This compound has been synthesized with the initial research goal being the expansion of the scope of the concurrent N-H and a-C-H activation chemistry described in Chapter 3 of this Thesis. Besides being able to react with cyclic amines at RT, complex 3.8 also possesses a thermal reaction pathway. At 75 °C for 1 d it completely loses neopentane to form a reactive intermediate that performs C-H activations on certain hydrocarbons. This chapter summarizes the thermal reactivity of complex 3.8 with various organic solvents. Trapping the intermediate as a direct PMe 3 adduct has been unsuccessful, although other evidence strongly suggests that it is the allene intermediate Cp*W(NO)(r1 2 -CH2=C-- - CHPh) that is responsible for the observed chemistry. Furthermore, because of the relatively high temperature at which the intermediate is generated, not all products arising from direct C-H activation processes can be isolated as such. In most cases the final product consists of an inseparable mixture of organometallic species. In one case, however, an isomerization product has been isolated and fully characterized. 173 5.2^Results and Discussion 5.2.1 Thermal Properties of Cp*W(NO)(CH2CMe3)(113-CH2CHCHPh)  (3.8) The synthesis of complex 3.8 has been described in section 3.2 of this Thesis. As a solid, complex 3.8 can be kept for months at RT without signs of significant decomposition. In solution at the same temperature, 3.8 is stable for a few weeks. However, in solution at 75 °C for 1 d, complex 3.8 is completely consumed. 5.2.2 Reaction with Benzene The thermolysis of complex 3.8 in benzene at 75 °C for 1 d leads to the exclusive formation of a new organometallic species. This pale-yellow complex can be purified by chromatography and crystallized from pentane/Et 20 as needles, and an X-ray crystallographic analysis reveals it to be Cp*W(N0)(H)(q 3 -PhHCCHCHPh) (5.1) whose solid-state molecular structure is shown in Figure 5.1. In complex 5.1 the new phenyl fragment is attached to the previously unsubstituted terminal end of the phenylallyl ligand, thus converting it into the 1,3-diphenylally1 ligand. A metal-hydrogen link is also present, as evidenced by a characteristic hydride signal (singlet flanked by 183W satellites) at -0.15 ppm ( IJwH = 124 Hz) in the 1 H NMR spectrum of 5.1 in C6D6. Overall, this transformation is not unlike what has been previously observed for the reaction between Cp*W(N0)(CH 2CMe3)(1 3 -CH2CHCMe2) (3.1) and THF, 1 as depicted in Scheme 1.14 in chapter 1 of this Thesis. 174 Figure 5.1. Solid-state molecular structure of Cp*W(N0)(H)(ri 3 -PhHCCHCHPh) (5.1) with 50 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.422(10), W(1)-C(2) 2.303(9), W(1)-C(3) = 2.278(9), W(1)-N(1) = 1.759(7), N(1)-O(1) = 1.228(10), C(1)-C(2) = 1.405(15), C(2)-C(3) = 1.368(15), C(3)-C(4) = 1.464(14), C(1)-C(l0) = 1.450(15), C(1)-C(2)-C(3) = 120.5(10), C(2)-C(3)-C(4) — 123.0(10), C(2)-C(1)-C(10) = 126.7(10), W(1)-N(1)-0(1) = 170.0(7). At first glance it appears that a possible mechanism for this transformation might involve 1) the loss of neopentane via an a-hydrogen abstraction on the allyl ligand, 175 leading to the formation of a vinylalkylidene intermediate, and 2) 1,2-addition of a benzene C-H bond across the metal-alkylidene linkage (Scheme 1.1). Step 2, however is chemically counterintuitive, because from both steric and electronic (polarity) points of view one would expect the phenyl to add to W and the hydrogen to add to the alkylidene carbon. Scheme 5.1 C6H6, 75 °C -CMe4 3.8  -CMe4 C6H6 To substantiate or disprove this mechanism, a labeling experiment has been conducted in C6D6. Firstly, the results of this experiment indicate that in 5.1-d6 the phenylallyl meso-hydrogen is fully deuterated, as evidenced by a) the disappearance of the signal attributable to the meso-hydrogen at 5.90 ppm in the 1 HNMR spectrum of 5.1, and b) the doublets at 2.02 and 2.74 (allyl CHPh) in the spectrum of 5.1 now appear as 176 slightly broad singlets in the spectrum of 5.1-d6. Secondly, the tungsten hydride signal remains unchanged, indicating that the use of a deuterated substrate does not lead to the hydride being replaced by a deuteride. Therefore, the mechanism proposed in Scheme 1.1 is invalid. 2 Consequently, we now view the reaction as proceeding via the following steps: 1) an allene intermediate is formed under thermal conditions, as in the case of the well-studied Cp *W(N0)(CH2CMe3)( 11 3-CH2CHCMe2) (34 3 and 2) the C-H activation product, Cp*W(N0)(Ph)(r1 3-CH2CHCHPh) is next formed, but under the reaction conditions employed it isomerizes to the 1-3-diphenylallyl hydrido complex 5.1. To support the existence of the allene intermediate Cp*W(NO)(r1 2 - CH2=C=CHPh) (A), complex 3.8 has been thermolyzed in PMe 3 and cyclohexene, respectively. While the former reaction leads to the formation of two phosphorus- containing species4 (as evidenced by 31 P NMR spectroscopy) amidst a mixture of complexes that we have yet to purify, the reaction between 3.8 and cyclohexene is informative, since the complex Cp*W(N0)(H)(1) 3-CH2C(3-cyclohexenyl)CHPh) (5.2) is formed as the principal organometallic product. Complex 5.2 is completely analogous to 3.3, the product obtained from the reaction between cyclohexene and Cp*W(N0)(r1 2 - CH2=C=CMe2), the allene intermediate arising from the thermolysis of 3.1. 3 The solid- state molecular structure of 5.2 is shown in Figure 5.2. 177 Figure 5.2. Solid-state molecular structure of Cp*W(N0)(H)(r1 3 -CH2C(3- cyclohexenyl)CHPh) (5.2) with 50 % probability thermal ellipsoids shown. Selected interatomic distances (A) and angles (deg): W(1)-C(1) = 2.262(3), W(1)-C(2) = 2.328(2), W(1)-C(3) = 2.360(2), W(1)-N(1) = 1.763(2), N(1)-O(1) = 1.216(3), C(1)-C(2) = 1.403(3), C(2)-C(3) = 1.403(3), C(3)-C(4) = 1.492(3), C(2)-C(10) = 1.521(3), C(10)- C(11) = 1.492(3), C(11)-C(12) = 1.317(4), C(1)-C(2)-C(3) = 119.0(2), C(2)-C(3)-C(4) -- 125.6(2), C(1)-C(2)-C(10) = 122.9(2), C(2)-C(10)-C(11) = 114.8(2), C(10)-C(11)-C(12) = 123.4(2), W(1)-N(1)-0(1) = 169.4(2). 178 To obtain some evidence for isomerization of the initial C-H activation product Cp*W(N0)(Ph)(r1 3-CH2CHCHPh), the thermolysis of 3.8 in C6D6 has been conducted at a lower temperature in a J-Young NMR tube and monitored by 1 E1 NMR spectroscopy. After 6 h of thermolysis at 50 °C, one new organometallic species B (selected signals (ppm) in its 1 H NMR spectrum: 1.35 (C 5Me5), 2.14 (s, 1H), 2.32 (s, 1H), 3.55 (s, 1H)) is observed. After 28 h signals attributable to 5.1 (1.61 (C 5Me5), 2.02 (s, 1H) and 2.74 (s, 1H)) are visible, and complex 5.1 is present in a ca. 1:4 ratio to B. When the sample is removed from the heat and left at RT overnight (16 h) the composition of the sample remains essentially unchanged. Thermolysis for a further 22 h results in a 5.1:B ratio of ca. 3:4. When thermolysis is conducted to the point at which the starting material 3.8 has been completely consumed (ca. 72 h), complex 5.1 is present as the ca. 3:2 major species. Intermediate B completely disappears after a further 24 h of thermolysis at 70 °C, at which point complex 5.1 is the only organometallic species present in the mixture. In solution complex 5.1 is thermally stable at 70 °C for at least 1 d. Based on these preliminary 1 11 NMR spectroscopic observations — the chemical shifts and the multiplicities of the new signals — it is possible that intermediate B is the phenyl phenylallyl complex Cp*W(N0)(Ph-d5)(11 3 -CH2CDCHPh). To confirm its identity an obvious follow-up experiment would be to independently synthesize the protio isotopomer of B by metathesis, obtain its spectroscopic data, and perform its thermolysis to see whether it does isomerize into 5.1. Regrettably, multiple attempts to synthesize protio isotopomer B from Cp*W(N0)(Ph)C1 and the bis(allyl)magnesium reagent (CH2CHCHPh)2Mg x(dioxane) have been unsuccessful to date. This failure is 179 frustrating especially considering the fact that B is stable in solution at RT for a sufficiently long period of time (vide infra). In addition, attempts to separate mixtures of 5.1 and B by chromatography have been unsuccessful. Regardless, if all the assumptions are valid, the transformation from B to 5.1 can be considered to be a rearrangement reaction initiated by the intramolecular nucleophilic attack of the metal-bound phenyl on the phenylallyl CH2 terminal (Scheme 1.2), a process that to our knowledge has no literature precedent. Scheme 1.2 5.2.3 Reactions with Other Hydrocarbons Complex 3.8 has been thermolyzed in a variety of other hydrocarbons. To date, none of these reactions has yielded a single organometallic species. Thermolysis of 3.8 in mesitylene leads to the formation of a monosubsituted allyl-containing organometallic product amidst other as yet unidentified species, possibly the benzyl C-H activation product Cp*W(N0)(CH2-3,5-C6H3Me2)(r1 3-CH2CHCHPh). 5 However, attempts to isolate this species by either fractional crystallization or chromatography have been 180 unsuccessful. Thermolysis of 3.8 in pentane leads to a product mixture that yields an indecipherable 'H NMR spectrum. Thermolysis of 3.8 in toluene leads to a mixture of products, some of which share similar spectral features with 5.1 — in addition to a myriad of signals in the aryl region, the 'H NMR spectrum of the mixture contains three groups of multiplets, likely diphenylallyl C-H resonances, centred around 5.90, 2.75 and 2.05 ppm respectively. Furthermore, there are three W-hydride signals located between -0.10 to -0.19 ppm. These peaks could well belong to the three diarylallyl hydrido species Cp*W(N0)(H)(i 3 -2-MeC6H4CHCHCHPh), Cp*W(NO)(H)(r1 3-3-McC6H4CHCHCHPh) and Cp*W(N0)(H)(11 3 -4-MeC6H4CHCHCHPh), which are the results of the isomerization of the initial aryl C-H activation products. In addition, a characteristic multiplet at 5.10 ppm, a doublet at 3.50 ppm and a Cp* Me signal at 1.41 ppm indicate the presence of a fourth organometallic species, possibly the benzyl phenylallyl complex Cp*W(NO)(CH2C6F1s)(11 3-CH2CHCHPh). The integration between the signal at 5.10 ppm and the group of signals at 5.90 ppm is approximately 1 :4. With the assumption that the product assignments are correct, the aryl vs benzyl regioselectivity exhibited by this allene intermediate during the C-H activation of toluene is comparable to those exhibited by other well-studied Cp*W(NO)-containing intermediates. 3 '5 The signals for this fourth species persist after the NMR sample of crude product mixture has been heated at 70 °C for a further 1 d, suggesting that the benzyl C-H activation product is not prone to isomerization. 181 5.3^Conclusion The preliminary results of reactivity studies on Cp*W(N0)(CH2CMe3)(11 3 - CH2CHCHPh) (3.8) have been presented in this chapter. Complex 3.8 has been shown to lose neopentane at elevated temperatures, in the process forming an allene intermediate that reacts with benzene to quantitatively form Cp*W(N0)(H)(ri 3-PhHCCHCHPh) (5.1). Complex 5.1 is likely formed by the initial C-H activation of benzene followed by an intramolecular rearrangement reaction. While the chemical transformations described in this chapter seem to have little significance in terms of their synthetic organic applicability, they do illustrate a new mode of intramolecular reactivity of transition- metal aryl-allyl complexes. 5.4^Experimental Procedures 5.4.1 General Considerations All reactions and subsequent manipulations involving organometallic reagents were performed under anaerobic and anhydrous conditions either under high vacuum or an inert atmosphere of prepurified dinitrogen. Purification of inert gases was achieved by passing them first through a column containing MnO and then a column of activated 4 A molecular sieves. Conventional glove-box and vacuum-line Schlenk techniques were utilized throughout. The glove boxes utilized were Innovative Technologies LabMaster 100 and MS-130 BG dual-station models equipped with freezers maintained at — 30 °C. 182 Most of the reactions were performed in thick-walled glass vessels possessing Kontes greaseless stopcocks and side-arm inlets for vacuum-line attachment. Small-scale reactions and NMR spectroscopic analyses were conducted in J. Young NMR tubes which were also equipped with Kontes greaseless stopcocks. All solvents were dried with appropriate drying agents under a dinitrogen atmosphere and were distilled prior to use, or they were transferred directly under vacuum from the appropriate drying agent. Hydrocarbon solvents, diethyl ether, and tetrahydrofuran were dried and distilled from sodium benzophenone ketyl. The synthesis of (CH2CHCHPh)MgBr from cinnamyl bromide (Aldrich) and magnesium (Strem) was carried out in a manner similar to that described previously for the synthesis of other allylmagnesium reagents, 3 and it was converted into the bis(allyl)magnesium reagent in the usual manner. 