This study is concerned with the nature of the relatively unusual bonding which occurs in organolithium compounds as a direct result of the oligomerization and possible explanations for that bonding.

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by Weng Linhong. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaf 162). / ACKNOWLEDGMENTS --- p.i / ABSTRACT --- p.ii / ABBREVIATIONS --- p.iv / LEGEND OF COMPOUNDS --- p.v / Chapter CHAPTER1 --- METALLATION OF α-SUBSTITUTED PICOLINE DERIVATIVES --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- Overview of Lithiation of Alkyl --- p.1 / Chapter 1.1.2 --- General Review of N-functionalized Alkyl Ligand --- p.3 / Chapter 1.1.3 --- The Substituted Methylpyridine Ligands and Their Derivatives --- p.6 / Chapter 1. --- Properties of Some α-Substituted Methylpyridine Ligand --- p.6 / Chapter 2. --- Electronic Properties of Substituted Methylpyridyl Ligand --- p.7 / Chapter 3. --- Some Structure of the Metal Derivatives of the N-Functionalised Alkyl Ligand --- p.8 / Chapter 4. --- Coordination Behavior of the Alkyl Ligand --- p.12 / Chapter 1.2 --- Results and Discussion --- p.14 / Chapter 1.2.1 --- Syntheses of N-Functionalised Lithium Alkyl Complexes --- p.14 / Chapter 1. --- "Synthesis of (tert-Butyldimethylsilyl)methylpyridine, CH2(SiButMe2)C5H4N-2 33 (picß H)" --- p.14 / Chapter 2. --- Lithiation of [CH(SiButMe2)C5H4N-2]´ؤPreparation of Compound 34 --- p.15 / Chapter 3. --- The Alkylation of [Li{CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.15 / Chapter 4. --- Metallation of Benzylpyridine CH2(Ph)C5H4N-2 (picφH)´ؤPreparation of Compound 36 --- p.17 / Chapter 5. --- Preparation of Compounds CHPh(SiMe3)C5H4N-2 37 (picφ'H) and its Lithium Compound [{CPh(SiMe3)C5H4N-2}Li(tmeda)] 38 --- p.17 / Chapter 6. --- The Lithiation of CH2(SiButMe2)C5H4N-2 33 and CHPh(SiMe3)C5H4N-2 37 in the absence of tmeda --- p.18 / Chapter 1.2.2 --- Characterization of the Ligands and Their Lithium Derivatives --- p.19 / Chapter 1. --- NMR characterization of ligand CH2(SiButMe2)C5H4N-2 33 --- p.19 / Chapter 2. --- NMR characterization of [Li{CH2(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.20 / Chapter 3. --- NMR of CH(Me)(SiButMe2)C5H4N-2 35 --- p.29 / Chapter 4. --- 1H and 13C NMR of CH(Ph)(SiMe3)C5H4N-2 37 --- p.29 / Chapter 5. --- 1H and 13C NR spectra of Ligand [ {CPh(SiMe3)C5H4N-2} (tmeda)] 38 --- p.30 / Chapter 6. --- NMR characterization of [{CH(SiButMe2)C5H4N-2}Li(Et20)]2 39 --- p.37 / Chapter 7. --- The 7Li NMR of the Lithium N-functionalized Alkyl compounds --- p.37 / Chapter 8. --- Mass spectroscopy of some picoline derivatives --- p.38 / Chapter 1.2.3 --- "The X-Ray Structures of Lithium Complexes 34, 36, 38 and 39" --- p.39 / Chapter 1. --- The structure of [Li{CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.39 / Chapter 2. --- "The structure of [Li(CHPhC5H4N-2)(tmeda)]2-tmeda, 36.tmeda" --- p.43 / Chapter 3. --- The Structure of [Li{CPh(SiMe3)C5H4N-2}(tmeda)] 38 --- p.46 / Chapter 4. --- Structure of [Li{CH(SiButMe2)C5H4N-2} (Et2O)]2 39 --- p.49 / Chapter 5. --- "Comparison of Structural Data of Lithium Complexes 34, 36, 38, and 39" --- p.52 / Chapter 1.3. --- Experimental Section --- p.60 / References --- p.64 / Chapter CHAPTER2 --- SYNTHESES AND STRUCTURES OF ORGANOTIN COMPLEXES WITH