by Lee Hung Kay. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references. / Table of Contents --- p.i / Acknowledgements --- p.vi / Abstracts --- p.vii / Abbreviations --- p.ix / Chapter CHAPTER I. --- GENERAL INTRODUCTION / Chapter I.1 --- A Brief Review on the Background of Organometallic Chemistry --- p.1 / Chapter I.2 --- Stability of Organotransition Metal Complexes --- p.2 / Chapter I.3 --- Decomposition Pathways of Transition Metal σ Hydrocarbyls --- p.5 / Chapter I.4 --- Preparation of Transition Metal σ-Alkyl Complexes --- p.10 / Chapter I.5 --- A Survey on the Use of Functionalized Alkyl and Aryl Ligands in Synthesis of Transition Metal σ-Hydrocarbyls --- p.15 / Chapter I.6 --- 2-(Trimethylsilyl)methylpyridine (3) and 2-Bis(trimethylsilyl)- methylpyridine (4) as Ligand Precursors --- p.20 / Chapter I.7 --- A Brief Review of Previous Results on Synthesis of Metal Alkyl Complexes Using (1) and (2) as Ligands --- p.23 / Chapter I.8 --- Objective of This Work --- p.28 / Chapter I.9 --- References for Chapter I --- p.29 / Chapter CHAPTER II. --- "SYNTHESIS, STRUCTURES AND REACTIVITY OF IRON(n) AND COBALT(II) DIALKYL COMPLEXES" / Chapter II. 1 --- Introduction / Chapter II. 1.1 --- Synthesis of Iron(II) and Cobalt(II) Alkyl Complexes --- p.34 / Chapter IL1.1.1 --- Iron(II) Alkyl Complexes --- p.34 / Chapter II.1.1.2 --- Cobalt(II) Alkyl Complexes --- p.41 / Chapter II.1.2 --- Reactions of Transition Metal Alkyl Complexes with Protic Reagents and Halogens --- p.45 / Chapter II. 1.3 --- The Chemistry of Transition Metal Alkoxides and Thiolates 一 A Brief Review --- p.48 / Chapter II.2 --- Results and Discussion / Chapter II.2.1 --- "Synthesis of Homoleptic Iron(II) and Cobalt(II) Dialkyl Complexes [M {C(SiMe3)2C5H4N-2} 2] (M=Fe 55,Co 56)" --- p.51 / Chapter II.2.2 --- Attempted Reaction of [FeCl2(PPh3)2] with [{R2Li}2] --- p.52 / Chapter II.2.3 --- Attempted Synthesis of Monoalkyliron(II) Complexes --- p.53 / Chapter II.2.4 --- "Synthesis of Homoleptic Iron(II) and Cobalt(II) Dialkyl Complexes [M{(CHSiMe3)C9H6N-8}2] (M = Fe57, Co 58)" --- p.54 / Chapter II.2.5 --- Molecular Structures of [M{C(SiMe3)2C5H4N-2}2] (M =Fe 55.Co 56) and [Co{(CHSiMe3)C9H6N-8}2] (58) --- p.56 / Chapter II.2.6 --- Spectroscopic and Magnetic Properties of Compounds 55-58 --- p.63 / Chapter II.2.7 --- Electrochemistry of [Co(R2)2] (56) and [Co(R3)2] (58) --- p.66 / Chapter II.2.8 --- "Reactivities of [M{C(SiMe3)2C5H4N-2}2] (M = Fe55, Co 56)" --- p.70 / Chapter II.3 --- Experimentals for Chapter II --- p.83 / Chapter II.4 --- References for Chapter II --- p.86 / Chapter CHAPTER III. --- SYNTHESIS AND STRUCTURES OF DIALKYL COMPLEXES OF NICKEL(II) AND PALLADIUM(II) / Chapter III. 1 --- Introduction / Chapter III. 1.1 --- Nickel(II) Alkyl Complexes 一 A General Survey --- p.91 / Chapter III.1.1.1 --- η5-Cyclopentadienylnickel Alkyl and Aryl Complexes --- p.91 / Chapter III.1.1.2 --- Nickel Dialkyls --- p.96 / Chapter III. 1.2 --- Palladium(II) Alkyl Complexes ´ؤ A General Survey --- p.99 / Chapter III.1.2.1 --- Palladium Dialkyls --- p.99 / Chapter III. 1.2.2 --- Cyclopalladated Compounds --- p.101 / Chapter III.2 --- Results and Discussion / Chapter III.2.1 --- Synthesis of Nickel(II) Alkyl Complexes --- p.104 / Chapter III.2.1.1 --- Reactions of [{R1Li(Et2O)}2] and [{R2Li}2] with Nickelocenes ´ؤ Synthesis of η5 - Cyclopentadienylnickelalkyl Complexes (78-80) --- p.104 / Chapter III.2.1.2 --- Synthesis of the Substituted Nickelocene [Ni{{466}5- C5H3(SiMe3)2}2] (81) --- p.106 / Chapter III.2.1.3 --- Spectroscopic Properties of Compounds 78-80 --- p.107 / Chapter III.2.1.4 --- Molecular Structures of [(η5- C5H5)Ni{C(SiMe3)2C5H4N-2}] (78) and [{(η5- C5H5)Ni{CH(SiMe3)C5H4N-2}}2] (80) --- p.110 / Chapter III.2.1.5 --- "Reactions of [{R2Li}2] with NiCl2 and [NiCl2L2] (L2 = TMEDA, 2PPh3) ´ؤ Synthesis of Nickel Dialkyl Complex [Ni{C(SiMe3)2C5H4N-2}2] (82)" --- p.115 / Chapter III.2.1.6 --- Molecular Structure of [Ni{C(SiMe2)2C5H4N- 2}2] (82) --- p.118 / Chapter III.2.1.7 --- Spectroscopic Properties of [Ni{C(SiMe3)2C5H4N-2}2] (82) --- p.121 / Chapter III.2.1.8 --- Electrochemistry of [Ni{C(SiMe3)2C5H4N-2}2] (82) --- p.122 / Chapter III2.1.9 --- Reactivities of Ni[C(SiMe3)2C5H4N-2]2 (82) --- p.124 / Chapter III.2.1.10 --- "Reactions of [{R2Li}2] with [NiCl2(diphos)] [diphos = 1,2-bis(diphenylphosphino)ethane]" --- p.125 / Chapter III.2.1.11 --- Molecular Structure of [Ni{C(SiMe3)2C5H4N- 2}{5-(2'-C5H4NC(SiMe3)2C5H4N-2- CH(SiMe3)2}Cl] (83) --- p.127 / Chapter III.2.1.12 --- "Reactions of [{R1Li(Et2O)}2] and [R5Li] [-R5 = -CH2C5H4N-2] with NiCl2 and [NiCl2L2] (L2 = TMEDA, 2PPh3)" --- p.130 / Chapter III.2.1.13 --- Molecular Structure of [{CH(SiMe3)C5H4N- 2}2] (86) --- p.136 / Chapter III.2.2 --- Synthesis of Palladium(II) Alkyl Complexes --- p.139 / Chapter III.2.2.1 --- "Reactions of [{R2Li}2] with [PdX2L2] (L = PPh3, Et2S; X=Cl, Br) ´ؤ Synthesis of [Pd(R2)2] (88) and [Pd(R2)(PPh3)X] [X 二 Cl 89, Br 90]" --- p.139 / Chapter III.2.2.2 --- "Molecular Structures of Compounds [P'd{C(SiMe3)2C 5H 4N-2}2] (8 8), [Pd{C(SiMe3)2C5H4N-2}(PPh3)Cl] (89)，and [Pd{C(SiMe2)2C5H4N-2}(PPh3)Br] (90)" --- p.140 / Chapter III.2.2.3 --- Spectroscopic Properties of Compounds 88-90 --- p.146 / Chapter III.2 2.4 --- Electrochemistry of [Pd{C(SiMe3)2C5H4N-2}2] (88) --- p.147 / Chapter III.2.2.5 --- "Studies on Stereo specificity of the Reactions between [{R2Li}2] and [PdX2(PPh3)2] (X = Cl, Br)" --- p.150 / Chapter III.2.2.6 --- Attempted Synthesis of [Pd(R1)2] and [Pd(R1)(PPh3)Cll --- p.152 / Chapter III.2.2.7 --- Attempted Synthesis of [{Pd(R2)Cl}2]via Intramolecular C-H Activation --- p.153 / Chapter III.2.2.8 --- Molecular Structure of [{CH(SiMe3)2C5H4N- 2}2PdCl2} (91) --- p.154 / Chapter III.3 --- Experimentals for Chapter III --- p.157 / Chapter III.4 --- References for Chapter III --- p.165 / Chapter CHAPTER IV. --- SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF ZIRCONIUM(IV) AND HAFNIUM(IV) ALKYL COMPLEXES / Chapter IV. 1 --- Introduction --- p.169 / Chapter IV. 1.1 --- Homoleptic and Heteroleptic Complexes --- p.170 / Chapter IV. 1.2 --- Organo-Zirconium(IV) and -Hafnium(IV) Compounds Containing Functionalized Alkyl Ligands --- p.177 / Chapter IV.2 --- Results and Discussion / Chapter IV.2.1 --- "Synthesis of Zirconium(IV) and Hafnium(IV) Dialkyl Dichloride Compounds [M(R2)2C12] (M = Zr 103,Hf 104" --- p.181 / Chapter IV.2.2 --- Attempted Synthesis of Titanium(IV) Alkyl by the Reaction of TiCl4 with [{R2Li}2] --- p.182 / Chapter IV.2.3 --- Attempted Synthesis of Zirconium(IV) and Hafnium(IV) Alkyls with -R 1[= -CH(SiMe3)C5H4N-2] as Ligand --- p.182 / Chapter IV.2.4 --- Molecular Structure of [Zr{C(SiMe3)2C5H4N- 2}2C12] (103) --- p.183 / Chapter IV.2.5 --- Spectroscopic Properties of {C(SiMe3)2C5H4N- 2}2C12] (M = Zr 103，Hf 104) --- p.187 / Chapter IV.3 --- Experimentals for Chapter IV --- p.188 / Chapter IV.4 --- References for Chapter IV --- p.190 / Chapter CHAPTER V. --- COMPARISON OF BONDING PARAMETERS AMONG METAL ALKYL COMPLEXES WHICH CONTAIN ALKYL LIGANDS -R2 --- p.193 / References for Chapter V --- p.201 / APPENDIX I / Chapter A. --- General Procedures --- p.202 / Chapter B. --- Physical and Analytical Measurements --- p.202 / APPENDIX II / Magnetic Moment Measurements --- p.205 / APPENDIX III / "Table A-l. Selected Crystallographic Data for Compounds 55, 56, 58,and63" --- p.207 / "Table A-2. Selected Crystallographic Data for Compounds 78, 80，82 and83" --- p.208 / "Table A-3. Selected Crystallographic Data for Compounds 86, 88, 89 and90" --- p.209 / Table A-4. Selected Crystallographic Data for Compounds 91 and 103.… --- p.210