1 '3 The synthesis of Cp*W(N0)(CH2CMe3)01 3-CH2 CHCHPh) (3.8) has been described in section 3.4 of this Thesis. The progress of most reactions was monitored by NMR spectroscopy, but the isolated yields of all new complexes have not been optimized. All IR samples were prepared as Nujol mulls, and their spectra were recorded on a Thermo Nicolet 4700 FT-IR spectrometer. NMR spectra were recorded at room temperature on Broker AV-300 or AV-400 spectrometers. All chemical shifts are reported in ppm, and all coupling constants are reported in Hz. 1 H NMR spectra are referenced to the residual protio isotopomer present in a particular solvent, and 13C NMR spectra are referenced to the natural-abundance carbon signal of the solvent employed. When necessary, 1 H- 1 H COSY, 1 H- 13C HMQC and 13C APT experiments were carried out to correlate and assign 1 H and 13 C NMR signals. Low-resolution mass spectra (EI, 70 183 eV) were recorded by the staff of the UBC mass spectrometry facility using a Kratos MS- 50 spectrometer. Elemental analyses were performed by Mr. Minaz Lakha of the UBC microanalytical facility. 5.4.2 Preparation of Cp*W(N0)(H)(1 3-PhHCCHCHPh) (5.1) Complexes 5.1 and 5.2 were synthesized and purified in an identical manner, and the procedures for complex 5.1 are described below. In a glove box a glass bomb was charged with Cp*W(N0)(CH2CMe3)(1 3-CH2CHCHPh) (3.8) (53.7 mg, 0.100 mmol) and benzene (2 mL). At a vacuum line the mixture was degassed with three freeze-pump- thaw cycles, and the bomb was placed in a 75 °C water-ethylene glycol bath for 1 d. The volatiles were removed in vacuo from the final reaction mixture, and the yellow-brown residue was redissolved in pentane. The pentane solution was transferred to the top of an alumina column (6 x 0.5 cm) supported on glass wool in a Pasteur pipette. The column was washed with 1:1 Et20/pentane, and a light-yellow band eluted and was collected. Concentration of the eluate followed by storage at -30 °C for 1 d induced the deposition of Cp*W(N0)(H)(11 3-PhHCCHCHPh) (5.1) as yellow needles (42 mg, 75%) Characterization data for 5.1: IR (cm 1 ): 1564 (s,^1H NMR (400MHz, C6D6): 8 -0.15 (s, 1 JwH = 124, 1H, WH), 1.61 (s, 15H, C5Me5), 2.02 (d, 3JHH = 10.0, 1H, allyl PhCH), 2.74 (m, 3JHH = 12.6, 1H, ally! PhCH), 5.90 (dd, 34-m = 12.6, 3JHH = 10.0, 1H, allyl CH), 7.00 (t, 3JHH = 7.6, 1H, para CH), 7.09 (t, 3JHH = 7.6, 1H, para CH), 7.16 (obs, m, 2H meta CH), 7.33 (overlapping m, 4H, ortho and meta CH), 7.55 (d, 3JHH = 7.6, 2H, 184 ortho CH). 13C { 1 H} (100MHz, C6D 6): 8 10.2 (C 5/11e5), 62.7 (ally! PhCH), 75.6 (ally! PhCH), 103.9 (ally! CH), 105.0 (C5Me5), 125.3, 126.4, 127.1, 128.6, 128.7 (Aryl C), 143.0, 145.1 (Aryl ipso C). MS (LREI, probe temp. 100 °C) m/z 543 [Mt]. Anal. Calcd. for C25H29NOW: C 55.26, H 5.38, N 2.58. Found: C 55.16, H 5.28, N 2.54. 5.4.3 Preparation of Cp*W(N0)(H)(1 3-CH2C(3-cyclohexenyl)CHPh) (5.2) Complex 5.2 was synthesized by the thermolysis of 3.8 (53.7 mg, 0.100 mmol) in cyclohexene (2 mL) at 75 °C for 1 d. Complex 5.2 was crystallized as yellow-orange rods from pentane (33 mg, 66%). Characterization data for 5.2: IR (cm 1 ): 1560 (s, vN0). 1 H NMR (400MHz, C6D6): 8 0.20 (s, 1JWH = 126, 1H, WH), 1.61 (s, 15H, C5Me5), 2.00 (br s, 1H, allyl CH2), 3.10 (m, 1H, cyclohexenyl tertiary CH), 3.50 (m, 1 H, ally! CH2), 5.86 (m, 1H, cyclohexenyl CH=), 6.14 (br s, 1H, ally! CHPh), 6.16 (m, 1H, cyclohexenyl CH=), 6.70 (t, 3JHH = 8.0, 1H, para CH), 6.91 (t, 3JHH = 8.0, 2H, meta CH), 7.01 (d, 3JHH = 7.6, 2H, ortho CH). 13C { 1 H} (100MHz, C6D6): 8 9.9 (C5Me5), 21.3, 25.8 (cyclohexenyl CH2), 33.5 (cyclohexenyl CH2CH—), 44.9 (cyclohexenyl CHCH=), 51.4 (ally! CH2), 73.0 (ally! CHPh), 105.5 (C5Me5), 124.9 (para C), 125.4 (ally! C), 128.2 (meta C), 129.5 (cyclohexenyl CH=), 129.6 (ortho C), 130.1 (cyclohexenyl CH=), 139.7 (phenyl ipso C). MS (LREI, probe temp. 100 °C) m/z 547 [M4 ]. Anal. Calcd. for C25H33NOW: C 54.86, H 6.08, N 2.56. Found: C 55.01, H 6.10, N 2.47. 185 5.4.4 X-Ray Crystallography Data collection for each compound was carried out at —100 ±1 °C on either a Rigaku AFC7/ADSC CCD diffractometer or a Bruker X8 APEX diffractometer, using graphite-monochromated Mo Ka radiation. Data for 5.1 were collected to a maximum 20 value of 60.6 ° in 0.5 ° oscillations. The structure was solved by direct methods 8 and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically; hydrogen atoms H01 (hydride), Hla, Hlb, H3, H10, H11 and H12 were refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 6219 observed reflections and 286 variable parameters. X-ray crystallographic data for the structure are presented in Table A.B. Data for 5.2 were collected to a maximum 20 value of 56.4 ° in 0.5 ° oscillations. The structure was solved by direct methods 8 and expanded using Fourier techniques. The crystal was a racemic twin, and the crystallographic solution had one Et20 solvent molecule per two 5.2 molecules. The hydride of the first 5.2 molecule could be modeled on the basis of the residual electron density. The disordered nitrosyl ligand of the second 5.2 molecule was modeled in two positions, but the hydride could not be modeled. Disorder in the Et20 molecule could also not be fully modeled. All non-hydrogen atoms were refined anisotropically; hydrogen atom H01 (hydride) was refined isotropically, and all other hydrogen atoms were included in fixed positions. The final cycle of full-matrix least-squares analysis was based on 11491 observed reflections and 580 variable parameters. X-ray crystallographic data for the structure are presented in Table A.8. 186 187 5.5^References and Notes (1) Fujita-Takayama, C. Unpublished Observations (2) If Scheme 5.1 is valid, we would expect to observe a tungsten-deuteride and a fully protiated backbone of the phenylallyl ligand. (3) Ng, S.H.K.; Adams, C. S.; Hayton, T. W.; Legzdins, P.; Patrick, B. 0. , J. Am. Chem. Soc. 2003, 125 , 15210. (4) Possible identities for these two phosphorus-containing species are the expected allene-PMe3 adducts, with the phenyl groups oriented differently. (5)^C-H activation on mesitylene by Cp*W(NO)-containing fragments occurs exclusively at the benzylic positions. In addition to reference 3, see: Adams, C. S.; Legzdins, P. and Tran, E. Organometallics 2002, 21, 1474-1486. 188 CHAPTER 6 Conclusion and Future Work 6.1^Research Summary The research described in this thesis is efforts directed at understanding the C-H activating capability of Cp*W(NO)-containing complexes, and developing synthetically useful protocols that are centred around this process. In chapter 2 it has been shown that the alkylidene intermediate Cp*W(NO)(=CHCMe3), formed from the loss of neopentane from the complex Cp*W(NO)(CH2CMe3)2 (2.1) under thermal conditions, is able to selectively activate ortho C-H bonds of certain substituted arenes. 1 Unlike a few other reported systems, 2 the aryl C-H activation by Cp*W(NO)(=CHCMe3) does not proceed with 100% ortho regioselectivity. Rather, the ortho-isomer is formed as the major, thermodynamic isomer in all cases via intramolecular isomerization from the meta and para-activated products, and the exact regioselectivity depends mostly on steric factors, with smaller substituents such as a fluorine atom providing higher ortho-regioselectivity (up to 97%). The reaction between the fluorobenzene ortho-activated product Cp*W(N0)(CH2CMe3)(2-C6H4F) (2.2a) and CO was an attempt to derivatize the newly- formed 2-fluorophenyl fragment. It has been hoped that CO would preferentially insert into the W-phenyl bond. Instead, the CO inserts exclusively between the W-neopentyl bond, most likely due to steric reasons.3 189 In chapter 3 the synthesis of a series of alkyl-ally' complexes has been described. These new complexes have been sought after as we attempt to generalize previously observed reactivity demonstrated by the well-studied dimethylallyl complex Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCMe2) (3.1). Experimental results show that the presence of a methyl group on a terminal ally! carbon, as in the case of Cp*W(N0)(CH2CMe3)(1) 3-CH2CHCHMe) (3.7), leads to the facile loss of neopentane under thermal conditions. Meanwhile, the meso hydrogen on the ally! ligand can be abstracted during neopentane elimination if the ally' ligand is sufficiently bulky, as in the case of Cp*W(N0)(CH2CMe3)(1) 3 -CH2CHCHPh) (3.8) which loses neopentane at 75 °C, as opposed to Cp*W(N0)(CH2CMe3)(r1 3-C3H5) (3.5) which is thermally robust. Finally, complexes bearing bulky allyl ligands undergo facile concurrent N-H and a-C-H activation, a process that takes place at RT and does not require the formation of a 16e Cp*W(NO)-allene or diene-type intermediate. Curiously, the concurrent N-H and a-C-H activation is a general process only for cyclic amines. 4 In chapter 4 the thermal reactivity of Cp*W(N0)(CH2CMe3)(11 3 -CH2CHCHMe) (3.7) is thoroughly discussed. Complex 3.7 loses neopentane and forms a C-H activating 2^•^•-diene intermediate at RT — a mild condition that is ideal for aliphatic alkane single C- H activation, an otherwise challenging transformation for transition metal-based systems. The regioselectivity is exclusive for terminal (methyl) C-H bonds, which is a highly- desirable feature for future development of synthetic organic methodologies based on this organometallic complex. Heteroatom-containing organic substrates can be C-H activated in this manner as long as sites of unsaturation are absent on the molecule. Most 190 unsaturated organic substrates undergo an olefin-coupling reaction with the ri g -diene intermediate, resulting in the formation of metallocyclic allyl complexes. The newly- formed organic fragment can be released from the metal complex in a derivatized form as an iodoalkane by treatment with the metal complex with 12 in cold CHC13 solutions. 5 In chapter 5 the thermal reactivity of Cp*W(N0)(CH2CMe3)(i 3 -CH2CHCHPh) (3.8) is presented. Preliminary results indicate that complex 3.8 forms an allene intermediate that is capable of activating C-H bonds. However, under the thermal conditions employed, the initial C-H activation product is unstable, as in the case of the reaction with benzene, and isomerizes into an allyl-hydrido species. 6.2^Future Directions The chemical transformations described in this thesis are interesting in their own right. Some of the reactions are unprecedented in the literature. Others proceed at remarkably gentle conditions and/or yield products with desirable regioselectivities. Unfortunately, none of the transformations discussed in this Thesis are catalytic in nature, which implies that these Cp*W(NO)-based organometallic species are still some way away from finding their places in the area of synthetic organic chemistry, which is the Holy Grail of organometallic C-H activation research. 191 Multiple attempts have been made to functionalize the newly formed C-H activated fragment and release it from the metal centre. For example, the final reaction described in chapter 2, namely, the reaction between the fluorobenzene ortho-C-H- activated product Cp*W(N0)(CH2CMe3)(o-C6H4F) (2.2a) and NEt4CN, is an attempt to generate a 4-legged Cp*W(NO) piano stool complex, one that possesses the appropriate molecular geometry to undergo reductive elimination,6 in the process forming o- fluorobenzonitrile or 3,3-dimethylbutyronitrile, which would be a not-trivial way of generating an organic nitrile. 7 Unfortunately, heating of [NEt4] +[Cp*W(N0)(CH2CMe3)(CN)(o-C6H4F)T ([NEtd + [2.15] -) in benzene solutions only laeds to the reformation of 2.2a and NEt4CN. Possible future work will involve tuning the steric and electronic properties of the organometallic complexes by changing the ancillary ligands (e.g. making the metal centre more electron poor in order to counter the effect of the overall negative charge), in order to allow reductive elimination to occur in favor of simple cyanide dissociation. In chapter 4 , the net conversion of n-pentane into 1-iodopentane by Cp*W(NO)(CH2CMe3 )(r1 3 -CH2 CHCHMe) (3.7) has been described. However, there are two major drawbacks to the overall chemistry. First, the overall transformation is a stoichiometric conversion. Second, 1-iodopentane is liberated amidst other organic species such as methallyl iodide, and this leads to separation problems. A potential catalytic cycle built on the strength of the C-H activating ability of Cp*W(N0)(CH2CMe3)(11 3-CH2CHCHMe) (3.7) has been proposed and presented near the end of Section 4.3 of this Thesis. The major challenge in this chemistry are 1) to find 192 suitable electrophiles that would preferentially attack the W-alkyl bond over the W-allyl bond, and 2) to find a suitable Lewis base that can liberate HX from Cp*W(N0)(X)(1 3 - CH2CHCHMe) without coordinating to the catalytically active species, the n 2-diene intermediate. The incorporation of our C-H activation chemistry into catalytic processes will be our main research goal in the near future. 193 6.3^References and Notes (1) Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P.; Patrick, B. 0. Organomtallics 2006, 25, 4215. (2) (a) Ben-Ari, E.; Gandelman, M.; Rozenberg, H.; Shimon, 1. J. W. and Milstein, D. Organometallics. 