β- FUNCTIONALISED ALKYL LIGANDS --- p.67 / Chapter 2.1 --- Introduction --- p.67 / Chapter 2.1.1 --- A general Review of Divalent Tin Alkyl Chemistry --- p.67 / Chapter 2.1.2 --- Structures of Some Sn(II) compounds --- p.69 / Chapter 2.1.3 --- Reactivities of Dialkyltin Compounds --- p.71 / Chapter 2.1.4 --- General View on Hypervalent Organotin Chemistry --- p.72 / Chapter 2.2 --- Results and discussion --- p.76 / Chapter 2.2.1 --- Synthesis of Low-valent Tin Complexes with the β N-Functionalised Alkyl Ligands --- p.76 / Chapter 2.2.2 --- NMR Spectra of Tin(II) Alkyl Complexes --- p.78 / Chapter 1. --- NMR Spectra of [Sn{CH(SiButMe2)C5H4N-2}3][Li(tmeda)Cl}2] 77 --- p.78 / Chapter 2. --- 1H NMR spectrum of [Sn{CH(SiButMe2)C5H4N-2} Cl]2 78 --- p.80 / Chapter 3. --- lH NMR Spectrum of Product from the Reaction of [{CH(SiButMe2)C5H4N-2}Cl] 2 78 and [Li {CH(SiButMe2)C5H4N-2} (tmeda)]2 34 --- p.80 / Chapter 4. --- 1H NMR Spectrum of Compound [Sn{CPh(SiMe3)C5H4N-2}2] 79 --- p.84 / Chapter 5. --- 119Sn NMR Spectra of Tin(II) Compounds with Ligand anionic {CH(SiButMe2)C5H4N-2}- --- p.84 / Chapter 2.2.3 --- "Syntheses of Sn(IV) Compounds Sn(CRR 'C5H4N)R"" 2X" --- p.84 / Chapter 2.2.4 --- NMR Characterization of Sn(CRR ´ة C5H4N)R2X (X= Cl or Br) --- p.85 / Chapter 1. --- NMR Spectra of Compound Sn{CH(SiButMe2)C5H4N-2}But2Cl 85 --- p.85 / Chapter 2. --- 1H NMR Spectrum of Compound [Sn{CPh(SiMe3)C5H4N-2}Me2Br 86 --- p.89 / Chapter 3. --- 119Sn NMR Spectra of Compounds [Sn{CH(SiButMe2)(C5H4N-2}But2Cl] 85 and [Sn{CPh(SiMe3)C5H4N- 2}Me2Br 86 --- p.89 / Chapter 4. --- Mass Spectra of Compounds [Sn{CH(SiButMe2)C5H4N-2}But2Cl ] 85 and [Sn{CPh(SiMe3)C5H4N- 2}Me2Br] 86 --- p.90 / Chapter 2.2.5 --- "The Structure of Tin (II) Alkyl Complexes [Sn{CH(SiButMe2)C5H4N-2}3] - [Li {Li (tmeda) Cl} 2]77, [Sn{CH(SiButMe2)C5H4N-2}Cl]2 78 , and [Sn{CPh(SiMe3)C5H4N-2}2] 79" --- p.91 / Chapter 1. --- The Structure of Lithium Trialkylstannate(II) Complex --- p.91 / Chapter 2. --- The Molecular Structure of [Sn{CH(SiButMe2)C5H4N-2}Cl]2 78 --- p.96 / Chapter 3. --- The Structure of Complex[Sn{CPh(SiMe3)C5H4N-2}2] 79 --- p.99 / Chapter 4. --- Comparison of Structures of Divalent Tin Alkyl Complexes --- p.102 / Chapter 2.2.6 --- The Structure of Sn(pic?)R2X (X = Cl or Br --- p.105 / Chapter 1. --- The Structure of [2- {t-butyldimethylsilyl)methylene}pyridyl]-di(t-butyl)tin Chloride 85 --- p.105 / Chapter 2. --- The Molecular Structure of [Sn{CPh(SiMe3)C5H4N-2}Me2Br] 86 --- p.108 / Chapter 2.3 --- Experimental --- p.110 / Chapter 2.3.1 --- Syntheses of Subvalent Tin Alkyl Compounds --- p.110 / Chapter 2.3.2 --- Synthesis of Tetravalent-Tin Complexes with Substituted Methyl Pyridine Ligand --- p.112 / REFERENCES --- p.114 / Chapter CHAPTER3 --- TRANSITION METAL DERIVATIVES WITH β-FUNCTIONALIZED ALKYL LIGAND --- p.117 / Chapter 3.1 --- Introduction --- p.117 / Chapter 3.1.1 --- The Decomposition Pathways of Organometallic Compounds --- p.117 / Chapter 3.1.2 --- Iron (II) and Cobalt (II) Alkyl Complexes --- p.119 / Chapter 3.1.3 --- Homoleptic Iron(II) and Cobalt(II) Alkyls --- p.119 / Chapter 3.2 --- Results and Discussion --- p.121 / Chapter 3.2.1 --- Syntheses of M(II) (M = Fe or Co) N-functionalized Alkyl Complexes --- p.121 / Chapter 1. --- The reaction of MC12 with [Li {CH(SiButMe2)C5H4N-2}(tmeda)]2 34 --- p.121 / Chapter 2 --- The reaction of MC12 with [Li {CPh(SiMe3)C5H4N-2} (tmeda)] 38 --- p.123 / Chapter 3. --- The Reaction of [CPh2C5H4N]- with S and Synthesis of Complex [Ni{SC(Ph)2C5H4N}2] 119 --- p.127 / Chapter 3.2.2 --- Characterization of Iron (II) and Cobalt (II) Alkyl Complexes --- p.128 / Chapter 1. --- The Magnetic Properties of Compounds [Co {CPh(SiMe3)C5H4-2} 2] 113 and [Fe{CPh(SiMe3)C5H4- 2}(tmeda)Cl] 115 --- p.128 / Chapter 2. --- Mass Spectra of the Iron(II) and Cobalt(II) Compounds --- p.128 / Chapter 3.2.3 --- The X-ray Structures of the Complexes --- p.129 / Chapter 1. --- Structure of [Fe{CH(SiButMe2)C5H4N-2}2]2109 --- p.129 / Chapter 2. --- Structure of complex [Co{CH(SiButMe2)C5H4N-2}2]2110 --- p.132 / Chapter 3. --- Structure of Compound [Co{CPh(SiMe3)C5H4N-2}2] 113 --- p.135 / Chapter 4. --- The Structure of Compound [Fe {CPh(SiMe3)C5H4N-2} (tmeda)Cl] 115 --- p.138 / Chapter 5. --- "Comparison of the structures of the iron(II) and cobalt(II) alkyls 109，110, 113 and 115" --- p.140 / Chapter 3.2.4 --- The Structure of Complex [Ni{SC(Ph)2C5H4N}2] 119 --- p.142 / Chapter 3.3 --- Experimental --- p.145 / REFERENCES --- p.148 / Chapter CHAPTER4 --- ZIRCONOCENE DERIVATIVES WITH THE SUBSTITUTED METHYL PYRIDINE LIGANDS --- p.150 / Chapter 4.1 --- Introduction --- p.150 / Chapter 4.1.1 --- A General Review of Zirconocene Derivatives --- p.150 / Chapter 4.2.1 --- Syntheses of Zirconocene Compounds Cp2Zr(CRR ´ةC5H4N)Cl --- p.152 / Chapter 4.2.2 1 --- H NMR spectra of Cp2Zr(CRR ´ةC5H4N)Cl --- p.153 / Chapter 4.2.3 --- The Molecular Structure of [ZrCp2(CPh2C5H4N-2)Cl] 127 --- p.156 / Chapter 4.3 --- Experimental --- p.160 / REFERENCES --- p.162 / APPENDIX A: PHYSICAL MEASUREMENTS AND TABLES OF CRYSTAL DATA AND REFINEMENT PARAMETERS --- p.163 / APPENDIX B: TABLES OF ATOMIC COORDINATES AND THERMAL PARAMETERS --- p.172

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Mixed alkyllithium / lithium alkoxide aggregates in the form (RLi)n(ROLi)m were formed by addition of corresponding alcohol compounds at different Li/O ratios. Variable temperature 13C and 6Li NMR spectroscopy were used to verify the formation of the mixed aggregates and to study their behavior in hydrocarbon solution. Spectra for the lithium n-propoxide / n-propyllithium and iso-butyllithium / lithium iso-butoxide systems each indicated at least one mixed aggregate.

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A variable temperature 1H, 13C, and 6Li NMR study of n-propyl-6Li-lithium showed five different aggregates, similar to that in the literature as (RLi)n, n= 6, 8, 9, 9, 9. There were also a number of additional new species, identified as lithium hydride containing aggregates. Unexpectedly, a series of 13C{1H} 1-D NMR experiments with selective 6Li decoupling showed evidence for 13C-6Li spin-spin coupling between the previously reported (RLi)n aggregates and various hydride species.

by Lawrence Tin-chi Law. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1993. / Includes bibliographical references (leaves 96). / acknowledgements --- p.iii / ABSTRACT --- p.iv / CONTENTS --- p.v / ABBREVIATION --- p.vii / Chapter CHAPTER I --- METALLATION OF 8-METHYLQUINOLINE / Chapter 1.1 --- INTRODUCTION --- p.1 / Chapter 1.1.1 --- A Brief Review of Metal-Alkyl Chemistry --- p.1 / