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Synthesis, structures and reactivities of sterically hindered N-functionalized transition metal alkyl complexes.

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

Identiferoai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_318322
Date January 1995
ContributorsLee, Hung Kay., Chinese University of Hong Kong Graduate School. Division of Chemistry.
PublisherChinese University of Hong Kong
Source SetsThe Chinese University of Hong Kong
LanguageEnglish
Detected LanguageEnglish
TypeText, bibliography
Formatprint, x, 210 leaves : ill. ; 30 cm.
RightsUse of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/)

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