2006, 25, 3190 and references therein. (b) Zhang, X.; Kanzelberger, M.; Emge, T. J. and Goldman, A. S. J. Am. Chem. Soc. 2004, 126, 13192. (c) Zhang, F.; Kirby, C. W.; Hairshine, D. W.; Jennings, M. C. and Puddephatt, R. J. I Am. Chem. Soc. 2005, 127, 14196. (d) Renkema, K. B.; Bosque, R.; Streib, W. E.; Maseras, F.; Eisenstein, 0. and Caulton, K. G. J. Am. Chem. Soc. 1999, 121, 10895. (3) Debad, J. D.; Legzdins, P.; Batchelor, R. J.; Einstein, F. W. B. Organometallics 1993, 12, 2094. (4) Tsang, J. Y. K.; Fujita-Takayama, C.; Buschhaus, M. S. A.; Patrick, B. O.; Legzdins, P. 1 Am. Chem. Soc. 2006, 128, 14762. (5) Tsang, J. Y. K.; Buschhaus, M. S. A.; Legzdins, P. J. Am. Chem. Soc. 2007, 129, 5372. (6) For a recent example of a 4-legged Cp*W(NO)-piano-stool complex capable of reductive elimination, see: Lee, K.; Legzdins, P.; Pamplin, C. B. and Wada, K. Organometallics 2005, 24, 638. (7)^Reductive elimination involving the cyano ligand CN - is rare. For an example of this transformation, see: Garcia, J. J.; Brunkan, N. M. and Jones, W. D. I Am. Chem. Soc., 2002, 124, 9547. 194 APPENDIX A Crystallographic Data Refinement, Structural Solution, Tables of Bond Lengths and Bond Angles for Structurally Characterized Complexes Described in this Thesis 195 Table A.1.^Crystal Data, Data Refinement and Structural Solution for Compounds 2.2a, 2.5a and 2.6a. Crystal Data^2.2a^2.5a^2.6a Empirical formula C21H30NOFW^C221133NO2W^C291-135NOW Crystal Habit, color^Irregular, red^Prism, dark red^Plate, purple Crystal size (mm) 0.30 x 0.15 x 0.09^0.50 x 0.50 x 0.10^0.20 x 0.15 x 0.05 Crystal system^Triclinic^Monoclinic^Triclinic Space group P_1 P2i/n P_1 1041.71(19) 2143.2(3) 1284.4(2) 8.2185(9) 10.6196(11) 8.8372(8) 9.2843(9) 18.1403(13) 9.1967(8) 14.5576(15) 11.2112(10) 16.620(2) 74.260(4) 90 75.253(4) 89.287(4) 97.101(3) 79.602(4) 77.311(4) 90 88.771(4) 2 4 2 1.643 1.634 1.545 5.561 5.405 4.517 508 1048 596 34992 18559 56192 4883 4666 5848 R1 = 0.0221, wR2 = R1 = 0.0356, wR2 = R1 = 0.0245, wR2 = 0.0586 0.0925 0.0686 1.092 1.096 1.212 1.963 and -1.918 4.605 and -3.493 1.282 and -1.263 Volume (A3) a (A) b (À) c (A) a (°) 13 (°) 7 (°) Z Density (calculatedd) (Mg/m 3) Absorption coefficient (mm') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indicesa Goodness-of-fit on F2 b Largest cliff. peak and hole (e - A-3) a R1 on F = E (1F01- IFcI)1/ E IF01, (-1 > 200); wR2 = [ (E ( F02 Fc2 )2 ) E w(F02 )2 :1 1/2 (all data); w = [ (Y2F02 ] -1 ; b GOF = [ E (w ( IFo l -^)2 )/ degrees of freedomr2 196 Table A.2.^Crystal Data, Data Refinement and Structural Solution for Compounds 2.7, 2.10c and 2.16. Crystal Data Empirical formula Crystal Habit, color Crystal size (mm) Crystal system Space group Volume (A3) a (Á) b (A) c (A) a (°) 3 (°) y (°) Z Density (calculatedd) (Mg/m 3 ) Absorption coefficient (mm -1) F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices' Goodness-of-fit on F2 b Largest cliff. peak and hole (e" A -) a R1 on F = E I Vol - !Fel) I / E IF01, (I> 26(1)); wR2 = [ (E ( F02 - Fc2 )2 ) / E w(F02 )2 71 1/2 (all data); w = [ G2F02 ] - i ; b OOF = [ E (w (1Foi - IFcl )2 ) / degrees offreedomr2 . 2.7 2.10c 2.16 C271145NOW C211129N0F2W C22H30NO2FW Plate, orange-red Rod, red Flat needle, yellow 0.20 x 0.20 x 0.05 0.50 x 0.20 x 0.20 0.40 x 0.12 x 0.03 Monoclinic Triclinic Monoclinic P21/n 13_1 1321/n (#14) 2565.9(3) 1047.99(15) 2159.2(4) 10.7920(10) 8.0777(6) 11.889(2) 16.4400(10) 9.4908(8) 15.862(2) 14.4680(10) 14.7275(13) 12.043(1) 90 72.039(3) 90 91.629(3) 89.092(2) 108.061(5) 90 77.726(2) 90 4 2 4 1.510 1.690 1.671 4.519 5.537 5.374 1184 524 1072 22737 20467 29400 5404 4972 5031 R1 = 0.0328, wR2 = R1 = 0.0126, wR2 = R1 = 0.031, wR2 = 0.0809 0.0310 0.061 1.123 1.052 1.03 2.423 and -1.740 0.691 and -0.496 2.29 and -0.98 197 Table A.3.^Crystal Data, Data Refinement and Structural Solution for Compounds 3.5, 3.7 and 3.8. Crystal Data^3.5^3.7^3.8 Empirical formula CI8H311■TOW^C10H33NOW^C24H35NOW Crystal Habit, color^Prism, orange^Prism, yellow^Rod, yellow-orange Crystal size (mm) 0.35 x 0.22 x 0120^0.45 x 0.30 x 0.20^1.4 x 0.1 x 0.1 Crystal system^Monoclinic^Monoclinic^Monoclinic Space group P21/c P21/c P21/c 1837.2(2) 1940.63(8) 2223.15(17) 10.6510(6) 9.0412(2) 12.7252(6) 11.5052(6) 14.2430(3) 11.7231(5) 15.1007(8) 15.6092(4) 15.2438(7) 90 90 90 96.778(3) 105.103(1) 102.146(2) 90 90 90 4 4 4 1.667 1.627 1.606 6.286 5.955 5.209 912 944 1072 31681 29663 27675 5306 4599 5262 R1 = 0.039, wR2 = R1 = 0.0178, wR2 = R1 = 0.0210, wR2 = 0.102 0.0423 0.0660 1.11 1.080 1.153 1.26 and -1.35 1.185 and -0.806 1.504 and -1.371 Volume (A 3) a (A) b (A) c (A) a (°) R (o) 7 (0) Z Density (calculatedd) (Mg/m 3 ) Absorption coefficient (mm- ') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices' Goodness-of-fit on F2 b Largest cliff peak and hole (e - A-3) " R1 on F = E (1F01 - iFel) E^(I> 2a(1)); wR2 = [ (E ( F02 - Fc2 )2 ) E w(F02 )2]"2 (all data); w = [ a2F02 ] -1 ; b GOF = [ E (w (^-^)2 )/ degrees of freedomr2 . 198 Table A.4.^Crystal Data, Data Refinement and Structural Solution for Compounds 3.9 A / B, 3.10 and 3.14. Crystal Data^3.9 A / B^3.10^3.14 Empirical formula C18H33NOSiW^C211137N3OW^C231140N2OW Crystal Habit, color^Prism, orange^Needle, yellow^Prism, yellow Crystal size (mm) 0.8 x 0.5 x 0.5^0.55 x 0.075 x 0.05^0.40 x 0.175 x 0.075 Crystal system^Monoclinic^Triclinic^Monoclinic Space group P21/c P-1 P21/c 1997.7(5) 2217.0(6) 2347.98(14) 9.4739(14) 8.0022(10) 12.6452(4) 13.991(2) 16.383(3) 8.1081(3) 15.631(2) 17.082(3) 22.9995(8) 90 84.451(6) 90 105.378(7) 89.925(6) 95.311(2) 90 84.088(6) 90 4 4 4 1.634 1.592 1.540 5.845 5.224 4.934 976 1064 1096 33457 11672 36666 5957 11672 5392 R1 = 0.0456, wR2 = R1 = 0.0315, wR2 = R1 = 0.0200, wR2 = 0.1103 0.0553 0.0500 1.181 0.883 1.061 5.310 and -7.005 1.925 and -0.957 1.731 and -0.674 Volume (A3 ) a (A) b (A) c (A) a (°) R (o) y (°) Z Density (calculated) (Mg/m 3 ) Absorption coefficient (mm') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices' Goodness-of-fit on F2 b Largest cliff. peak and hole (e- A-3) °R1 on F = E I (IFor - IFc1) I / EiF0i, (1 > 2a(i)); wR2 = [ (E ( F0 2 - Fe2 )2 ) / E w(F02 )2 :1 1/2 (all data); w = [ G2F02 ] -1 ; b GOF = [ E (w ( iFo l - IF,1)2 ) I degrees of freedom] I/2 . 199 Table A.S.^Crystal Data, Data Refinement and Structural Solution for Compounds 4.1, 4.2 and 4.6. Crystal Data^4.1^4.2^4.6 Empirical formula C19H33NOW^C17H30NOPW^C16H27NOW Crystal Habit, color^Rod, yellow Prism, yellow^Prism, yellow Crystal size (mm) 0.35 x 0.20 x 0.10^0.35 x 0.20 x 0.20^0.35 x 0.30 x 0.05 Crystal system^Monoclinic^Monoclinic^Monoclinic Space group P21/n P21/n P21/n Volume (A 3) a (A) b (A) c (A) a (0) R (°) 7 (0) Z Density (calculated) (Mg/m 3) Absorption coefficient (mm') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices' Goodness-of-fit on F2 b Largest cliff. Peak and hole (e - k3) a R1 on F = E I (IF01- IFcI) I / E IF0I, (I> 2a(-0); wR2 = [ (E ( F0 2 - Fc2 )2 ) / E w(F02 )2r2 (all data); w = [ a2Fo2 ] -1 ; b GOF = [ E (w (iFoi - iFel ) 2 ) / degrees offreedomr2 . 1919.05(17) 1875.15(16) 1622.3(4) 8.9209(5) 8.1936(4) 11.7746(16) 18.9252(9) 15.3514(8) 9.4294(13) 11.3669(6) 14.9078(7) 14.829(2) 90 90 90 90.286(3) 90.020(1) 99.830(7) 90 90 90 4 4 4 1.645 1.698 1.774 6.022 6.245 7.114 944 944 848 36501 15837 21587 4679 4503 3767 R1 = 0.0232, wR2 = R1 = 0.0216, wR2 = R1 = 0.0211, wR2 =- 0.0526 0.0536 0.0498 1.038 1.014 1.064 1.619 and -0.774 1.579 and -0.932 0.959 and -0.830 200 Table A.6.^Crystal Data, Data Refinement and Structural Solution for Compounds 4.11, 4.13 and 4.14. Crystal Data Empirical formula Crystal Habit, color Crystal size (mm) Crystal system Space group Volume (A3) a (A) b (A) c (A) a 0 0 (°) y (0) Z Density (calculated) (Mg/m 3) Absorption coefficient (mm -1 ) F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices' Goodness-of-fit on F 2 b Largest cliff. Peak and hole (e A-3) R1 on F=E I (IF o! -^I E IFo l, (I> 2a(1)); wR2 = [ (E ( F. 2 - Fe2 )2 ) E w(F0 2 )2] "2 (all data); w = [ cr2F o2 ]'; b GOF = [ E (w (1Fol -IF,1 )2 ) / degrees of freedom r 2 . 4.11 4.13 4.14 C20H3INOW CI9H311\102W CI8H27NOW Rod, yellow Plate, orange Prism, orange 0.35 x 0.07 x 0.07 0.5 x 0.5 x 0.1 0.5 x 0.4 x 0.3 Triclinic Monoclinic Monoclinic P..1 P21/n P21/n 1830.3(12) 1877.8(2) 1660.9(3) 8.813(3) 9.2125(8) 10.2949(9) 14.376(6) 14.4236(12) 12.0055(13) 14.850(6) 14.8434(3) 13.5878(14) 103.120(10) 90 90 91.290(10) 107.809(4) 98.512(5) 92.040(10) 90 90 4 4 4 1.761 1.731 1.829 6.316 6.161 6.954 960 968 896 8753 19800 21396 8753 4493 3834 RI = 0.0906, wR2 = R1 = 0.0256, wR2 = RI = 0.0186, wR2 = 0.2577 0.0694 0.0464 1.085 1.059 1.063 6.086 and -6.859 1.625 and -1.802 1.048 and -1.122 201 Table A.7.^Crystal Data, Data Refinement and Structural Solution for Compounds 4.15 and 4.16. Crystal Data Empirical formula Crystal Habit, color Crystal size (mm) Crystal system Space group Volume (A3) a (A) b (A) c (A) a (0) (°) 7 (0) Z Density (calculated) (Mg/m3) Absorption coefficient (mm') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indicesa Goodness-of-fit on F2 b Largest cliff. peak and hole (e k3) a RI on F= E 0F01-1F0 1) / E^2,7(-0); wR2 = [ (E (Fo2 -Fc2 )2 ) 1E w(F02 )2r2 (all data); W = [ CS2F02 ]"i; b GOF = [ E (w (1F01 - IF01 )2 ) / degrees offreedomr2 4.15 4.16 C201133NOW C211129NOW • IA (0C4148) Irregular, orange Prism, yellow 0.40 x 0.30 x 0.30 0.20 x 0.20 x 0.05 Monoclinic Orthorhombic C2/c P212121 4391.3(7) 1902.05(12) 30.129(3) 8.7093(3) 9.0268(9) 13.8379(5) 17.0499(13) 15.7822(6) 90 90 108.735(3) 90 90 90 8 4 1.583 1.730 5.273 6.080 2096 976 25263 17222 5277 4538 R1 = 0.0322, wR2 = R1 = 0.0273, wR2 = 0.0827 0.0581 1.050 1.087 2.099 and -1.051 0.931 and -0.877 202 Table A.B.^Crystal Data, Data Refinement and Structural Solution for Compounds 5.1 and 5.2. Crystal Data Empirical formula Crystal Habit, color Crystal size (mm) Crystal system Space group Volume (A3) a (A) b (A) c (A) a (0) 13 (°) 7 (°) Z Density (calculatedd) (Mg/m 3) Absorption coefficient (mm') F000 Data Collection and Refinement Measured Reflections: Total Measured Reflections: Unique Final R Indices a Goodness-of-fit on F 2 b Largest cliff. peak and hole (e . L 3) a R1 on F = E I (IF01 - IF0) I / E IF0I, (I> 2cT(I)); wR2 = [ (E ( F02 - Fc2 )2 ) / E w(F02 )2 71 1/2 (all data); w = [ (72F02 yi; b GOF = [ E (w ( IF01- IF,I )2 )/ degrees offreedom] 1/2 . 5.1 5.2 C25H20NOW C25H33NOW . Y2(C4 11100) Prism, yellow Prism, orange 0.40 x 0.20 x 0.12 0.6 x 0.6 x 0.35 Orthorhombic Triclinic P212121 P_1 4812.5(10) 1066.2(3) 9.3219(9) 9.4452(15) 22.502(3) 11.0514(17) 22.943(3) 11.6303(16) 90 71.176(7) 90 86.420(8) 90 68.403(8) 8 2 1.602 1.705 4.821 5.432 2312 544 38299 31022 11491 6219 R1 = 0.0530, wR2 = R1 = 0.0204, wR2 = 0.1327 0.0491 1.064 1.102 3.729 and -2.287 0.860 and -1.351 203 Table A.9.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.2a. W1 N1 1.775(2) W1 C7 2.101(3) WI Cl 2.162(3) W1 C13 2.314(3) W1 C12 2.319(3) W1 C14 2.412(3) WI C16 2.419(3) W1 C15 2.465(3) Fl C2 1.373(4) 01 N1 1.228(3) C5 C4 1.385(5) C5 C6 1.398(5) C15 C14 1.425(4) C15 C16 1.429(4) C15 C20 1.510(4) C16 C12 1.439(4) C16 C21 1.509(4) C12 C13 1.438(4) C12 C17 1.507(4) C8 C10 1.525(4) C8 C9 1.531(4) C8 C11 1.547(4) C8 C7 1.552(4) Cl C2 1.397(4) Cl C6 1.397(4) C3 C2 1.380(4) C3 C4 1.389(5) C14 C13 1.424(4) C14 C19 1.503(4) C13 C18 1.503(5) Table A.10.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.2a. N1 W1 C7 99.01(11) C14 W1 C15 33.96(10) C9 C8 C7 111.6(2) N1 W1 Cl 92.31(11) C16 W1 C15 34.01(10) C11 C8 C7 108.8(2) C7 W1 Cl 113.38(11) 01 N1 W1 169.4(2) C8 C7 W1 130.9(2) N1 W1 C13 94.17(11) C4 C5 C6 119.9(3) C2 Cl C6 114.5(3) C7 W1 C13 111.61(11) C14 C15 C16 107.9(3) C2 Cl W1 121.5(2) Cl W1 C13 132.81(11) C14 C15 C20 125.5(3) C6 Cl W1 123.9(2) N1 W1 C12 98.75(11) C16 C15 C20 126.5(3) C2 C3 C4 118.0(3) C7 W1 C12 144.20(11) C14 C15 W1 71.00(16) C13 C14 C15 108.6(3) Cl WI C12 96.65(11) C16 C15 W1 71.23(16) C13 C14 C19 126.5(3) C13 W1 C12 36.17(11) C20 C15 W1 125.6(2) C15 C14 C19 124.6(3) N1 W1 C14 122.45(11) C15 C16 C12 108.1(3) C13 C14 W1 68.73(17) C7 W1 C14 85.72(11) C15 C16 C21 126.1(3) C15 C14 W1 75.05(16) Cl W1 C14 138.08(10) C12 C16 C21 125.5(3) C19 C14 W1 127.3(2) C13 W1 C14 34.99(11) C15 C16 W1 74.76(16) C14 C13 C12 107.9(3) C12 W1 C14 58.55(10) C12 C16 W1 68.54(16) C14 C13 C18 126.2(3) N1 W1 C16 131.60(11) C21 C16 W1 127.2(2) C12 C13 C18 125.8(3) C7 W1 C16 127.14(11) C13 C12 C16 107.4(3) C14 C13 W1 76.28(18) Cl W1 C16 82.86(10) C13 C12 C17 126.9(3) C12 C13 W1 72.08(17) C13 W1 C16 58.64(11) C16 C12 C17 125.6(3) C18 C13 W1 120.6(2) C12 W1 C16 35.29(11) C13 C12 W1 71.74(17) C5 C4 C3 119.9(3) C14 W1 C16 57.08(10) C16 C12 W1 76.17(17) Fl C2 C3 117.4(3) N1 W1 C15 151.88(11) C17 C12 W1 121.0(2) Fl C2 Cl 117.4(3) C7 W1 C15 94.22(11) C10 C8 C9 109.5(3) C3 C2 Cl 125.2(3) Cl W1 C15 105.06(10) C10 C8 C11 108.7(3) C5 C6 Cl 122.4(3) C13 W1 C15 57.81(10) C9 C8 C11 108.8(3) C12 W1 C15 57.97(10) C10 C8 C7 109.3(3) 204 Table A.11.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.5a. W1 N1 1.765(3) W1 C8 2.122(4) W1 Cl 2.149(3) W1 C16 2.318(3) W1 C17 2.324(3) W1 C15 2.402(3) W1 C13 2.427(3) W1 C14 2.458(3) N1 02 1.223(4) 01 C2 1.378(4) 01 C7 1.432(4) C16 C17 1.431(5) C16 C15 1.432(5) C16 C21 1.501(5) C14 C13 1.415(5) C14 C15 1.430(4) C14 C19 1.502(4) C15 C20 1.497(5) C17 C13 1.434(5) C17 C22 1.505(5) C8 C9 1.530(5) C12 C9 1.521(5) C13 C18 1.513(4) C5 C4 1.385(5) C5 C6 1.395(5) C9 C10 1.527(7) C9 C11 1.535(6) C2 C3 1.396(4) C2 Cl 1.406(4) C4 C3 1.385(5) Cl C6 1.406(5) Table A.12.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.5a. N1 W1 C8 98.56(13) C15 W1 C14 34.20(11) C13 C17 W1 76.41(19) N1 W1 Cl 91.28(12) C13 W1 C14 33.65(11) C22 C17 W1 121.8(2) C8 W1 Ci 110.84(13) 02 N1 W1 171.6(3) C9 C8 W1 129.7(2) N1 W1 C16 92.96(12) C2 01 C7 117.6(3) C14 C13 C17 108.2(3) C8 W1 C16 115.16(14) C17 C16 C15 107.6(3) C14 C13 C18 127.4(3) Cl W1 C16 132.53(13) C17 C16 C21 126.1(4) C17 C13 C18 124.2(3) N1 W1 C17 101.67(13) C15 C16 C21 126.1(4) C14 C13 W1 74.37(18) C8 WI C17 144.92(13) C17 C16 W1 72.28(18) C17 C13 W1 68.53(18) Cl W1 C17 97.11(12) C15 C16 W1 75.57(18) C18 C13 WI 127.0(2) C16 W1 C17 35.92(13) C21 C16 W1 121.9(2) C4 C5 C6 119.7(3) N1 W1 C15 118.91(12) C13 C14 C15 108.3(3) C12 C9 C10 110.1(4) C8 W1 C15 86.63(13) C13 C14 C19 127.8(3) C12 C9 C8 109.5(3) Cl W1 C15 143.10(11) C15 C14 C19 123.9(3) C10 C9 C8 108.5(3) C16 W1 C15 35.27(12) C13 C14 W1 71.98(16) C12 C9 C11 109.1(4) C17 W1 C15 58.50(12) C15 C14 W1 70.74(17) C10 C9 C11 108.2(4) N1 W1 C13 135.51(13) C19 C14 WI 125.4(2) C8 C9 C11 111.5(3) C8 W1 C13 123.54(12) C14 C15 C16 108.1(3) 01 C2 C3 123.2(3) Cl W1 C13 86.85(11) C14 C15 C20 125.4(3) 01 C2 Cl 114.8(3) C16 W1 C13 58.41(11) C16 C15 C20 126.3(3) C3 C2 Cl 122.0(3) C17 W1 C13 35.06(12) C14 C15 W1 75.07(17) C5 C4 C3 120.4(3) C15 W1 C13 57.02(11) C16 C15 W1 69.16(17) C6 Cl C2 116.6(3) N1 W1 C14 150.69(12) C20 C15 W1 125.9(2) C6 Cl W1 123.5(2) C8 W1 C14 91.92(12) C16 C17 C13 107.9(3) C2 Cl W1 119.7(2) Cl WI C14 110.48(11) C16 C17 C22 126.8(4) C5 C6 Cl 121.8(3) C16 W1 C14 57.93(11) C13 C17 C22 125.1(4) C4 C3 C2 119.4(3) C17 W1 C14 57.61(12) C16 C17 WI 71.80(19) 205 Table A.13.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.6a. W1 N1 1.767(3) Cl C2 1.415(6) C22 C21 1.432(6) W1 C15 2.118(4) C16 C19 1.533(6) C22 C27 1.507(6) W1 Cl 2.156(4) C16 C18 1.537(6) C13 C14 1.387(7) W1 C22 2.325(4) C16 C17 1.539(6) C13 C12 1.407(7) W1 C21 2.334(4) C16 C15 1.544(5) C8 C7 1.203(6) W1 C23 2.403(4) C5 C4 1.377(7) C8 C9 1.442(6) W1 C20 2.424(4) C5 C6 1.420(6) C2 C3 1.393(6) W1 C24 2.464(4) C23 C22 1.410(6) C4 C3 1.394(7) 01 N1 1.225(5) C23 C24 1.428(6) C6 C7 1.451(6) C20 C24 1.419(6) C23 C28 1.512(6) C10 C9 1.412(6) C20 C21 1.438(6) C11 C12 1.367(7) C29 C24 1.514(6) C20 C25 1.506(6) C11 C10 1.387(6) C14 C9 1.397(6) Cl C6 1.409(6) C26 C21 1.500(7) Table A.14.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.6a. N1 W1 C15 98.62(16) C24 C20 C25 125.9(4) C14 C13 C12 119.6(4) N1 W1 Cl 91.97(15) C21 C20 C25 125.8(4) C7 C8 C9 175.9(4) C15 W1 Cl 113.99(15) C24 C20 W1 74.7(2) C3 C2 Cl 122.7(4) N1 W1 C22 92.48(15) C21 C20 W1 69.0(2) C5 C4 C3 119.3(4) C15 W1 C22 114.95(15) C25 C20 W1 127.6(3) Cl C6 C5 121.5(4) Cl W1 C22 129.49(15) C6 Cl C2 115.7(4) Cl C6 C7 122.4(3) N1 W1 C21 100.42(16) C6 Cl W1 123.5(3) C5 C6 C7 116.1(4) C15 W1 C21 145.30(15) C2 Cl Wi 120.7(3) C22 C21 C20 107.6(4) Cl W1 C21 94.08(14) C19 C16 C18 108.4(4) C22 C21 C26 126.4(4) C22 W1 C21 35.79(14) C19 C16 C17 109.0(4) C20 C21 C26 125.8(4) N1 W1 C23 118.57(15) C18 C16 C17 109.2(4) C22 C21 W1 71.8(2) C15 Wi C23 87.41(14) C19 C16 C15 110.9(3) C20 C21 W1 75.8(2) Cl W1 C23 140.35(14) C18 C16 C15 109.7(4) C26 C21 W1 121.7(3) C22 W1 C23 34.66(15) C17 C16 C15 109.6(3) C8 C7 C6 173.8(4) C21 W1 C23 58.00(14) C4 C5 C6 120.6(4) C11 C12 C13 120.1(4) N1 W1 C20 134.19(15) 01 N1 W1 170.3(3) C11 C10 C9 120.1(4) C15 W1 C20 124.75(15) C22 C23 C24 108.8(4) C16 C15 W1 129.6(3) Cl WI C20 83.84(14) C22 C23 C28 125.8(4) C13 C14 C9 120.6(4) C22 W1 C20 58.36(13) C24 C23 C28 125.1(4) C20 C24 C23 107.8(4) C21 W1 C20 35.13(14) C22 C23 W1 69.7(2) C20 C24 C29 126.8(4) C23 W1 C20 56.94(13) C24 C23 W1 75.3(2) C23 C24 C29 125.3(4) N1 W1 C24 149.91(14) C28 C23 W1 126.2(3) C20 C24 W1 71.6(2) C15 W1 C24 92.99(15) C12 C11 C10 120.7(4) C23 C24 W1 70.6(2) Cl W1 C24 108.51(14) C23 C22 C21 107.9(4) C29 C24 WI 126.5(3) C22 W1 C24 57.52(14) C23 C22 C27 126.5(4) C2 C3 C4 120.1(4) C21 W1 C24 57.46(15) C21 C22 C27 125.4(4) C14 C9 C10 118.7(4) C23 W1 C24 34.09(13) C23 C22 W1 75.7(2) C14 C9 C8 122.7(4) C20 W1 C24 33.74(14) C21 C22 W1 72.5(2) C10 C9 C8 118.6(4) C24 C20 C21 107.8(3) C27 C22 WI 122.0(3) 206 Table A.15.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.7. Cl C2 1.416(6) C10 H1OB 0.9800 C19 C20 1.527(6) C 1 C5 1.426(7) C10 H10C 0.9800 C19 W1 2.396(4) Cl C6 1.513(7) C11 C16 1.456(6) C20 C21 1.511(7) Cl W1 2.324(4) C11 C12 1.535(6) C20 H2OA 0.9900 C2 C3 1.418(6) Cll W1 2.328(4) C20 H2OB 0.9900 C2 C7 1.505(6) C11 H11 0.94(6) C21 H21A 0.9800 C2 W1 2.400(4) C12 C15 1.517(7) C21 H21B 0.9800 C3 C4 1.410(7) C12 C13 1.526(8) C21 H21C 0.9800 C3 C8 1.501(7) C12 C14 1.533(8) C22 C25 1.336(6) C3 W1 2.452(4) C13 H13A 0.9800 C22 C23 1.507(6) C4 C5 1.430(7) C13 H13B 0.9800 C23 C24 1.523(7) C4 C9 1.513(7) C13 H13C 0.9800 C23 H23A 0.9900 C4 W1 2.424(4) C14 H14A 0.9800 C23 H23B 0.9900 C5 C10 1.507(7) C14 H14B 0.9800 C24 H24A 0.9800 C5 W1 2.332(4) C14 H14C 0.9800 C24 H24B 0.9800 C6 H6A 0.9800 C15 H15A 0.9800 C24 H24C 0.9800 C6 H6B 0.9800 C15 H15B 0.9800 C25 C26 1.511(6) C6 H6C 0.9800 C15 H15C 0.9800 C25 W1 2.192(4) C7 H7A 0.9800 C16 C19 1.408(6) C26 C27 1.531(6) C7 H7B 0.9800 C16 C17 1.516(5) C26 H26A 0.9900 C7 H7C 0.9800 C16 W1 2.294(4) C26 H26B 0.9900 C8 H8A 0.9800 C17 C18 1.525(6) C27 H27A 0.9800 C8 H8B 0.9800 C17 H17A 0.9900 C27 H27B 0.9800 C8 H8C 0.9800 C17 H17B 0.9900 C27 H27C 0.9800 C9 H9A 0.9800 C18 H18A 0.9800 N1 01 1.216(5) C9 H9B 0.9800 C18 H18B 0.9800 N1 W1 1.785(4) C9 H9C 0.9800 C18 H18C 0.9800 C10 H10A 0.9800 C19 C22 1.498(6) Table A.16.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.7. C2 CI C5 108.3(4) C2 Cl C6 126.3(5) C5 Cl C6 125.1(4) C2 Cl W1 75.5(3) C5 Cl W1 72.5(3) C6 CI W1 122.9(3) Cl C2 C3 107.8(4) Cl C2 C7 128.2(5) C3 C2 C7 123.4(4) Cl C2 W1 69.6(2) C3 C2 W1 75.0(2) C7 C2 W1 127.9(3) C4 C3 C2 108.5(4) C4 C3 C8 125.8(5) C2 C3 C8 124.4(5) C4 C3 W1 72.1(2) C2 C3 W1 71.0(2) C8 C3 W1 132.8(3) C3 C4 C5 108.1(4) C3 C4 C9 124.3(5) C5 C4 C9 126.8(5) C3 C4 W1 74.3(2) C5 C4 W1 69.0(2) C9 C4 W1 130.7(3) Cl C5 C4 107.2(4) Cl C5 C10 123.4(5) C4 C5 C10 129.0(5) Cl C5 W1 71.9(3) C4 C5 W1 76.1(3) C10 C5 W1 123.0(3) Cl C6 H6A 109.5 Cl C6 H6B 109.5 H6A C6 H6B 109.5 Cl C6 H6C 109.5 H6A C6 H6C 109.5 H6B C6 H6C 109.5 C2 C7 H7A 109.5 C2 C7 H7B 109.5 H7A C7 H7B 109.5 C2 C7 H7C 109.5 H7A C7 H7C 109.5 H7B C7 H7C 109.5 C3 C8 H8A 109.5 C3 C8 H8B 109.5 H8A C8 H8B 109.5 C3 C8 H8C 109.5 H8A C8 H8C 109.5 H8B C8 H8C 109.5 C4 C9 H9A 109.5 C4 C9 H9B 109.5 H9A C9 H9B 109.5 207 C4 C9 H9C 109.5 H9A C9 H9C 109.5 H9B C9 H9C 109.5 C5 C10 H10A 109.5 C5 C10 H1OB 109.5 H10A C10 H1OB 109.5 C5 C10 H10C 109.5 H10A C10 H10C 109.5 H1OB C10 H10C 109.5 C16 C11 C12 127.5(4) C16 C11 W1 70.4(2) C12 C11 W1 130.8(3) C16 C11 H11 114(3) C12 C11 H11 107(3) W1 C11 H11 102(3) C15 C12 C13 109.2(6) C15 C12 C14 106.7(5) C13 C12 C14 107.3(5) C15 C12 C11 108.4(4) C13 C12 C11 115.9(4) C14 C12 C11 109.1(4) C12 C13 H13A 109.5 C12 C13 H13B 109.5 H13A C13 H13B 109.5 C12 C13 H13C 109.5 H13A C13 H13C 109.5 H13B C13 H13C 109.5 C12 C14 H14A 109.5 C12 C14 H14B 109.5 H14A C14 H14B 109.5 C12 C14 H14C 109.5 H14A C14 H14C 109.5 H14B C14 H14C 109.5 C12 C15 H15A 109.5 C12 C15 H15B 109.5 H15A C15 H15B 109.5 C12 C15 H15C 109.5 H15A C15 H15C 109.5 H15B C15 H15C 109.5 C19 C16 C11 116.1(3) C19 C16 C17 119.3(4) C11 C16 C17 124.3(4) C19 C16 WI 76.5(2) C11 C16 W1 72.9(2) C17 C16 W1 115.7(3) C16 C17 C18 111.7(4) C16 C17 H17A 109.3 C18 C17 H17A 109.3 CI6 C17 H17B 109.3 C18 C17 H17B 109.3 H17A C17 H17B 107.9 C17 C18 H18A 109.5 C17 C18 H18B 109.5 H18A C18 H18B 109.5 C17 C18 H18C 109.5 H18A C18 H18C 109.5 H18B C18 H18C 109.5 C16 C19 C22 119.2(3) C16 C19 C20 121.9(4) C22 C19 C20 118.2(3) C16 C19 W1 68.6(2) C22 C19 WI 90.9(3) C20 C19 W1 118.6(3) C21 C20 C19 111.0(4) C21 C20 H2OA 109.4 C19 C20 H2OA 109.4 C21 C20 H2OB 109.4 C19 C20 H2OB 109.4 H2OA C20 H2OB 108.0 C20 C21 H21A 109.5 C20 C21 H21B 109.5 H21A C21 H21B 109.5 C20 C21 H21C 109.5 H21A C21 H21C 109.5 H21B C21 H21C 109.5 C25 C22 C19 105.3(4) C25 C22 C23 129.6(4) C19 C22 C23 125.0(4) C22 C23 C24 113.9(4) C22 C23 H23A 108.8 C24 C23 H23A 108.8 C22 C23 H23B 108.8 C24 C23 H23B 108.8 H23A C23 H23B 107.7 C23 C24 H24A 109.5 C23 C24 H24B 109.5 H24A C24 H24B 109.5 C23 C24 H24C 109.5 H24A C24 H24C 109.5 H24B C24 H24C 109.5 C22 C25 C26 126.4(4) C22 C25 WI 104.9(3) C26 C25 W1 128.5(3) C25 C26 C27 110.4(4) C25 C26 H26A 109.6 C27 C26 H26A 109.6 C25 C26 H26B 109.6 C27 C26 H26B 109.6 H26A C26 H26B 108.1 C26 C27 H27A 109.5 C26 C27 H27B 109.5 H27A C27 H27B 109.5 C26 C27 H27C 109.5 H27A C27 H27C 109.5 H27B C27 H27C 109.5 01 N1 W1 170.2(4) Ni W1 C25 90.13(16) Ni W1 C16 90.65(15) C25 W1 C16 79.08(15) Ni W1 Cl 92.32(16) C25 W1 Cl 99.77(16) C16 W1 Cl 176.82(14) N1 WI C11 94.86(16) C25 W1 C11 115.50(15) C16 W1 C11 36.72(14) Cl W1 C11 143.92(16) N1 W1 C5 95.24(17) C25 W1 C5 135.17(16) C16 WI C5 145.04(17) Cl W1 C5 35.69(18) C11 W1 C5 108.34(16) N1 WI C19 116.34(15) C25 W1 C19 58.68(15) C16 W1 C19 34.84(14) Cl WI C19 142.15(15) C11 W1 C19 61.92(14) C5 WI C19 146.95(16) Ni W1 C2 121.60(16) C25 WI C2 81.22(15) C16 W1 C2 142.03(14) Cl W1 C2 34.84(14) C11 W1 C2 140.70(15) C5 W1 C2 58.25(15) C19 W1 C2 107.54(14) N1 WI C4 127.53(18) C25 W1 C4 133.28(16) C16 W1 C4 120.82(16) Cl W1 C4 57.90(17) C11 WI C4 90.49(16) C5 W1 C4 34.93(18) C19 W1 C4 112.06(16) C2 WI C4 56.81(16) N1 WI C3 149.05(16) C25 W1 C3 99.82(15) C16 W1 C3 119.92(14) Cl WI C3 57.24(15) C11 W1 C3 106.76(15) C5 W1 C3 57.36(16) C19 W1 C3 93.61(14) C2 WI C3 33.96(15) C4 WI C3 33.60(16) 208 Table A.17.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.10c. W1 N1 1.7686(14) C7 C8 1.545(2) C13 C14 1.436(3) W1 C7 2.1002(17) C16 C12 1.419(2) C8 C11 1.531(3) W1 Cl 2.1657(17) C16 C15 1.424(3) C8 C10 1.540(2) W1 C14 2.3093(17) C16 C21 1.506(2) C2 C3 1.381(3) W1 C13 2.3112(17) C12 C13 1.436(3) C2 Cl 1.396(2) W1 C15 2.4004(17) C12 C17 1.507(3) C15 C14 1.431(2) W1 C12 2.4091(17) C9 C8 1.529(3) C15 C20 1.503(2) W1 C16 2.4528(17) C18 C13 1.510(2) C6 Cl 1.388(2) 01 N1 1.2280(19) C19 C14 1.507(3) C6 C5 1.388(3) Fl C2 1.376(2) C4 C5 1.382(3) F2 C6 1.365(2) C4 C3 1.383(3) Table A.18.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.10c. N1 W1 C7 97.88(7) C15 W1 C16 34.10(6) Cll C8 C7 109.66(15) N1 W1 Cl 95.95(6) C12 W1 C16 33.91(6) C10 C8 C7 108.95(15) C7 W1 Cl 112.40(7) C8 C7 W1 131.50(12) Fl C2 C3 116.70(16) N1 W1 C14 92.05(6) C12 C16 C15 108.06(15) Fl C2 Cl 116.70(15) C7 W1 C14 111.68(7) C12 C16 C21 126.67(17) C3 C2 Cl 126.60(18) Cl W1 C14 133.50(6) C15 C16 C21 125.19(16) C2 C3 C4 117.61(18) N1 W1 C13 99.17(6) C12 C16 W1 71.36(10) C16 C15 C14 108.54(15) C7 W1 C13 143.79(7) C15 C16 WI 70.93(10) C16 C15 C20 125.17(17) Cl W1 C13 97.30(6) C21 C16 W1 126.01(12) C14 C15 C20 125.94(17) C14 W1 C13 36.22(6) C16 C12 C13 108.29(16) C16 C15 W1 74.96(10) N1 W1 C15 119.46(6) C16 C12 C17 125.89(17) C14 C15 W1 68.87(10) C7 W1 C15 85.10(6) C13 C12 C17 125.54(16) C20 C15 W1 127.32(12) Cl W1 C15 138.53(6) C16 C12 W1 74.73(10) F2 C6 Cl 118.67(16) C14 W1 C15 35.30(6) C13 C12 W1 68.60(9) F2 C6 C5 116.04(17) C13 W1 C15 58.70(6) C17 C12 W1 127.06(12) Cl C6 C5 125.28(18) N1 W1 C12 132.95(6) C5 C4 C3 119.94(18) C4 C5 C6 118.76(19) C7 W1 C12 125.95(6) C12 C13 C14 107.68(15) C15 C14 C13 107.41(16) Cl W1 C12 83.41(6) C12 C13 C18 125.99(17) C15 C14 C19 126.29(17) C14 W1 C12 58.82(6) C14 C13 C18 126.17(17) C13 C14 C19 126.13(17) C13 W1 C12 35.34(6) C12 C13 W1 76.06(10) C15 C14 WI 75.83(10) C15 W1 C12 57.15(6) C14 C13 W1 71.82(10) C13 C14 W1 71.96(10) N1 W1 C16 150.19(6) C18 C13 W1 121.46(12) C19 C14 W1 121.54(12) C7 W1 C16 93.21(6) C9 C8 C11 108.89(16) C6 Cl C2 111.80(16) Cl W1 C16 105.24(6) C9 C8 C10 108.95(15) C6 Cl W1 127.40(13) C14 W1 C16 58.15(6) C11 C8 C10 109.15(16) C2 Cl W1 120.79(13) C13 W1 C16 58.01(6) C9 C8 C7 111.21(15) 01 Ni W1 169.27(13) 209 Table A.19.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 2.16. Cl C2 1.421(6) C9 H9B 0.9800 C19 C22 1.537(6) Cl C5 1.436(6) C9 H9C 0.9800 C20 H2OA 0.9800 Cl C6 1.508(7) C10 H10A 0.9800 C20 H2OB 0.9800 Cl W1 2.319(4) C10 H1OB 0.9800 C20 H2OC 0.9800 C2 C3 1.439(7) C10 H10C 0.9800 C21 H21A 0.9800 C2 C7 1.518(6) C11 C12 1.3900 C21 H21B 0.9800 C2 W1 2.388(4) C11 C16 1.3900 C21 H21C 0.9800 C3 C4 1.429(6) C11 W1 2.250(6) C22 H22A 0.9800 C3 C8 1.511(6) C12 Fl 1.373(9) C22 H22B 0.9800 C3 W1 2.442(4) C12 C13 1.3900 C22 H22C 0.9800 C4 C5 1.423(6) C13 C14 1.3900 N1 01 1.233(5) C4 C9 1.516(6) C13 H13 0.9500 N1 W1 1.788(4) C4 W1 2.414(4) C14 C15 1.3900 02 W1 2.219(3) C5 C10 1.514(6) C14 H14 0.9500 W1 C11B 2.211(9) C5 W1 2.327(4) C15 C16 1.3900 C11B C12B 1.3900 C6 H6A 0.9800 C15 H15 0.9500 C11B C16B 1.3900 C6 H6B 0.9800 C161116 0.9500 C12B F1B 1.371(10) C6 H6C 0.9800 C17 02 1.248(5) C12B C13B 1.3900 C7 H7A 0.9800 C17 C18 1.504(6) C13B C14B 1.3900 C7 H7B 0.9800 C17 W1 2.067(4) C13B H13B 0.9500 C7 H7C 0.9800 C18 C19 1.546(6) C14B C15B 1.3900 C8 H8A 0.9800 C18 H18A 0.9900 C14B H14B 0.9500 C8 H8B 0.9800 C18 H18B 0.9900 C15B C16B 1.3900 C8 H8C 0.9800 C19 C20 1.533(7) C15B H15B 0.9500 C9 H9A 0.9800 C19 C21 1.535(6) Cl6B H16B 0.9500 Table A.20.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 2.16. C2 Cl C5 107.6(4) C5 C4 W1 69.2(2) C3 C8 H8A 109.5 C2 Cl C6 128.6(4) C3 C4 W1 74.0(2) C3 C8 H8B 109.5 C5 Cl C6 123.6(4) C9 C4 W1 127.2(3) H8A C8 H8B 109.5 C2 Cl W1 75.1(2) C4 C5 Cl 107.8(4) C3 C8 H8C 109.5 C5 Cl W1 72.3(2) C4 C5 C10 127.0(4) H8A C8 H8C 109.5 C6 Cl W1 122.3(3) Cl C5 C10 124.7(5) H8B C8 H8C 109.5 Cl C2 C3 109.0(4) C4 C5 W1 75.9(2) C4 C9 H9A 109.5 Cl C2 C7 125.5(5) Cl C5 W1 71.7(2) C4 C9 H9B 109.5 C3 C2 C7 125.1(4) C10 C5 W1 124.8(3) H9A C9 H9B 109.5 Cl C2 W1 69.8(2) Cl C6 H6A 109.5 C4 C9 H9C 109.5 C3 C2 W1 74.8(2) Cl C6 H6B 109.5 H9A C9 H9C 109.5 C7 C2 W1 127.2(3) H6A C6 H6B 109.5 H9B C9 H9C 109.5 C4 C3 C2 106.5(4) Cl C6 H6C 109.5 C5 C10 H10A 109.5 C4 C3 C8 126.8(5) H6A C6 H6C 109.5 C5 C10 H1OB 109.5 C2 C3 C8 126.5(4) H6B C6 H6C 109.5 H10A C10 H1OB 109.5 C4 C3 W1 71.8(2) C2 C7 H7A 109.5 C5 C10 H10C 109.5 C2 C3 W1 70.6(2) C2 C7 H7B 109.5 H10A C10 H10C 109.5 C8 C3 W1 125.9(3) 117A C7 H7B 109.5 H1OB C10 H10C 109.5 C5 C4 C3 109.1(4) C2 C7 117C 109.5 C12 C11 C16 120.0 C5 C4 C9 125.6(4) H7A C7 H7C 109.5 C12 C11 WI 120.4(5) C3 C4 C9 125.1(5) H7B C7 H7C 109.5 C16 C11 W1 119.5(5) 210 Fl C12 C11 119.8(6) H21A C21 H21B 109.5 Cl W1 C2 35.11(15) Fl C12 CI3 119.9(6) C19 C21 H21C 109.5 C5 WI C2 58.52(15) C11 C12 C13 120.0 H21A C21 H21C 109.5 Ni W1 C4 128.07(16) C14 C13 C12 120.0 H21B C21 H21C 109.5 C17 WI C4 133.31(16) C14 C13 H13 120.0 C19 C22 H22A 109.5 C11B WI C4 80.5(6) C12 C13 H13 120.0 C19 C22 H22B 109.5 02 WI C4 128.03(15) C15 C14 C13 120.0 H22A C22 1122B 109.5 C11 W1 C4 81.2(5) C15 C14 H14 120.0 C19 C22 H22C 109.5 Cl W1 C4 58.36(16) C13 C14 H14 120.0 H22A C22 H22C 109.5 C5 W1 C4 34.87(16) C14 C15 C16 120.0 H22B C22 H22C 109.5 C2 W1 C4 57.20(15) C14 C15 H15 120.0 01 Ni WI 168.4(3) N1 W1 C3 150.68(16) C16 C15 H15 120.0 C17 02 W1 66.5(2) C17 WI C3 99.33(16) C15 C16 C11 120.0 Ni W1 C17 95.05(17) C11B W1 C3 99.9(5) C15 C16 H16 120.0 N1 W1 CHB 96.9(5) 02 WI C3 103.89(14) C11 C16 H16 120.0 C17 W1 CHB 115.0(5) C11 W1 C3 102.7(4) 02 C17 C18 122.8(4) Ni W1 02 102.23(14) Cl W1 C3 58.50(16) 02 C17 W1 79.9(3) C17 W1 02 33.62(15) C5 W1 C3 58.25(15) C18 C17 WI 157.3(4) C11B WI 02 81.4(5) C2 WI C3 34.64(16) C17 C18 C19 114.1(4) N1 W1 C11 92.7(4) C4 WI C3 34.22(15) C17 C18 H18A 108.7 C17 W1 C11 118.0(4) C12B Cl lB C16B 120.0 C19 C18 H18A 108.7 CHB WI C11 4.8(7) C12B C1 1B W1 121.5(9) C17 C18 H18B 108.7 02 WI C11 84.7(4) C16B C1 1B WI 118.5(9) C19 C18 H18B 108.7 Ni WI Cl 92.64(16) F1B C12B C13B 118.5(11) H18A C18 H18B 107.6 C17 W1 Cl 109.47(17) F1B C12B CHB 121.3(11) C20 C19 C21 109.4(4) C1 1B W1 Cl 133.3(5) C13B C12B C11B 120.0 C20 C19 C22 109.0(4) 02 W1 Cl 140.42(14) C12B C13B C14B 120.0 C21 C19 C22 109.8(4) C11 WI Cl 131.5(4) C12B C13B H13B 120.0 C20 C19 C18 111.3(4) N1 WI C5 95.94(16) C14B C13B H13B 120.0 C21 C19 C18 110.5(4) C17 W1 C5 144.11(17) C13B C14B C15B 120.0 C22 C19 C18 106.8(4) C11B W1 C5 97.4(5) C13B C14B H14B 120.0 C19 C20 H2OA 109.5 02 W1 C5 161.80(15) C15B C14B H14B 120.0 C19 C20 H2OB 109.5 C11 W1 C5 95.5(4) C16B C15B C14B 120.0 H2OA C20 H2OB 109.5 Cl W1 C5 36.00(15) C16B C15B H15B 120.0 C19 C20 H2OC 109.5 Ni W1 C2 122.07(17) C14B C15B H15B 120.0 H2OA C20 H2OC 109.5 C17 W1 C2 86.86(16) C15B C16B CIIB 120.0 H2OB C20 H2OC 109.5 Cl 1B WI C2 134.1(6) C15B C16B H16B 120.0 C19 C21 H21A 109.5 02 W1 C2 109.58(14) CHB C16B H16B 120.0 C19 C21 H21B 109.5 C11 WI C2 136.3(4) 211 Table A.21.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.5. Cl C2 1.361(10) C7 H7A 0.9800 ^ C13 W1 2.336(6) Cl W1 2.416(6) ^ C7 H7B 0.9800 C14 H14A 0.9800 Cl H1A 0.89(7) C7 H7C 0.9800 C14 H14B 0.9800 Cl H1B 1.10(9) C8 H8A 0.9800 ^ C14 H14C 0.9800 C2 C3 1.425(10) ^ C8 H8B 0.9800 C15 H15A 0.9800 C2 W1 2.339(6) C8 H8C 0.9800 C15 H15B 0.9800 C2 112 0.94(7) C9 C13 1.416(9) ^ C15 H15C 0.9800 C3 W1 2.252(6) ^ C9 C10 1.431(8) C16 H16A 0.9800 C3 H3A 0.98(7) C9 C14 1.514(8) C16 H16B 0.9800 C3 H3B 0.87(9) C9 W1 2.338(6) ^ C16 H16C 0.9800 C4 C5 1.558(8) ^ C10 C11 1.430(8) C17 H17A 0.9800 C4 WI 2.267(6) C10 C15 1.496(9) C17 H17B 0.9800 C4 H4A 0.9900 C10 W1 2.409(5) ^ C17 H17C 0.9800 C4 H4B 0.9900 ^ C11 C12 1.425(9) C18 H18A 0.9800 C5 C6 1.535(8) C11 C16 1.513(8) C18 H18B 0.9800 C5 C7 1.539(8) C11 W1 2.432(6) ^ C18 H18C 0.9800 C5 C8 1.547(8) ^ C12 C13 1.446(8) N1 01 1.236(7) C6 H6A 0.9800 C12 C17 1.493(9) N1 W1 1.770(5) C6 H6B 0.9800 C12 W1 2.418(5) C6 H6C 0.9800 ^ C13 C18 1.520(8) Table A.22.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.5. C2 Cl W1 70.3(4) C2 Cl H1A 121(4) W1 Cl H1A 99(4) C2 Cl H1B 124(5) W1 Cl H1B 127(5) H1A Cl H1B 108(6) Cl C2 C3 118.3(7) Cl C2 W1 76.5(4) C3 C2 W1 68.6(3) Cl C2 H2 115(4) C3 C2 H2 126(4) W1 C2 H2 117(4) C2 C3 W1 75.3(4) C2 C3 H3A 124(4) W1 C3 H3A 120(4) C2 C3 H3B 108(6) W1 C3 H3B 96(6) H3A C3 H3B 122(7) C5 C4 W1 124.3(4) C5 C4 H4A 106.3 W1 C4 H4A 106.3 C5 C4 H4B 106.3 W1 C4 H4B 106.3 H4A C4 H4B 106.4 C6 C5 C7 107.9(5) C6 C5 C8 108.7(5) C7 C5 C8 108.7(5) C6 C5 C4 114.1(5) C7 C5 C4 107.9(5) C8 C5 C4 109.4(5) C5 C6 H6A 109.5 C5 C6 H6B 109.5 H6A C6 H6B 109.5 C5 C6 H6C 109.5 H6A C6 H6C 109.5 H6B C6 H6C 109.5 C5 C7 H7A 109.5 C5 C7 H7B 109.5 H7A C7 H7B 109.5 C5 C7 H7C 109.5 H7A C7 H7C 109.5 H7B C7 H7C 109.5 C5 C8 H8A 109.5 C5 C8 H8B 109.5 H8A C8 H8B 109.5 C5 C8 H8C 109.5 H8A C8 H8C 109.5 H8B C8 H8C 109.5 C13 C9 C10 108.8(5) C13 C9 C14 125.9(6) C10 C9 C14 125.2(6) C13 C9 W1 72.3(3) C10 C9 W1 75.2(3) C14 C9 W1 121.7(4) C11 C10 C9 107.0(5) C11 C10 C15 127.4(5) C9 C10 C15 125.0(6) C11 C10 W1 73.7(3) C9 C10 W1 69.8(3) C15 C10 W1 128.2(4) C12 C11 C10 109.1(5) C12 C11 C16 125.1(6) C10 C11 C16 125.6(6) C12 C11 W1 72.4(3) C10 C11 W1 71.9(3) C16 C11 W1 125.9(4) C11 C12 C13 107.0(5) C11 C12 C17 124.4(5) C13 C12 C17 128.5(6) C11 C12 W1 73.5(3) C13 C12 W1 69.2(3) C17 C12 W1 126.6(4) C9 C13 C12 108.0(5) C9 C13 C18 125.6(5) C12 C13 C18 126.0(6) C9 C13 W1 72.4(3) C12 C13 WI 75.4(3) C18 C13 W1 124.0(4) 212 C9 C14 H14A 109.5 C9 C14 H14B 109.5 H14A C14 H14B 109.5 C9 C14 H14C 109.5 H14A C14 H14C 109.5 H14B C14 H14C 109.5 C10 C15 H15A 109.5 C10 C15 H15B 109.5 H15A C15 H15B 109.5 C10 C15 H15C 109.5 H15A C15 H15C 109.5 H15B C15 H15C 109.5 C11 C16 H16A 109.5 C11 C16 H16B 109.5 H16A C16 H16B 109.5 C11 C16 H16C 109.5 H16A C16 H16C 109.5 H16B C16 H16C 109.5 C12 C17 H17A 109.5 C12 C17 H17B 109.5 H17A C17 H17B 109.5 C12 C17 H17C 109.5 H17A C17 H17C 109.5 H17B C17 H17C 109.5 C13 C18 H18A 109.5 C13 C18 H18B 109.5 H18A C18 H18B 109.5 C13 C18 H18C 109.5 H18A C18 H18C 109.5 H18B C18 H18C 109.5 01 Ni WI 171.2(5) Ni WI C3 92.2(3) Ni W1 C4 93.1(2) C3 W1 C4 134.0(2) Ni W1 C13 100.9(2) C3 WI C13 136.3(2) C4 WI C13 87.1(2) Ni W1 C9 90.4(2) C3 W1 C9 104.1(2) C4 WI C9 121.5(2) C13 W1 C9 35.3(2) Ni WI C2 89.3(3) C3 WI C2 36.1(2) C4 WI C2 98.3(2) C13 WI C2 168.2(2) C9 WI C2 140.2(2) Ni WI C10 114.6(2) C3 WI C10 78.2(2) C4 WI C10 138.1(2) C13 WI C10 58.4(2) C9 W1 C10 35.06(19) C2 WI C10 112.0(2) N1 WI Cl 113.1(2) C3 WI Cl 61.5(2) C4 WI Cl 74.5(2) C13 WI Cl 141.8(2) C9 W1 Cl 151.8(2) C2 WI CI 33.2(2) C10 WI Cl 117.1(2) Ni WI C12 135.6(2) C3 WI C12 123.6(2) C4 WI C12 80.6(2) C13 WI C12 35.36(19) C9 WI C12 58.3(2) C2 WI C12 135.0(2) C10 W1 C12 57.6(2) Cl WI C12 107.4(2) Ni W1 C11 147.3(2) C3 WI C11 89.7(2) C4 W1 C11 108.8(2) C13 W1 C11 57.83(19) C9 WI C11 57.63(19) C2 WI C11 110.4(2) C10 W1 C11 34.4(2) Cl W1 C11 96.4(2) C12 W1 C11 34.2(2) 213 Table A.23.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.7. W1 Ni 1.764(2) C11 C10 1.428(4) C13 C18 1.500(4) W1 C5 2.257(3) C11 C12 1.430(4) C12 C17 1.503(4) W1 C3 2.282(3) C11 C16 1.498(4) C6 C7 1.524(4) W1 C12 2.337(3) C2 Cl 1.372(5) C6 C5 1.556(4) W1 C11 2.339(3) C2 C3 1.425(4) C14 C10 1.422(4) W1 C2 2.346(3) C8 C6 1.533(4) C14 C19 1.497(4) W1 C13 2.399(3) 01 N1 1.221(3) C15 C10 1.500(4) W1 Cl 2.401(3) C9 C6 1.531(4) C3 C4 1.509(4) W1 C10 2.412(2) C13 C12 1.418(4) WI C14 2.423(3) C13 C14 1.434(4) Table A.24.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.7. N1 W1 C5 92.53(11) C3 W1 C10 124.11(10) C18 C13 W1 130.3(2) N1 W1 C3 91.85(11) C12 W1 C10 58.13(9) C13 C12 C11 108.1(2) C5 W1 C3 133.68(11) C11 W1 C10 34.93(9) C13 C12 C17 126.2(3) Ni W1 C12 90.92(10) C2 W1 C10 134.02(10) C11 C12 C17 125.5(3) C5 Wl. C12 121.50(10) C13 W1 C10 57.26(9) C13 C12 W1 74.99(15) C3 W1 C12 104.50(10) Cl W1 C10 105.87(11) C11 C12 W1 72.26(15) N1 WI. C11 101.46(10) N1 W1 C14 148.25(10) C17 C12 W1 122.5(2) C5 W1 C11 86.85(10) C5 W1 C14 108.68(10) C7 C6 C9 109.1(3) C3 W1 C11 136.96(10) C3 W1 C14 90.13(10) C7 C6 C8 107.1(3) C12 W1 C11 35.62(9) C12 W1 C14 58.02(9) C9 C6 C8 108.0(3) Ni W1 C2 90.19(11) C11 W1 C14 58.00(9) C7 C6 C5 114.3(2) C5 W1 C2 98.05(11) C2 W1 C14 109.18(10) C9 C6 C5 110.2(2) C3 W1 C2 35.83(11) C13 W1 C14 34.59(9) C8 C6 C5 107.9(2) C12 W1 C2 140.33(10) Cl W1 C14 94.47(11) C6 C5 W1 123.4(2) C11 W1 C2 167.18(10) C10 W1 C14 34.21(9) C10 C14 C13 107.6(2) N1 W1 C13 115.22(10) C10 C11 C12 107.7(2) C10 C14 C19 126.6(3) C5 W1 C13 137.95(10) C10 C11 C16 126.9(2) C13 C14 C19 125.4(3) C3 W1 C13 79.02(10) C12 C11 C16 124.9(3) C10 C14 W1 72.46(14) C12 W1 C13 34.80(9) C10 C11 W1 75.31(15) C13 C14 W1 71.80(15) C11 W1 C13 58.22(9) C12 C11 W1 72.12(15) C19 C14 W1 126.6(2) C2 W1 C13 111.97(10) C16 C11 W1 124.96(19) C2 C3 C4 120.4(3) N1 W1 Cl 114.31(12) Cl C2 C3 119.3(3) C2 C3 W1 74.53(16) C5 W1 Cl 74.33(11) Cl C2 W1 75.43(17) C4 C3 W1 121.1(2) C3 W1 Cl 61.99(11) C3 C2 W1 69.64(15) C14 C10 C11 108.3(2) C12 W1 Cl 150.62(11) 01 N1 W1 170.5(2) C14 C10 C15 125.0(3) C11 W1 Cl 139.81(11) C12 C13 C14 108.2(2) C11 C10 C15 126.4(2) C2 W1 Cl 33.58(11) C12 C13 C18 125.7(3) C14 C10 W1 73.33(14) C13 W1 Cl 116.33(11) C14 C13 C18 125.3(3) C11 C10 W1 69.75(14) N1 W1 C10 135.72(10) C12 C13 W1 70.21(15) C15 C10 W1 127.85(18) C5 WI. C10 80.74(9) C14 C13 W1 73.62(15) C2 Cl W1 70.99(17) 214 Table A.25.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.8. W1 N1 1.772(3) C3 C2 1.437(5) C19 C24 1.509(5) W1 C10 2.265(3) C3 C4 1.494(4) C15 C20 1.507(5) W1 C3 2.304(3) C16 C17 1.420(5) C13 C11 1.545(5) W1 C18 2.326(3) C16 C15 1.420(5) C17 C22 1.501(5) W1 C17 2.327(3) C16 C21 1.502(5) C10 C11 1.564(4) W1 C2 2.345(3) Cl C2 1.365(5) C11 C14 1.534(4) W1 Cl 2.397(3) C18 C19 1.432(5) C5 C6 1.389(5) W1 C19 2.410(3) C18 C17 1.439(5) C6 C7 1.388(5) W1 C16 2.428(3) C18 C23 1.516(5) C8 C9 1.386(5) W1 C15 2.460(3) C4 C5 1.400(4) C8 C7 1.391(5) Ni 01 1.223(4) C4 C9 1.404(5) C12 C11 1.530(5) C19 C15 1.422(5) Table A.26.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.8. N1 W1 C10 90.06(11) C2 W1 C16 111.38(11) C5 C4 C3 120.6(3) N1 W1 C3 90.25(12) Cl W1 C16 108.16(12) C9 C4 C3 122.5(3) C10 W1 C3 131.78(11) C19 W1 C16 56.87(11) C15 C19 C18 108.0(3) N1 W1 C18 96.26(12) N1 W1 C15 148.12(11) C15 C19 C24 123.5(3) C10 W1 C18 89.31(11) C10 W1 C15 106.07(11) C18 C19 C24 128.1(3) C3 W1 C18 138.48(12) C3 W1 C15 98.42(11) C15 C19 WI 74.96(17) N1 W1 C17 90.72(11) C18 W1 C15 57.60(11) C18 C19 W1 69.22(16) C10 W1 C17 125.00(12) C17 W1 C15 57.46(11) C24 C19 W1 127.0(2) C3 W1 C17 103.21(11) C2 W1 C15 110.00(11) C16 C15 C19 108.3(3) C18 W1 C17 36.04(12) Cl W1 C15 89.19(11) C16 C15 C20 125.6(3) N1 W1 C2 95.00(12) C19 W1 C15 33.94(11) C19 C15 C20 125.6(3) C10 W1 C2 96.02(11) C16 W1 C15 33.78(11) C16 C15 W1 71.88(17) C3 W1 C2 35.99(11) 01 Ni W1 169.7(2) C19 C15 W1 71.10(17) C18 W1 C2 167.54(11) C2 C3 C4 121.0(3) C20 C15 WI 128.9(2) C17 W1 C2 138.59(12) C2 C3 W1 73.56(17) C16 C17 C18 107.8(3) Ni W1 Cl 121.66(12) C4 C3 WI 121.1(2) C16 C17 C22 126.4(3) C10 W1 Cl 76.83(12) C17 C16 C15 108.4(3) C18 C17 C22 125.6(3) C3 W1 Cl 62.45(12) C17 C16 C21 124.9(3) C16 C17 W1 76.57(18) C18 W1 Cl 139.06(12) C15 C16 C21 126.0(3) C18 C17 W1 71.94(17) C17 W1 Cl 142.71(12) C17 C16 W1 68.77(17) C22 C17 W1 121.2(2) C2 W1 Cl 33.44(12) C15 C16 W1 74.34(17) C11 C10 W1 123.6(2) N1 W1 C19 129.56(11) C21 C16 W1 129.8(2) C12 C11 C14 109.3(3) C10 W1 C19 79.89(10) C2 Cl W1 71.17(19) C12 C11 C13 107.9(3) C3 W1 C19 132.35(11) C19 C18 C17 107.5(3) C14 C11 C13 107.5(3) C18 W1 C19 35.13(11) C19 C18 C23 127.5(3) C12 C11 C10 110.4(3) C17 W1 C19 58.50(11) C17 C18 C23 124.8(3) C14 C11 C10 114.2(3) C2 W1 C19 134.97(12) C19 C18 W1 75.64(17) C13 C11 C10 107.3(3) Cl W1 C19 103.99(11) C17 C18 W1 72.02(17) C6 C5 C4 121.5(3) N1 W1 C16 118.88(11) C23 C18 W1 121.8(2) C7 C6 C5 120.9(3) C10 WI C16 136.62(11) Cl C2 C3 120.9(3) C9 C8 C7 121.0(3) C3 W1 C16 82.93(11) Cl C2 W1 75.39(19) C8 C9 C4 121.4(3) C18 WI C16 58.09(11) C3 C2 W1 70.45(17) C6 C7 C8 118.3(3) C17 W1 C16 34.66(12) C5 C4 C9 116.9(3) 215 Table A.27.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.9 A / B. C5 Sil 1.835(7) C12 C17 1.493(9) W1 C2A 2.339(10) C5 W1 2.212(6) C12 W1 2.369(6) W1 C1B 2.35(3) C9 C13 1.408(10) C13 C18 1.491(11) W1 C2B 2.39(2) C9 C10 1.413(9) C13 W1 2.406(7) OA C2A 1.392(16) C9 C14 1.487(10) Sil C7A 1.840(11) C2A C3A 1.415(16) C9 W1 2.381(7) Sil C8B 1.858(13) C3A C4A 1.504(14) C10 C11 1.417(8) Sil C6A 1.859(10) N1A 01A 1.210(11) C10 C15 1.488(9) Sil C6B 1.863(15) C1B C2B 1.40(2) C10 W1 2.298(5) Sil C8A 1.881(11) C2B C3B 1.41(2) C11 C12 1.407(9) Sil C7B 1.884(15) C3B C4B 1.50(2) Cll C16 1.482(9) W1 N1A 1.690(8) 01B N1B 1.275(17) C11 W1 2.306(6) W1 N1B 1.863(15) C12 C13 1.426(10) W1 C3A 2.278(8) Table A.28.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.9 A / B. Sil C5 W1 119.4(4) C5 Sil C8B 126.6(8) C5 W1 C11 124.0(2) C13 C9 C10 108.2(6) C7A Sil C8B 75.4(11) C3A W1 C11 104.3(3) C13 C9 C14 124.9(7) C5 Sil C6A 111.4(10) C10 W1 C11 35.8(2) C10 C9 C14 126.5(7) C7A Sil C6A 111.0(12) N1A W1 C2A 90.2(5) C13 C9 W1 73.9(4) C8B Sil C6A 113.8(15) N1B W1 C2A 108.4(8) C10 C9 W1 69.2(4) C5 Sil C6B 112(2) C5 W1 C2A 95.3(4) C14 C9 W1 128.2(5) C7A Sil C6B 111(3) C3A W1 C2A 35.7(4) C9 C10 C11 107.9(6) C8B Sil C6B 113(2) C10 W1 C2A 164.1(4) C9 C10 C15 125.8(6) C6A Sil C6B 0(4) C11 W1 C2A 140.0(4) C11 C10 C15 125.8(6) C5 Sil C8A 111.7(5) N1A W1 C1B 66.7(9) C9 C10 W1 75.7(4) C7A Sil C8A 110.2(9) N1B W1 C1B 81.0(11) C11 C10 W1 72.4(3) C8B Sil C8A 34.8(9) C5 W1 C1B 137.0(6) C15 C10 Wi 123.9(5) C6A Sil C8A 99.2(15) C3A W1 C1B 28.9(8) C12 C11 C10 108.2(6) C6B Sil C8A 99(2) C10 W1 C1B 131.8(6) C12 C11 C16 126.0(6) C5 Sil C7B 99.8(12) C11 W1 C1B 96.0(6) C10 C11 C16 125.7(6) C7A Sil C7B 24.4(11) C2A W1 C1B 50.2(7) C12 C11 WI 75.0(4) C8B Sil C7B 99.8(15) N1A W1 C12 118.3(4) C10 C11 W1 71.8(3) C6A Sil C7B 98.9(16) N1B Wi C12 111.5(8) C16 C11 W1 122.0(5) C6B Sil C7B 99(3) C5 W1 C12 138.7(2) C11 C12 C13 107.8(6) C8A Sil C7B 134.4(13) C3A W1 C12 77.2(3) C11 C12 C17 125.0(6) N1A W1 N1B 18.3(7) C10 W1 C12 58.7(2) C13 C12 C17 126.3(6) N1A W1 C5 92.7(4) C11 W1 C12 35.0(2) C11 C12 WI 70.1(3) N1B W1 C5 89.2(8) C2A WI C12 110.1(4) C13 C12 W1 74.1(4) N1A W1 C3A 93.8(4) C1B W1 C12 82.9(6) C17 C12 W1 130.0(5) N1B W1 C3A 109.5(8) N1A W1 C9 139.0(4) C9 C13 C12 107.9(6) C5 W1 C3A 130.4(3) N1B Wi C9 120.7(8) C9 C13 C18 126.5(7) N1A W1 C10 104.9(4) C5 W1 C9 81.1(2) C12 C13 C18 125.3(7) N1B W1 C10 86.9(8) C3A W1 C9 121.0(3) C9 C13 W1 71.9(4) C5 W1 C10 88.9(2) C10 W1 C9 35.1(2) C12 C13 W1 71.2(4) C3A W1 C10 135.9(3) C11 W1 C9 58.4(2) C18 C13 W1 127.4(7) N1A W1 C11 94.6(4) C2A W1 C9 130.6(4) C5 Sil C7A 112.7(7) N1B W1 C11 81.8(8) C1B W1 C9 139.2(7) 216 C12 W1 C9 57.7(2) N1A W1 C2B 65.9(7) N1B W1 C2B 84.2(10) C5 W1 C2B 103.2(5) C3A W1 C2B 38.7(7) C10 W1 C2B 164.8(6) C11 W1 C2B 130.2(5) C2A W1 C2B 25.5(7) C1B W1 C2B 34.4(5) C12 W1 C2B 113.7(6) C9 W1 C2B 155.0(7) N1A W1 C13 151.8(4) N1B W1 C13 139.5(8) C5 W1 C13 108.0(3) C3A W1 C13 87.2(3) C10 W1 C13 58.0(3) C11 W1 C13 58.1(2) C2A W1 C13 106.2(4) C1B W1 C13 106.3(7) C12 W1 C13 34.7(2) C9 W1 C13 34.2(2) C2B W1 C13 124.5(7) C2A CIA W1 69.1(5) CIA C2A C3A 118.0(11) CIA C2A W1 77.1(6) C3A C2A W1 69.8(5) C2A C3A C4A 119.3(10) C2A C3A W1 74.5(5) C4A C3A W1 118.3(7) 01A N1A W1 167.5(10) C2B C1B W1 74.5(13) C1B C2B C3B 118(3) C1B C2B W1 71.1(13) C3B C2B W1 73.6(16) C2B C3B C4B 120(3) C2B C3B W1 72.2(15) C4B C3B W1 128(2) 01B N1B W1 171(2) 217 Table A.29.^Bond Distances (A) in the Solid-State Molecular Structure Deteimined for 3.10. C21A Cl6A 1.509(7) C14A C15A 1.417(7) N1A C7A 1.473(6) C5A C6A 1.527(8) Cl4A Cl3A 1.424(8) C8A N2A 1.503(6) C5A C4A 1.532(8) C14A W1A 2.457(5) C14 W1 2.434(5) C8 C9 1.466(8) C4 N1 1.457(7) C2 Cl 1.537(7) C8 N2 1.488(6) C4 C5 1.536(7) C2 C3 1.544(6) C9 C10 1.499(7) C21 C16 1.529(7) C2 W1 2.198(6) C10 C11 1.483(7) C13 C14 1.403(7) C6 C5 1.516(8) C12 C16 1.410(8) C13 C18 1.515(7) C12A C16A 1.413(8) C12 C13 1.440(7) C13 W1 2.378(5) C12A C17A 1.539(8) C12 C17 1.514(8) C2A OA 1.531(7) C12A W1A 2.329(5) C12 W1 2.337(5) C2A C3A 1.545(7) C16A C15A 1.412(8) C19 C14 1.520(7) C2A W1A 2.181(6) C16A W1A 2.390(5) CllA ClOB 1.466(17) C16 C15 1.413(7) C6A C7A 1.526(7) CI lA N2A 1.479(6) C16 W1 2.390(5) C3 N1 1.462(7) CllA ClOA 1.518(10) C20A C15A 1.496(8) N3 01 1.246(5) C9A ClOA 1.471(11) C13A C12A 1.408(7) N3 W1 1.749(5) C9A C8A 1.506(7) C13A C18A 1.521(8) N3A 01A 1.242(5) C9A ClOB 1.561(16) C13A W1A 2.369(5) N3A W1A 1.750(5) C20 C15 1.483(8) C15 C14 1.441(7) N2A W1A 1.924(4) C7 N1 1.450(6) C15 WI 2.441(5) C11 N2 1.501(6) C7 C6 1.507(8) N1A C4A 1.462(6) N2 W1 1.926(4) C19A C14A 1.509(7) N1A C3A 1.472(7) C15A W1A 2.447(6) Table A.30.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.10. C6A C5A C4A 103.2(5) C9 C8 N2 106.3(5) C8 C9 C10 104.8(5) C11 C10 C9 104.9(5) C16 C12 C13 107.2(5) C16 C12 C17 126.1(5) C13 C12 C17 126.5(6) C16 C12 W1 74.7(3) C13 C12 W1 73.8(3) C17 C12 W1 121.8(4) ClOB CllA N2A 108.1(8) C1OB Cl 1A ClOA 43.6(7) N2A CllA ClOA 103.9(5) ClOA C9A C8A 104.7(6) ClOA C9A ClOB 42.8(7) C8A C9A ClOB 104.9(7) N1 C7 C6 103.8(5) C15A C14A C13A 107.7(5) C15A C14A C19A 124.9(6) C13A C14A C19A 127.1(5) C15A C14A W1A 72.8(3) C13A C14A W1A 69.5(3) Cl9A Cl4A W1A 128.4(4) N1 C4 C5 105.9(5) C14 C13 C12 107.9(5) C14 C13 C18 128.3(5) C12 C13 C18 123.6(6) C14 C13 W1 75.2(3) C12 C13 W1 70.7(3) C18 C13 WI 123.4(3) CIA C2A C3A 109.3(4) CIA C2A W1A 111.5(4) C3A C2A W1A 111.4(4) C12 C16 C15 109.7(5) C12 C16 C21 126.4(6) C15 C16 C21 123.9(6) C12 C16 W1 70.6(3) C15 C16 W1 75.0(3) C21 C16 W1 121.8(3) C12A C13A C14A 107.7(5) C12A C13A C18A 125.1(6) C14A C13A C18A 126.9(5) C12A C13A W1A 71.0(3) C14A C13A W1A 76.2(3) C18A C13A W1A 123.3(4) C16 C15 C14 106.4(5) C16 C15 C20 127.1(5) C14 C15 C20 125.6(6) C16 C15 W1 71.0(3) C14 C15 W1 72.5(3) C20 C15 W1 129.8(4) C4A N1A C3A 112.0(5) C4A N1A C7A 104.5(4) C3A N1A C7A 114.5(4) N2A C8A C9A 105.9(5) C13 C14 C15 108.8(5) C13 C14 C19 126.9(5) C15 C14 C19 123.8(6) C13 C14 W1 70.9(3) C15 C14 W1 73.1(3) C19 C14 W1 127.9(3) CI C2 C3 110.0(4) Cl C2 W1 112.1(4) C3 C2 W1 110.2(4) C7 C6 C5 102.7(5) C13A C12A C16A 108.7(6) C13A C12A C17A 125.1(6) Cl6A Cl2A Cl7A 126.2(5) C13A C12A W1A 74.2(3) C16A C12A W1A 75.0(3) C17A C12A W1A 120.1(4) NIA C3A C2A 113.4(5) 218 C15A C16A C12A 107.7(5) C15A C16A C21A 126.1(7) Cl2A Cl6A C21A 126.2(6) C15A C16A W1A 75.3(3) C12A C16A W1A 70.2(3) C21A C16A W1A 121.9(4) N1A C4A C5A 102.3(5) C7A C6A C5A 104.8(5) C6 C5 C4 104.9(5) Ni C3 C2 114.3(5) 01 N3 WI 168.8(4) 01A N3A W1A 169.5(4) CllA N2A C8A 106.9(4) CllA N2A W1A 125.7(3) C8A N2A W1A 127.4(3) N1A C7A C6A 106.1(5) C10 C11 N2 107.0(4) C7 N1 C4 104.5(4) C7 NI C3 112.9(5) C4 N1 C3 114.0(4) C8 N2 C11 106.2(4) C8 N2 WI 128.7(3) C11 N2 W1 125.1(3) C16A C15A C14A 108.2(6) Cl6A Cl5A C20A 126.1(6) C14A C15A C20A 124.7(6) C16A C15A W1A 70.8(3) C14A C15A W1A 73.6(3) C20A C15A W1A 129.8(4) N3 W1 N2 99.42(19) N3 W1 C2 93.7(2) N2 W1 C2 100.09(19) N3 WI C12 92.38(19) N2 W1 C12 123.80(19) C2 W1 C12 133.9(2) N3 W1 C13 121.9(2) N2 W1 C13 96.51(18) C2 W1 C13 137.4(2) C12 WI C13 35.56(17) N3 WI C16 96.55(19) N2 W1 C16 153.99(18) C2 WI C16 99.2(2) C12 WI C16 34.70(18) C13 WI C16 57.52(18) N3 WI C14 149.55(19) N2 W1 C14 101.65(18) C2 W1 C14 103.9(2) C12 WI C14 57.55(19) C13 WI C14 33.88(18) C16 W1 C14 56.59(18) N3 WI C15 127.5(2) N2 WI C15 132.87(19) C2 W1 C15 83.16(19) C12 WI C15 57.7(2) C13 WI C15 57.34(19) C16 W1 C15 34.00(17) C14 W1 C15 34.40(17) N3A W1A N2A 97.79(19) N3A W1A C2A 94.8(2) N2A WIA C2A 101.41(19) N3A W1A C12A 93.2(2) N2A W1A Cl2A 122.5(2) C2A W1A C12A 133.7(2) N3A W1A C13A 121.3(2) N2A W1A C13A 95.57(18) C2A W1A C13A 137.5(2) C12A W1A C13A 34.86(17) N3A W1A C16A 97.9(2) N2A W1A C16A 153.11(19) C2A W1A C16A 98.9(2) C12A W1A C16A 34.8(2) C13A W1A C16A 57.56(19) N3A W1A C15A 129.3(2) N2A W1A C15A 132.33(19) C2A W1A Cl5A 83.6(2) C12A W1A C15A 57.0(2) C13A W1A C15A 56.8(2) C16A W1A C15A 33.92(19) N3A W1A C14A 150.04(19) N2A W1A C14A 101.38(18) C2A W1A Cl4A 103.6(2) C12A W1A C14A 57.0(2) C13A W1A C14A 34.26(18) C16A W1A C14A 56.42(18) C15A W1A C14A 33.59(17) C9A ClOA CllA 103.4(7) Cl lA ClOB C9A 101.6(10) 219 Table A.31.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 3.14. W1 N1 1.763(2) C16 C21 1.502(4) C10 C11 1.506(4) WI N2 1.938(2) C3 C2 1.530(4) C10 C9 1.537(4) W1 Cl 2.184(3) N2 C6 1.493(4) C14 C19 1.507(4) W1 C17 2.335(3) N2 C9 1.496(3) C9 C8 1.531(4) W1 C16 2.385(3) C17 C18 1.432(4) C5 C2 1.526(4) W1 C18 2.397(3) C17 C22 1.499(4) C4 C2 1.537(4) W1 C14 2.459(3) CI5 C14 1.426(4) C8 C7 1.509(5) W1 C15 2.459(3) C15 C20 1.501(4) C12 C11 1.324(5) N1 01 1.239(3) C6 C7 1.514(4) CI C2 1.551(4) C16 C15 1.419(4) C18 C14 1.422(4) C11 C13 1.487(6) C16 C17 1.433(4) C18 C23 1.505(4) Table A.32.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 3.14. N1 W1 N2 98.61(10) C14 W1 C15 33.72(10) C14 C18 W1 75.37(16) N1 W1 Cl 97.15(11) 01 N1 W1 168.7(2) C17 C18 W1 70.01(15) N2 W1 Cl 103.49(10) C15 C16 C17 108.0(3) C23 C18 W1 124.3(2) N1 W1 C17 93.08(10) C15 C16 C21 125.9(3) C11 C10 C9 112.8(2) N2 W1 C17 122.05(10) C17 C16 C21 126.1(3) C18 C14 C15 107.6(3) Cl W1 C17 131.08(10) C15 C16 W1 75.85(16) C18 C14 C19 126.7(3) N1 W1 C16 96.53(11) C17 C16 W1 70.40(15) C15 C14 C19 125.5(3) N2 W1 C16 153.64(10) C21 C16 W1 121.3(2) C18 C14 W1 70.60(15) Cl W1 C16 95.86(10) C6 N2 C9 108.2(2) C15 C14 W1 73.15(16) C17 WI C16 35.33(10) C6 N2 W1 124.65(18) C19 C14 WI 126.28(19) N1 W1 C18 122.71(10) C9 N2 W1 127.17(18) N2 C9 C8 104.7(2) N2 W1 C18 95.92(10) C18 C17 C16 107.4(3) N2 C9 C10 110.9(2) Cl WI C18 132.25(10) C18 C17 C22 126.4(3) C8 C9 C10 112.8(2) C17 WI C18 35.20(10) C16 C17 C22 126.0(3) C7 C8 C9 103.6(2) C16 WI C18 57.73(10) C18 C17 W1 74.79(15) C8 C7 C6 103.5(3) N1 W1 C14 150.26(10) C16 C17 W1 74.27(15) C2 Cl W1 124.56(18) N2 W1 C14 101.92(10) C22 C17 W1 121.3(2) C5 C2 C3 110.5(2) Cl W1 C14 98.71(10) C16 C15 C14 108.6(3) C5 C2 C4 108.3(3) C17 W1 C14 57.72(10) C16 C15 C20 126.0(3) C3 C2 C4 107.8(2) C16 WI. C14 56.96(10) C14 C15 C20 125.0(3) C5 C2 Cl 111.9(2) C18 W1 C14 34.03(9) C16 C15 W1 70.13(15) C3 C2 Cl 110.8(2) N1 W1 C15 127.72(11) C14 C15 W1 73.13(16) C4 C2 Cl 107.4(2) N2 W1 C15 133.25(10) C20 C15 W1 128.27(19) C12 C11 C13 122.5(4) Cl WI C15 79.17(9) N2 C6 C7 105.9(2) C12 C11 C10 121.6(4) C17 W1 C15 57.46(10) C14 C18 C17 108.5(3) C13 C11 C10 116.0(3) C16 WI. C15 34.02(10) C14 C18 C23 126.3(3) C18 W1 C15 56.47(9) C17 C18 C23 125.0(3) 220 Table A.33.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.1. W1 N1 1.788(3) N1 01 1.216(3) C14 C19 1.504(4) W1 C5 2.242(3) C9 C8 1.515(5) C2 Cl 1.363(5) W1 C3 2.294(3) C16 C11 1.498(4) C2 C3 1.414(5) WI C2 2.313(3) C13 C14 1.427(5) C17 C12 1.496(5) W1 Cl 2.333(4) C13 C12 1.431(4) C15 C10 1.498(5) W1 C12 2.354(3) C13 C18 1.499(5) C12 C11 1.417(5) WI C11 2.370(3) C8 C7 1.518(4) C10 C11 1.429(4) W1 C13 2.370(3) C6 C5 1.521(4) C3 C4 1.501(5) W1 C14 2.409(3) C6 C7 1.530(4) W1 C10 2.411(3) C14 C10 1.423(4) Table A.34.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.1. Ni W1 C5 86.31(13) C5 W1 C14 116.37(12) C13 C14 W1 71.13(17) N1 W1 C3 89.70(12) C3 W1 C14 89.36(11) C19 C14 W1 126.3(2) C5 W1 C3 131.93(12) C2 W1 C14 107.78(12) Cl C2 C3 118.8(3) N1 W1 C2 88.66(12) Cl W1 C14 92.33(13) Cl C2 W1 73.8(2) C5 W1 C2 96.24(12) C12 W1 C14 57.96(11) C3 C2 W1 71.42(18) C3 W1 C2 35.73(12) C11 W1 C14 57.67(10) C2 Cl W1 72.1(2) N1 W1 Cl 114.15(13) C13 W1 C14 34.73(12) C11 C12 C13 108.1(3) C5 W1 Cl 76.09(14) N1 W1 C10 142.92(11) C11 C12 C17 124.8(3) C3 W1 Cl 62.19(13) C5 WI C10 85.01(11) C13 C12 C17 126.9(3) C2 W1 Cl 34.12(13) C3 W1 C10 122.18(11) C11 C12 W1 73.15(17) N1 W1 C12 94.45(11) C2 W1 C10 128.09(12) C13 C12 W1 72.99(17) C5 W1 C12 115.47(12) Cl W1 C10 98.54(13) C17 C12 W1 123.5(2) C3 W1 C12 112.60(12) C12 Wi C10 57.87(12) C14 C10 C11 107.9(3) C2 W1 C12 148.27(12) C11 W1 C10 34.77(11) C14 C10 C15 125.8(3) Cl WI C12 150.29(13) C13 W1 C10 57.71(11) C11 C10 C15 126.1(3) N1 W1 C11 108.45(11) C14 W1 C10 34.33(11) C14 C10 W1 72.78(17) C5 WI C11 84.10(11) 01 N1 W1 174.9(2) C11 C10 W1 71.04(16) C3 W1 C11 141.50(11) C14 C13 C12 107.7(3) C15 C10 W1 125.5(2) C2 W1 C11 162.85(12) C14 C13 C18 125.5(3) C12 C11 C10 108.2(3) Cl W1 C11 131.17(13) C12 C13 C18 126.3(3) C12 C11 C16 125.2(3) C12 W1 C11 34.92(11) C14 C13 W1 74.14(17) C10 C11 C16 125.8(3) N1 W1 C13 114.77(12) C12 C13 W1 71.73(17) C12 C11 W1 71.92(16) C5 W1 C13 140.52(11) C18 C13 W1 126.1(2) C10 C11 Wi 74.18(16) C3 W1 C13 83.45(11) C9 C8 C7 112.9(3) C16 C11 W1 127.5(2) C2 W1 C13 116.17(11) C5 C6 C7 113.7(3) C2 C3 C4 120.6(3) Cl W1 C13 118.63(13) C10 C14 C13 108.1(3) C2 C3 W1 72.85(19) C12 W1 C13 35.27(10) C10 C14 C19 125.0(3) C4 C3 W1 121.8(2) C11 W1 C13 58.21(11) C13 C14 C19 126.6(3) C8 C7 C6 115.0(3) N1 WI C14 149.28(12) C10 C14 W1 72.88(16) C6 C5 W1 116.5(2) 221 Table A.35.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.2. W1 N1 1.774(3) P1 C6 1.813(4) C8 C9 1.412(4) W1 C2 2.218(3) P1 C7 1.816(4) C8 C13 1.514(5) W1 Cl 2.221(4) P1 C5 1.829(4) C2 CI 1.453(5) W1 C10 2.327(3) N1 01 1.230(4) C2 C3 1.456(5) W1 C11 2.337(3) C4 C3 1.306(5) C9 C10 1.422(5) W1 C12 2.384(3) C16 C11 1.515(4) C9 C14 1.503(4) W1 C9 2.385(3) C12 C8 1.409(4) C10 C11 1.427(5) W1 C8 2.394(3) C12 C11 1.418(4) C10 C15 1.499(4) W1 P1 2.4335(8) C12 C17 1.500(4) Table A.36.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.2. N1 W1 C2 95.85(12) C12 W1 C8 34.30(10) C12 C8 W1 72.48(16) N1 W1 Cl 105.32(14) C9 W1 C8 34.38(11) C9 C8 W1 72.47(18) C2 W1 Cl 38.21(12) N1 W1 P1 87.15(9) C13 C8 W1 126.4(2) Ni W1 C10 94.42(12) C2 WI P1 113.33(9) Cl C2 C3 121.4(3) C2 W1 C10 105.29(12) Cl W1 P1 76.76(10) Cl C2 W1 71.01(18) Cl W1 C10 138.93(14) C10 W1 P1 140.99(9) C3 C2 W1 114.7(2) N1 W1 C11 96.98(12) C11 W1 P1 105.44(8) C8 C9 C10 108.2(3) C2 W1 C11 139.61(12) C12 WI P1 90.75(7) C8 C9 C14 125.6(3) Cl W1 C11 157.69(14) C9 W1 P1 144.40(8) C10 C9 C14 125.7(3) C10 W1 C11 35.63(12) C8 W1 P1 110.19(8) C8 C9 W1 73.15(17) N1 W1 C12 128.57(11) C6 P1 C7 102.5(2) C10 C9 W1 70.22(18) C2 W1 C12 131.17(12) C6 P1 C5 101.3(2) C14 C9 W1 128.7(2) Cl W1 C12 124.09(13) C7 P1 C5 101.08(19) C9 C10 C11 107.5(3) C10 W1 C12 58.32(10) C6 P1 W1 119.43(13) C9 C10 C15 126.2(3) C11 W1 C12 34.94(10) C7 P1 W1 112.34(14) C11 C10 C15 126.1(4) N1 W1 C9 123.94(12) C5 P1 W1 117.60(14) C9 C10 WI 74.67(18) C2 W1 C9 82.97(11) 01 N1 W1 170.1(3) C11 C10 W1 72.56(18) Cl W1 C9 106.88(14) C8 C12 C11 108.4(3) C15 C10 W1 122.2(2) C10 W1 C9 35.11(12) C8 C12 C17 124.6(3) C12 C11 C10 107.6(3) C11 W1 C9 58.24(11) C11 C12 C17 126.3(3) C12 C11 C16 127.1(3) C12 W1 C9 57.25(10) C8 C12 W1 73.22(17) C10 C11 C16 125.1(3) N1 W1 C8 152.02(12) C11 C12 W1 70.71(16) C12 C11 W1 74.35(17) C2 W1 C8 96.93(11) C17 C12 W1 129.1(2) C10 C11 W1 71.81(17) Cl WI C8 100.10(14) C12 C8 C9 108.2(3) C16 C11 W1 123.1(2) C10 W1 C8 58.18(11) C12 C8 C13 125.1(3) C4 C3 C2 126.7(4) C11 W1 C8 57.99(10) C9 C8 C13 126.4(3) C2 Cl W1 70.78(19) 222 Table A.37.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.6. C7 C11 1.397(5) C10 C15 1.503(6) W1 C5B 2.343(12) C7 C8 1.412(5) C10 W1 2.307(4) W1 C1B 2.347(18) C7 C12 1.513(5) C11 C16 1.503(5) W1 CIA 2.368(14) C7 W1 2.420(4) C11 W1 2.388(3) CIA C2A 1.320(17) C8 C9 1.416(5) N1 01 1.218(4) C2A C3A 1.398(12) C8 C13 1.497(6) N1 W1 1.772(3) C3A C4A 1.556(16) C8 W1 2.394(4) W1 C3B 2.162(11) C5A C6A 1.099(16) C9 C10 1.422(6) W1 C3A 2.174(12) C1B C2B 1.32(2) C9 C14 1.514(5) W1 C2B 2.257(10) C2B C3B 1.431(14) C9 W1 2.299(4) W1 C2A 2.285(8) C3B C4B 1.557(17) C10 C11 1.421(5) W1 C5A 2.332(11) C5B C6B 1.114(15) Table A.38.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.6. C11 C7 C8 108.7(3) C3B WI C2A 78.1(4) N1 WI CIA 114.8(3) C11 C7 C12 127.0(4) C3A W1 C2A 36.4(3) C3B WI CIA 57.3(7) C8 C7 C12 124.0(4) C2B WI C2A 40.4(4) C3A W1 CIA 61.3(6) C11 C7 WI 71.9(2) Ni WI C9 92.96(13) C2B W1 CIA 27.8(6) C8 C7 WI 71.9(2) C3B WI C9 139.2(4) C2A WI CIA 32.9(5) C12 C7 W1 126.3(3) C3A WI C9 105.6(3) C9 WI CM. 148.5(4) C7 C8 C9 107.7(3) C2B W1 C9 173.7(3) C10 WI CIA 143.7(4) C7 C8 C13 126.4(4) C2A WI C9 142.0(2) C5A WI CIA 76.0(6) C9 C8 C13 125.5(4) N1 W1 C10 95.25(13) C5B WI CIA 77.8(6) C7 C8 W1 74.0(2) C3B WI C10 103.3(4) C1B WI CIA 5.6(11) C9 C8 W1 68.8(2) C3A WI C10 141.1(3) NI W1 C11 127.33(13) C13 C8 W1 128.2(3) C2B WI C10 140.7(3) C3B W1 C11 86.1(4) C8 C9 C10 107.9(3) C2A WI C10 174.1(2) C3A WI C11 135.6(4) C8 C9 C14 127.5(4) C9 W1 C10 35.96(14) C2B WI C11 115.7(3) C10 C9 C14 124.4(4) Ni WI C5A 85.9(3) C2A WI C11 140.2(2) C8 C9 W1 76.1(2) C3B WI C5A 18.7(4) C9 WI C11 58.50(12) C10 C9 W1 72.3(2) C3A W1 C5A 131.6(4) C10 WI C11 35.18(12) C14 C9 W1 120.9(3) C2B WI C5A 55.2(4) C5A W1 C11 77.5(3) C11 CIO C9 107.4(3) C2A WI C5A 95.1(3) C5B WI C11 131.8(3) C11 C10 C15 126.0(4) C9 WI C5A 122.8(3) C1B WI C11 108.9(6) C9 C10 C15 126.4(4) C10 WI C5A 87.1(3) CIA WI C11 108.9(3) Cl 1 C10 WI 75.5(2) Ni WI C5B 86.0(4) C2A CIA W1 70.1(6) C9 C10 W1 71.7(2) C3B WI C5B 130.2(5) CIA C2A C3A 117.4(11) C15 C10 W1 122.5(3) C3A WI C5B 16.6(4) ClA C2A WI 77.0(7) C7 C11 C10 108.2(3) C2B WI C5B 92.5(5) C3A C2A W1 67.5(6) C7 C11 C16 125.1(4) C2A WI C5B 52.1(4) C2A C3A C4A 93.8(9) C10 C11 C16 126.3(4) C9 WI C5B 90.4(3) C2A C3A WI 76.1(6) C7 Cl I WI 74.4(2) C10 W1 C5B 126.4(3) C4A C3A WI 123.9(10) CIO C11 W1 69.3(2) C5A W1 C5B 146.1(4) C6A C5A W1 133.6(11) C16 C11 WI 127.6(3) Ni W1 C1B 117.6(5) C2B CIB WI 69.6(9) 01 Ni WI 169.3(3) C3B WI C1B 62.7(7) C1B C2B C3B 117.4(14) Ni W1 C3B 93.8(4) C3A WI C1B 57.2(8) C1B C2B WI 77.2(10) N1 W1 C3A 91.9(4) C2B WI C1B 33.2(5) C3B C2B W1 67.5(6) C3B W1 C3A 114.3(5) C2A W1 C1B 31.8(6) C2B C3B C4B 92.4(10) N1 W1 C2B 92.8(3) C9 WI C1B 143.5(6) C2B C3B W1 74.7(6) C3B W1 C2B 37.7(4) C10 W1 C1B 144.0(6) C4B C3B WI 120.4(8) C3A WI C2B 76.7(4) C5A WI C1B 81.3(8) C6B C5B WI 131.6(13) Ni WI C2A 90.3(2) C5B WI C1B 73.5(8) 223 Table A.39.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.11. Cl C2 1.43(3) C13 C14 1.42(3) C29 C30 1.50(3) Cl W1 2.267(19) C13 C18 1.52(3) C31 C35 1.40(3) C2 C3 1.39(3) C13 W1 2.39(2) C31 C32 1.40(3) C2 W1 2.301(19) C14 C15 1.39(3) C31 C36 1.54(3) C3 C4 1.49(3) C14 C19 1.50(3) C31 W2 2.40(2) C3 W1 2.44(2) C14 W1 2.30(2) C32 C33 1.45(3) C4 C5 1.54(3) C15 C20 1.53(3) C32 C37 1.48(3) C5 C6 1.46(3) C15 W1 2.29(2) C32 W2 2.36(2) C5 C10 1.57(4) C21 C22 1.44(3) C33 C34 1.43(3) C6 C7 1.57(3) C21 W2 2.21(3) C33 C38 1.50(3) C6 W1 2.22(2) C22 C23 1.33(3) C33 W2 2.279(19) C7 C8 1.55(3) C22 W2 2.30(2) C34 C35 1.36(3) C8 C9 1.50(4) C23 C24 1.52(3) C34 C39 1.48(3) C9 CIO 1.54(4) C23 W2 2.36(2) C34 W2 2.29(2) C11 C15 1.39(3) C24 C25 1.51(4) C35 C40 1.52(3) C11 C12 1.39(3) C25 C26 1.48(3) C35 W2 2.37(2) C11 C16 1.53(3) C25 C30 1.54(3) N1 01 1.19(3) C11 W1 2.38(2) C26 C27 1.56(3) N1 W1 1.78(2) C12 C13 1.44(3) C26 W2 2.26(2) N2 02 1.24(3) C12 C17 1.50(3) C27 C28 1.61(4) N2 W2 1.76(2) C12 W1 2.42(2) C28 C29 1.41(4) Table A.40.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.11. C2 Cl W1 73.1(11) C11 C12 C17 128(2) C23 C22 W2 76.2(14) C3 C2 Cl 120(2) C13 C12 C17 124(2) C21 C22 W2 68.0(13) C3 C2 W1 78.4(12) C11 C12 W1 71.5(13) C22 C23 C24 123(2) Cl C2 WI 70.5(11) C13 C12 W1 71.5(12) C22 C23 W2 70.7(13) C2 C3 C4 127(2) C17 C12 W1 125.5(17) C24 C23 W2 113.9(15) C2 C3 W1 67.7(12) C14 C13 C12 106.3(19) C25 C24 C23 107.5(18) C4 C3 W1 115.9(14) C14 C13 C18 129(2) C26 C25 C24 108.6(19) C3 C4 C5 104.3(19) C12 C13 C18 125(2) C26 C25 C30 114(2) C6 C5 C4 110(2) C14 C13 W1 68.8(12) C24 C25 C30 113(2) C6 C5 C10 114(2) C12 C13 W1 73.5(13) C25 C26 C27 112(2) C4 C5 C10 111.3(19) C18 C13 W1 127.1(15) C25 C26 W2 113.1(16) C5 C6 C7 111.1(19) C15 C14 C13 107.5(19) C27 C26 W2 112.1(16) C5 C6 W1 115.9(16) C15 C14 C19 130(2) C26 C27 C28 109(2) C7 C6 W1 111.6(15) C13 C14 C19 122(2) C29 C28 C27 114(2) C8 C7 C6 112(2) C15 C14 W1 72.0(12) C28 C29 C30 112(2) C9 C8 C7 110(2) C13 C14 W1 76.0(13) C29 C30 C25 112(2) C8 C9 C10 110(2) C19 C14 W1 123.3(16) C35 C31 C32 108.8(18) C9 C10 C5 111(2) C11 C15 C14 110.0(18) C35 C31 C36 129(2) C15 C11 C12 107.9(17) C11 C15 C20 126(2) C32 C31 C36 122(2) C15 C11 C16 127.0(19) C14 C15 C20 124(2) C35 C31 W2 71.8(12) C12 C11 C16 124(2) C11 C15 W1 76.0(13) C32 C31 W2 71.3(11) C15 C11 W1 69.4(12) C14 C15 W1 72.6(12) C36 C31 W2 126.2(15) C12 C11 W1 74.8(13) C20 C15 W1 119.7(17) C31 C32 C33 105.6(19) C16 C11 W1 129.8(15) C22 C21 W2 74.7(14) C31 C32 C37 125(2) C11 C12 C13 108.2(18) C23 C22 C21 115(2) C33 C32 C37 129(2) C31 C32 W2 74.5(12) Ni WI C11 129.4(8) C26 W2 C34 93.2(9) C33 C32 W2 68.7(11) C6 WI C11 81.6(8) C33 W2 C34 36.5(8) C37 C32 W2 129.2(16) Cl W1 C11 133.8(8) N2 W2 C22 89.4(10) C34 C33 C32 108.0(18) C15 W1 C11 34.5(7) C21 W2 C22 37.3(8) C34 C33 C38 127(2) C14 WI C11 58.3(7) C26 W2 C22 90.8(8) C32 C33 C38 124(2) C2 WI C11 140.3(8) C33 W2 C22 139.6(8) C34 C33 W2 72.3(11) N1 WI C13 123.3(8) C34 W2 C22 172.0(8) C32 C33 W2 75.0(12) C6 WI C13 138.0(8) N2 W2 C32 121.2(9) C38 C33 W2 121.8(14) Cl WI C13 82.6(8) C21 W2 C32 80.9(8) C35 C34 C33 107(2) C15 WI C13 57.9(7) C26 W2 C32 139.3(8) C35 C34 C39 130(2) C14 WI C13 35.2(7) C33 W2 C32 36.3(8) C33 C34 C39 123(2) C2 WI C13 113.6(8) C34 W2 C32 60.1(8) C35 C34 W2 76.2(13) C11 Wi C13 57.6(7) C22 W2 C32 112.8(8) C33 C34 W2 71.2(12) Ni WI C12 151.9(8) N2 W2 C23 116.2(9) C39 C34 W2 122.3(17) C6 WI C12 104.4(8) C21 W2 C23 61.4(8) C34 C35 C31 111(2) Cl WI C12 100.1(8) C26 W2 C23 72.5(8) C34 C35 C40 122(2) C15 W1 C12 56.9(7) C33 W2 C23 145.6(8) C31 C35 C40 127(2) C14 WI C12 58.1(8) C34 W2 C23 142.9(8) C34 C35 W2 69.9(13) C2 WI C12 114.9(8) C22 W2 C23 33.1(8) C31 C35 W2 74.2(12) C11 Wi C12 33.7(7) C32 W2 C23 109.3(7) C40 C35 W2 130.5(16) C13 W1 C12 34.9(8) N2 W2 C35 129.7(9) 01 N1 WI 170.6(17) Ni WI C3 114.5(8) C21 W2 C35 132.6(8) 02 N2 W2 169(2) C6 WI C3 70.2(8) C26 W2 C35 82.9(8) N1 WI C6 89.1(9) Cl WI C3 62.2(8) C33 W2 C35 57.7(7) Ni WI Cl 90.6(10) C15 WI C3 143.1(8) C34 W2 C35 34.0(8) C6 W1 Cl 127.1(8) C14 WI C3 146.4(8) C22 W2 C35 140.3(8) Ni WI C15 98.1(8) C2 WI C3 33.9(8) C32 W2 C35 57.5(7) C6 WI C15 94.7(7) C11 WI C3 108.6(7) C23 W2 C35 109.1(8) Cl WI C15 137.5(8) C13 Wi C3 111.3(8) N2 W2 C31 150.1(8) Ni WI C14 94.3(8) C12 W1 C3 93.4(8) C21 W2 C31 98.6(8) C6 WI C14 129.9(8) N2 W2 C21 89.6(10) C26 W2 C31 106.4(8) Cl WI C14 102.8(8) N2 W2 C26 90.3(9) C33 W2 C31 58.0(7) C15 W1 C14 35.3(7) C21 W2 C26 128.1(9) C34 W2 C31 57.8(7) N1 WI C2 89.0(9) N2 W2 C33 92.2(9) C22 W2 C31 114.4(8) C6 WI C2 90.7(8) C21 W2 C33 102.3(9) C32 W2 C31 34.3(7) Cl WI C2 36.4(8) C26 W2 C33 129.5(9) C23 W2 C31 92.8(7) C15 WI C2 171.1(7) N2 W2 C34 97.5(9) C35 W2 C31 34.0(7) C14 WI C2 139.2(8) C21 W2 C34 138.1(9) 224 225 Table A.41. Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.13. Cl C2 1.447(6) C6 C7 1.521(6) C12 C17 1.501(5) Cl W1 2.227(4) C8 C9 1.522(6) C12 W1 2.327(3) C2 C3 1.363(6) C10 C14 1.401(5) C13 C14 1.427(5) C2 W1 2.336(3) C10 C11 1.429(5) C13 C18 1.506(5) C3 C4 1.488(5) C10 C15 1.503(5) C13 W1 2.353(3) C3 W1 2.437(4) C10 W1 2.414(3) C14 C19 1.505(5) C4 C5 1.565(5) C11 C12 1.419(5) C14 W1 2.437(3) C5 02 1.413(4) C11 C16 1.498(5) N1 01 1.230(4) C5 C6 1.529(5) C11 W1 2.332(3) N1 W1 1.763(3) C5 C8 1.534(5) C12 C13 1.413(5) 02 W1 2.012(3) Table A.42.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.13. C2 Cl W1 75.7(2) C13 C12 W1 73.42(18) C11 W1 C2 165.31(14) C3 C2 Cl 117.9(4) C11 C12 W1 72.47(19) N1 W1 C13 105.02(13) C3 C2 W1 77.5(2) C17 C12 W1 121.8(2) 02 W1 C13 137.57(10) Cl C2 W1 67.5(2) C12 C13 C14 108.4(3) Cl W1 C13 83.15(14) C2 C3 C4 124.3(4) C12 C13 C18 124.5(3) C12 W1 C13 35.15(12) C2 C3 W1 69.4(2) C14 C13 C18 126.6(3) C11 W1 C13 58.48(12) C4 C3 W1 112.1(2) C12 C13 WI 71.44(19) C2 W1 C13 119.66(13) C3 C4 C5 109.0(3) C14 C13 W1 75.9(2) N1 W1 C10 143.18(13) 02 C5 C6 108.7(3) C18 C13 W1 124.2(2) 02 W1 C10 82.54(10) 02 C5 C8 111.7(3) CIO C14 C13 107.5(3) Cl W1 C10 115.72(15) C6 C5 C8 109.1(3) C10 C14 C19 126.2(3) C12 W1 C10 57.89(11) 02 C5 C4 107.8(3) C13 C14 C19 126.1(4) C11 W1 C10 34.99(12) C6 C5 C4 110.8(3) C10 C14 W1 72.33(19) C2 W1 C10 130.51(13) C8 C5 C4 108.8(3) C13 C14 W1 69.46(18) C13 W1 C10 57.15(12) C7 C6 C5 115.9(3) C19 C14 WI 127.4(2) N1 W1 C14 139.64(13) C9 C8 C5 114.9(3) 01 N1 W1 171.4(3) 02 W1 C14 113.33(11) C14 CIO C11 108.7(3) C5 02 WI 122.6(2) Cl W1 C14 84.87(14) C14 C10 C15 125.7(3) N1 W1 02 99.83(13) C12 W1 C14 57.79(11) C11 C10 C15 125.6(3) N1 W1 Cl 90.68(18) C11 W1 C14 57.60(12) C14 C10 W1 74.11(19) 02 W1 Cl 130.71(14) C2 W1 C14 111.71(13) C11 C10 W1 69.36(18) N1 W1 C12 88.64(13) C13 WI C14 34.61(12) C15 C10 W1 123.8(2) 02 W1 C12 113.75(11) C10 W1 C14 33.56(12) C12 C11 C10 107.5(3) Cl WI C12 114.52(15) N1 W1 C3 109.54(13) C12 C11 C16 127.8(3) N1 W1 C11 108.58(13) 02 W1 C3 69.19(12) C10 C11 C16 124.6(3) 02 W1 C11 81.30(11) Cl W1 C3 61.95(16) C12 C11 W1 72.08(19) Cl W1 C11 140.03(14) C12 W1 C3 161.14(13) C10 C11 W1 75.65(19) C12 W1 C11 35.46(12) C11 W1 C3 134.84(13) C16 C11 W1 121.0(2) N1 W1 C2 86.08(14) C2 W1 C3 33.10(13) C13 C12 C11 107.8(3) 02 W1 C2 95.60(12) C13 W1 C3 130.11(13) C13 C12 C17 125.3(3) Cl W1 C2 36.86(14) C10 W1 C3 105.61(12) C11 C12 C17 126.8(4) C12 W1 C2 150.66(14) C14 W1 C3 103.53(12) 226 Table A.43. Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.14. Cl C2 1.410(5) C6 W1 2.191(3) C11 W1 2.308(3) Cl W1 2.228(3) C9 C10 1.403(4) C12 C13 1.426(4) C2 C3 1.381(5) C9 C13 1.421(4) C12 C17 1.499(4) C2 W1 2.299(3) C9 C14 1.498(4) C12 W1 2.331(3) C3 C4 1.488(4) C9 W1 2.422(3) C13 C18 1.495(4) C3 W1 2.360(3) C10 C11 1.414(4) C13 W1 2.386(3) C4 C5 1.503(4) C10 C15 1.496(4) N1 01 1.212(4) C5 C6 1.325(4) C10 W1 2.391(3) N1 W1 1.766(3) C5 C8 1.506(4) C11 C12 1.416(4) C6 C7 1.515(4) C11 C16 1.500(4) Table A.44.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.14. C2 Cl W1 74.63(18) C12 C11 W1 73.11(16) N1 W1 C3 120.06(11) C3 C2 Cl 117.3(3) C16 C11 W1 120.7(2) C6 W1 C3 71.05(11) C3 C2 W1 75.16(18) C11 C12 C13 107.6(3) Cl W1 C3 62.55(12) Cl C2 WI 69.12(19) C11 C12 C17 125.3(3) C2 W1 C3 34.46(11) C2 C3 C4 125.0(3) C13 C12 C17 126.9(3) C11 W1 C3 134.93(11) C2 C3 W1 70.38(18) C11 C12 W1 71.34(16) C12 W1 C3 146.01(11) C4 C3 W1 117.1(2) C13 C12 W1 74.52(17) N1 WI C13 120.22(12) C3 C4 C5 108.9(2) C17 C12 W1 123.2(2) C6 W1 C13 82.72(10) C6 C5 C4 119.4(3) C9 C13 C12 107.6(3) Cl W1 C13 140.11(11) C6 C5 C8 126.4(3) C9 C13 C18 123.6(3) C2 W1 C13 145.30(11) C4 C5 C8 114.2(3) C12 C13 C18 128.3(3) C11 W1 C13 58.50(10) C5 C6 C7 118.9(3) C9 C13 W1 74.20(16) C12 W1 C13 35.18(10) C5 C6 WI 123.5(2) C12 C13 W1 70.31(16) C3 W1 C13 111.98(11) C7 C6 W1 117.1(2) C18 C13 W1 127.3(2) N1 W1 C10 131.08(12) C10 C9 C13 108.2(3) 01 N1 W1 169.8(2) C6 W1 C10 133.33(11) C10 C9 C14 126.0(3) Ni W1 C6 87.86(12) Cl W1 C10 84.04(11) C13 C9 C14 125.5(3) N1 W1 Cl 91.34(14) C2 W1 C10 109.68(11) C10 C9 W1 71.86(16) C6 W1 Cl 125.34(12) C11 W1 C10 34.97(11) C13 C9 W1 71.44(16) N1 W1 C2 92.95(12) C12 W1 C10 58.03(10) C14 C9 W1 127.7(2) C6 W1 C2 89.18(12) C3 W1 C10 100.64(10) C9 C10 C11 108.4(3) Cl W1 C2 36.26(12) C13 WI C10 57.23(9) C9 C10 C15 125.6(3) N1 W1 C11 98.07(11) N1 W1 C9 150.24(11) C11 C10 C15 125.5(3) C6 W1 C11 138.18(11) C6 W1 C9 99.44(10) C9 C10 W1 74.24(16) Cl W1 C11 96.02(12) Cl W1 C9 107.11(12) C11 C10 W1 69.29(15) C2 W1 C11 131.38(11) C2 W1 C9 115.81(11) C15 C10 W1 128.5(2) N1 Wi C12 92.49(11) C11 W1 C9 57.73(10) C10 C11 C12 108.1(3) C6 W1 C12 103.21(11) C12 W1 C9 57.77(10) C10 C11 C16 126.2(3) Cl Wi C12 131.41(12) C3 W1 C9 89.46(10) C12 C11 C16 125.6(3) C2 W1 C12 166.65(11) C13 W1 C9 34.36(10) C10 C11 WI 75.73(16) C11 W1 C12 35.55(10) C10 W1 C9 33.90(10) 227 Table A.45.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.15. Cl C2 1.357(9) C11 C12 1.404(7) C14 W1 2.339(5) Cl W1 2.361(6) C11 C15 1.406(9) C15 C20 1.499(7) C2 C3 1.417(8) C11 C16 1.516(9) C15 W1 2.366(5) C2 W1 2.302(6) C11 W1 2.397(6) Ni 01 1.224(7) C3 C4 1.485(10) C12 C13 1.410(8) Ni W1 1.761(6) C3 W1 2.290(6) C12 C17 1.495(8) 0001 0002 1.370(16) C5 C6 1.485(8) C12 W1 2.405(6) 0001 0005 1.431(18) C5 W1 2.261(5) C13 C14 1.405(8) 0001 0005 1.88(4) C6 C7 1.350(8) C13 C18 1.508(7) C002 0003 1.389(17) C6 C10 1.492(9) C13 W1 2.332(5) C003 0004 1.485(18) C7 C8 1.494(10) C14 C15 1.408(8) 0004 0005 1.55(2) C7 C9 1.509(8) C14 C19 1.509(9) Table A.46.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.15. C2 Cl W1 70.7(3) C13 C14 C19 126.7(6) N1 W1 C15 112.9(2) Cl C2 C3 120.4(7) C15 C14 C19 125.6(6) C5 W1 C15 138.9(2) Cl C2 W1 75.5(3) C13 C14 W1 72.2(3) C3 W1 C15 82.1(2) C3 C2 W1 71.6(3) C15 C14 W1 73.7(3) C2 W1 C15 115.0(2) C2 C3 C4 120.6(7) C19 C14 W1 122.0(5) C13 W1 C15 57.78(18) C2 C3 W1 72.5(3) C11 C15 C14 108.2(5) C14 W1 C15 34.8(2) C4 C3 W1 121.2(6) C11 C15 C20 127.0(7) Cl W1 C15 118.2(2) C6 C5 W1 121.6(4) C14 C15 C20 124.2(7) N1 W1 C11 146.4(2) C7 C6 C5 123.7(6) C11 C15 W1 74.0(3) C5 W1 C11 113.2(2) C7 C6 C10 121.2(6) C14 C15 W1 71.5(3) C3 W1 C11 90.4(2) C5 C6 C10 115.0(5) C20 C15 W1 127.4(5) C2 W1 C11 109.1(2) C6 C7 C8 124.3(6) 01 N1 W1 170.9(5) C13 W1 C11 57.37(19) C6 C7 C9 123.7(6) N1 W1 C5 89.5(2) C14 W1 C11 57.5(2) C8 C7 C9 111.9(5) N1 W1 C3 90.9(3) Cl W1 C11 94.0(2) C12 C11 C15 108.2(5) C5 WI C3 133.7(2) C15 W1 C11 34.3(2) C12 C11 C16 124.7(7) N1 W1 C2 90.9(3) N1 W1 C12 137.8(2) C15 C11 C16 126.6(6) C5 W1 C2 97.8(2) C5 W1 C12 83.0(2) C12 C11 W1 73.3(3) C3 W1 C2 35.9(2) C3 W1 C12 123.6(2) C15 C11 W1 71.6(4) N1 W1 C13 103.5(2) C2 W1 C12 131.2(2) C16 C11 W1 127.1(4) C5 W1 C13 84.41(19) C13 W1 C12 34.6(2) C11 C12 C13 107.6(5) C3 W1 C13 139.8(2) C14 W1 C12 57.5(2) C11 C12 C17 126.2(6) C2 W1 C13 165.5(2) Cl W1 C12 102.3(2) C13 C12 C17 126.0(6) Ni W1 C14 90.6(2) C15 W1 C12 56.98(19) C11 C12 W1 72.7(4) C5 W1 C14 117.0(2) C11 W1 C12 34.00(19) C13 C12 W1 69.9(3) C3 W1 C14 109.2(2) 0002 0001 0005 104.8(10) C17 C12 W1 126.9(4) C2 W1 C14 145.2(2) 0002 0001 0005 41.8(13) C14 C13 C12 108.4(5) C13 W1 C14 35.01(19) 0005 0001 0005 63.6(15) C14 C13 C18 125.1(6) N1 W1 Cl 116.1(2) 0001 0002 0003 106.6(10) C12 C13 C18 125.9(6) C5 WI Cl 76.26(19) 0002 0003 0004 93.9(12) C14 C13 W1 72.8(3) C3 W1 Cl 62.3(2) 0003 0004 0005 89.8(14) C12 C13 W1 75.5(3) C2 W1 Cl 33.8(2) 0001 0005 0004 94.9(13) C18 C13 W1 125.2(4) C13 W1 Cl 135.2(2) C13 C14 C15 107.6(5) C14 W1 Cl 151.1(2) 228 Table A.47.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 4.16. Cl C2 1.395(9) C8 C9 1.342(8) C14 C19 1.495(9) Cl W1 2.410(7) C9 C10 1.383(9) C14 W1 2.319(5) C2 C3 1.436(9) C10 C11 1.382(9) C15 C16 1.434(9) C2 W1 2.311(6) C12 C16 1.389(8) C15 C20 1.513(9) C3 C4 1.458(10) C12 C13 1.413(8) C15 W1 2.368(6) C3 W1 2.299(6) C12 C17 1.510(8) C16 C21 1.524(8) C5 C6 1.534(8) C12 WI 2.387(5) C16 W1 2.397(5) C5 W1 2.216(7) C13 C14 1.422(9) N1 01 1.190(6) C6 C11 1.366(8) C13 C18 1.518(8) N1 W1 1.770(5) C6 C7 1.396(8) C13 W1 2.323(5) C7 C8 1.387(8) C14 C15 1.396(10) Table A.48.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 4.16. C2 Cl W1 69.0(4) C15 C14 W1 74.6(3) N1 W1 C15 117.5(2) Cl C2 C3 120.5(6) C13 C14 W1 72.3(3) C5 WI C15 138.3(2) Cl C2 W1 76.8(4) C19 C14 W1 123.4(5) C3 WI C15 81.1(2) C3 C2 W1 71.4(3) C14 C15 C16 108.2(5) C2 W1 C15 113.3(2) C2 C3 C4 120.5(6) C14 C15 C20 126.7(7) C14 WI C15 34.6(2) C2 C3 W1 72.3(4) C16 C15 C20 124.2(7) C13 W1 C15 58.0(2) C4 C3 W1 121.0(5) C14 C15 W1 70.8(3) N1 W1 C12 136.1(2) C6 C5 W1 117.8(4) C16 C15 W1 73.6(3) C5 WI C12 81.2(2) C11 C6 C7 117.6(5) C20 C15 W1 129.8(4) C3 W1 C12 126.5(2) C11 C6 C5 121.4(6) C12 C16 C15 107.7(5) C2 W1 C12 133.1(2) C7 C6 C5 120.9(6) C12 C16 C21 126.4(7) C14 W1 C12 58.3(2) C8 C7 C6 119.9(5) C15 C16 C21 125.5(7) C13 WI C12 34.87(19) C9 C8 C7 122.5(6) C12 C16 W1 72.7(3) C15 WI C12 57.3(2) C8 C9 C10 117.7(6) C15 C16 W1 71.4(3) Ni W1 C16 150.5(2) C11 C10 C9 121.0(5) C21 C16 W1 126.8(4) C5 W1 C16 109.3(2) C6 C11 C10 121.2(6) 01 N1 W1 170.2(5) C3 W1 C16 92.9(2) C16 C12 C13 108.5(5) N1 W1 C5 88.5(2) C2 W1 C16 109.6(2) C16 C12 C17 125.8(6) N1 W1 C3 90.8(2) C14 W1 C16 58.2(2) C13 C12 C17 125.5(6) C5 Wil C3 133.7(2) C13 W1 C16 57.56(18) C16 C12 W1 73.5(3) Ni W1 C2 90.4(3) C15 W1 C16 35.0(2) C13 C12 W1 70.1(3) C5 W1 C2 97.4(2) C12 W1 C16 33.8(2) C17 C12 W1 126.0(4) C3 WI C2 36.3(2) N1 W1 CI 116.0(2) C12 C13 C14 108.0(5) N1 W1 C14 92.7(2) C5 W1 Cl 76.0(3) C12 C13 C18 126.0(6) C5 W1 C14 120.5(3) C3 W1 Cl 62.9(2) C14 C13 C18 125.5(6) C3 W1 C14 105.7(2) C2 W1 Cl 34.3(2) C12 C13 W1 75.0(3) C2 W1 C14 142.0(2) C14 W1 Cl 148.2(2) C14 C13 W1 72.0(3) N1 W1 C13 102.3(2) C13 W1 Cl 136.9(2) C18 C13 W1 125.0(4) C5 W1 C13 86.2(2) C15 WI Cl 114.4(2) C15 C14 C13 107.6(5) C3 WI C13 138.7(2) C12 WI Cl 102.8(2) C15 C14 C19 126.4(7) C2 W1 C13 167.0(2) C16 W1 Cl 91.6(2) C13 C14 C19 125.7(7) C14 W1 C13 35.7(2) 229 Table A.49.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 5.1. CI C2 1.405(15) C18 WI 2.312(9) C41 W2 2.361(10) Cl C10 1.450(15) C19 C20 1.429(14) C42 C43 1.398(15) Cl WI 2.422(10) C19 C24 1.493(16) C42 C47 1.541(17) C2 C3 1.368(15) C19 W1 2.338(10) C42 W2 2.297(12) C2 W1 2.303(9) C20 C25 1.501(14) C43 C44 1.414(15) C3 C4 1.464(14) C20 WI 2.385(9) C43 C48 1.472(15) C3 W1 2.278(9) C26 C27 1.410(17) C43 W2 2.305(10) C4 C5 1.305(16) C26 C35 1.454(19) C44 C45 1.410(15) C4 C9 1.375(15) C26 W2 2.360(13) C44 C49 1.498(16) C5 C6 1.507(17) C27 C28 1.412(17) C44 W2 2.304(12) C6 C7 1.298(19) C27 W2 2.286(11) C45 C50 1.493(13) C7 C8 1.369(18) C28 C29 1.464(19) C45 W2 2.385(9) C8 C9 1.362(16) C28 W2 2.321(11) N1 01 1.228(10) C10 C11 1.366(14) C29 C30 1.371(17) N1 W1 1.759(7) C10 C15 1.399(16) C29 C34 1.427(17) W2 N2A 1.704(14) C11 C12 1.345(16) C30 C31 1.369(19) W2 N2B 1.76(6) C12 C13 1.385(19) C31 C32 1.358(19) 02A 02B 1.09(3) C13 C14 1.335(18) C32 C33 1.373(18) 02A N2B 1.20(6) C14 C15 1.340(16) C33 C34 1.346(18) 02A N2A 1.343(19) C16 C20 1.372(14) C35 C36 1.370(16) 02B N2A 1.29(2) C16 C17 1.419(15) C35 C40 1.374(19) 02B N2B 1.55(6) C16 C21 1.521(14) C36 C37 1.33(2) N2A N2B 0.54(5) C16 WI 2.377(10) C37 C38 1.38(2) C51 C52 1.36(3) C17 C18 1.396(15) C38 C39 1.39(2) C52 03 1.40(2) C17 C22 1.447(15) C39 C40 1.34(2) 03 C53 1.40(3) C17 WI 2.312(10) C41 C42 1.394(14) C53 C54 1.38(2) C18 C19 1.435(15) C41 C45 1.404(14) C18 C23 1.509(13) C41 C46 1.520(14) Table A.50.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 5.1. C2 Cl C10 126.7(10) C12 C11 C10 121.8(12) C17 C18 W1 72.4(6) C2 Cl W1 68.1(5) C11 C12 C13 121.1(13) C19 C18 W1 73.0(5) C10 Cl W1 126.5(7) C14 C13 C12 117.3(12) C23 C18 W1 122.7(6) C3 C2 Cl 120.5(10) C15 C14 C13 122.5(13) C20 C19 C18 107.2(9) C3 C2 W1 71.6(6) C14 C15 C10 121.1(12) C20 C19 C24 125.4(11) Cl C2 W1 77.4(6) C20 C16 C17 109.8(10) C18 C19 C24 126.7(10) C2 C3 C4 123.0(10) C20 C16 C21 125.0(11) C20 C19 W1 74.2(6) C2 C3 W1 73.6(6) C17 C16 C21 124.9(10) C18 C19 W1 71.0(5) C4 C3 W1 122.8(6) C20 C16 W1 73.6(6) C24 C19 W1 127.6(8) C5 C4 C9 120.7(11) C17 C16 W1 69.9(6) C16 C20 C19 107.7(10) C5 C4 C3 116.6(11) C21 C16 W1 128.4(7) C16 C20 C25 127.4(11) C9 C4 C3 122.7(10) C18 C17 C16 107.6(9) C19 C20 C25 124.8(11) C4 C5 C6 117.1(12) C18 C17 C22 123.5(10) C16 C20 W1 72.9(6) C7 C6 C5 120.9(12) C16 C17 C22 128.8(11) C19 C20 W1 70.6(6) C6 C7 C8 119.4(13) C18 C17 W1 72.4(6) C25 C20 W1 125.8(8) C9 C8 C7 120.4(12) C16 C17 W1 74.9(6) C27 C26 C35 125.7(10) C8 C9 C4 121.2(10) C22 C17 W1 121.2(8) C27 C26 W2 69.5(7) C11 C10 C15 116.1(10) C17 C18 C19 107.7(8) C35 C26 W2 125.8(9) C11 C10 Cl 119.8(11) C17 C18 C23 128.6(10) C26 C27 C28 120.9(11) C15 C10 CI 124.1(10) C19 C18 C23 123.6(10) C26 C27 W2 75.2(7) 230 C28 C27 W2 73.5(6) N1 W1 C3 96.1(4) N2A W2 C28 102.4(6) C27 C28 C29 125.2(10) N1 W1 C2 91.0(4) N2B W2 C28 116.6(19) C27 C28 W2 70.8(7) C3 W1 C2 34.8(4) C27 W2 C28 35.7(4) C29 C28 W2 124.0(7) N1 W1 C18 91.5(3) C42 W2 C28 109.6(4) C30 C29 C34 117.4(13) C3 W1 C18 135.7(4) C43 W2 C28 144.9(4) C30 C29 C28 125.1(13) C2 W1 C18 170.5(4) C44 W2 C28 141.7(4) C34 C29 C28 117.4(10) N1 W1 C17 99.8(4) N2A W2 C26 103.9(5) C29 C30 C31 123.7(13) C3 W1 C17 100.7(3) N2B W2 C26 100(2) C32 C31 C30 117.2(12) C2 W1 C17 135.3(4) C27 W2 C26 35.3(4) C31 C32 C33 121.4(15) C18 W1 C17 35.1(4) C42 W2 C26 144.8(4) C34 C33 C32 121.9(13) N1 W1 C19 117.8(4) C43 W2 C26 140.2(4) C33 C34 C29 118.3(11) C3 W1 C19 141.9(4) C44 W2 C26 104.6(4) C36 C35 C40 118.6(14) C2 W1 C19 147.3(4) C28 W2 C26 63.2(4) C36 C35 C26 122.1(12) C18 W1 C19 36.0(4) N2A W2 C41 145.8(5) C40 C35 C26 119.4(11) C17 W1 C19 58.9(3) N2B W2 C41 146(2) C37 C36 C35 121.5(13) N1 WI C16 133.9(4) C27 W2 C41 118.3(4) C36 C37 C38 120.4(14) C3 W1 C16 87.1(4) C42 W2 C41 34.8(4) C37 C38 C39 118.7(16) C2 W1 C16 114.5(4) C43 W2 C41 58.9(4) C40 C39 C38 119.5(15) C18 W1 C16 57.9(3) C44 W2 C41 57.9(3) C39 C40 C35 121.3(13) C17 W1 C16 35.2(4) C28 W2 C41 90.8(3) C42 C41 C45 107.5(10) C19 W1 C16 57.3(4) C26 W2 C41 110.3(4) C42 C41 C46 125.3(10) N1 W1 C20 150.1(4) N2A W2 C45 150.7(5) C45 C41 C46 127.0(10) C3 WI C20 107.2(4) N2B W2 C45 135.4(17) C42 C41 W2 70.1(7) C2 W1 C20 118.9(4) C27 W2 C45 116.1(4) C45 C41 W2 73.7(6) C18 W1 C20 58.8(3) C42 W2 C45 57.6(3) C46 C41 W2 124.7(7) C17 W1 C20 58.2(4) C43 W2 C45 59.0(3) C41 C42 C43 110.7(10) C19 W1 C20 35.2(4) C44 W2 C45 35.0(4) C41 C42 C47 125.6(12) C16 W1 C20 33.5(3) C28 W2 C45 106.8(4) C43 C42 C47 123.5(12) N1 W1 Cl 113.2(4) C26 W2 C45 90.2(3) C41 C42 W2 75.1(7) C3 W1 Cl 61.6(3) C41 W2 C45 34.4(3) C43 C42 W2 72.7(7) C2 W1 Cl 34.5(4) 02B 02A N2B 85(3) C47 C42 W2 124.3(10) C18 W1 Cl 149.8(4) 02B 02A N2A 62.8(15) C42 C43 C44 105.1(9) C17 WI Cl 143.3(4) N2B 02A N2A 24(2) C42 C43 C48 125.8(11) C19 W1 Cl 114.0(4) 02A 02B N2A 68.3(17) C44 C43 C48 129.0(11) C16 W1 Cl 108.6(4) 02A 02B N2B 50(2) C42 C43 W2 72.0(7) C20 WI Cl 94.6(4) N2A 02B N2B 19(2) C44 C43 W2 72.1(6) N2A W2 N2B 17.8(17) N2B N2A 02B 109(8) C48 C43 W2 121.5(8) N2A W2 C27 88.5(5) N2B N2A 02A 63(7) C45 C44 C43 109.8(9) N2B W2 C27 95(2) 02B N2A 02A 48.9(12) C45 C44 C49 125.3(11) N2A W2 C42 111.3(5) N2B N2A W2 87(8) C43 C44 C49 124.6(11) N2B W2 C42 113(2) 02B N2A W2 156.8(17) C45 C44 W2 75.7(6) C27 W2 C42 144.8(5) 02A N2A W2 149.4(17) C43 C44 W2 72.2(6) N2A W2 C43 95.8(5) N2A N2B 02A 94(8) C49 C44 W2 123.9(10) N2B W2 C43 88(2) N2A N2B 02B 52(7) C41 C45 C44 106.9(8) C27 W2 C43 174.9(4) 02A N2B 02B 45(2) C41 C45 C50 126.5(10) C42 W2 C43 35.4(4) N2A N2B W2 76(7) C44 C45 C50 126.5(10) N2A W2 C44 115.8(6) 02A N2B W2 169(4) C41 C45 W2 71.9(6) N2B W2 C44 100.9(18) 02B N2B W2 125(3) C44 C45 W2 69.4(6) C27 W2 C44 139.4(4) C51 C52 03 126(2) C50 C45 W2 126.2(6) C42 W2 C44 58.1(4) C52 03 C53 128.5(19) 01 N1 W1 170.0(7) C43 W2 C44 35.7(4) C54 C53 03 125(2) 231 Table A.51.^Bond Distances (A) in the Solid-State Molecular Structure Determined for 5.2. Cl C2 1.403(3) C8 C9 1.377(3) ^ C17 C22 1.502(4) Cl W1 2.262(3) ^ C10 C11 1.492(3) C17 WI 2.375(2) C2 C3 1.403(3) C10 C15 1.533(3) C18 C19 1.414(4) C2 C10 1.521(3) C11 C12 1.317(4) ^ C18 C23 1.496(4) C2 W1 2.328(2) ^ C12 C13 1.493(4) C18 WI 2.315(3) C3 C4 1.492(3) C13 C14 1.512(4) C19 C20 1.409(4) C3 WI 2.360(2) C14 C15 1.520(4) ^ C19 C24 1.493(3) C4 C5 1.375(4) ^ C16 C17 1.397(4) C19 W1 2.326(2) C4 C9 1.401(3) C16 C20 1.432(3) C20 C25 1.491(4) C5 C6 1.382(3) C16 C21 1.497(4) ^ C20 WI 2.343(2) C6 C7 1.366(4) ^ C16 W1 2.398(2) N1 01 1.216(3) C7 C8 1.383(4) C17 C18 1.426(4) N1 WI 1.763(2) Table A.52.^Bond Angles (°) in the Solid-State Molecular Structure Determined for 5.2. C2 Cl W1 74.81(15) Cl C2 C3 119.0(2) Cl C2 C10 122.9(2) C3 C2 C10 117.5(2) Cl C2 W1 69.64(14) C3 C2 W1 73.84(14) C10 C2 W1 120.31(16) C2 C3 C4 125.6(2) C2 C3 WI 71.34(13) C4 C3 W1 109.98(15) C5 C4 C9 118.6(2) C5 C4 C3 123.2(2) C9 C4 C3 117.7(2) C4 C5 C6 121.2(3) C7 C6 C5 119.7(3) C6 C7 C8 120.4(2) C9 C8 C7 120.0(3) C8 C9 C4 120.2(3) C11 C10 C2 114.8(2) C11 C10 C15 109.7(2) C2 C10 C15 107.86(19) C12 C11 C10 123.4(2) C11 C12 C13 124.7(2) C12 C13 C14 111.7(2) C13 C14 C15 109.7(2) C14 C15 C10 111.3(2) C17 C16 C20 107.0(2) C17 C16 C21 126.7(3) C20 C16 C21 126.0(3) C17 C16 W1 72.09(14) C20 C16 W1 70.30(13) C21 C16 W1 127.37(18) C16 C17 C18 109.3(2) C16 C17 C22 126.9(3) C18 C17 C22 123.6(3) C16 C17 WI 73.89(14) C18 C17 W1 69.99(14) C22 C17 W1 126.00(18) C19 C18 C17 107.1(2) C19 C18 C23 125.5(3) C17 C18 C23 127.0(3) C19 C18 WI 72.68(15) C17 C18 W1 74.64(15) C23 C18 W1 123.41(18) C20 C19 C18 108.2(2) C20 C19 C24 127.1(2) C18 C19 C24 124.7(3) C20 C19 W1 73.09(14) C18 C19 W1 71.84(14) C24 C19 W1 120.94(18) C19 C20 C16 108.4(2) C19 C20 C25 125.7(2) C16 C20 C25 125.4(2) C19 C20 W1 71.77(14) C16 C20 WI 74.57(14) C25 C20 W1 126.09(18) 01 N1 WI 169.4(2) Ni Wl Cl 101.12(10) N1 W1 C18 98.58(10) Cl WI C18 143.18(9) Ni W1 C19 89.99(9) Cl W1 C19 113.69(9) C18 WI C19 35.49(9) N1 W1 C2 88.17(9) Cl W1 C2 35.56(8) C18 W1 C2 172.95(8) C19 W1 C2 147.42(9) N1 WI C20 115.66(9) Cl WI C20 84.59(9) C18 W1 C20 58.80(9) C19 WI C20 35.14(9) C2 W1 C20 119.95(9) N1 W1 C3 103.78(9) Cl WI C3 63.05(8) C18 W1 C3 139.99(9) C19 WI C3 166.19(9) C2 WI C3 34.82(8) C20 W1 C3 133.14(9) N1 WI C17 133.03(10) Cl WI C17 122.22(9) C18 W1 C17 35.38(9) C19 W1 C17 58.15(9) C2 WI C17 137.60(9) C20 W1 C17 57.63(9) C3 WI C17 111.08(8) Ni WI C16 148.15(9) Cl W1 C16 89.88(9) C18 WI C16 58.44(10) C19 W1 C16 58.35(9) C2 WI C16 116.10(9) C20 W1 C16 35.13(9) C3 W1 C16 107.83(8) C17 WI C16 34.02(9)

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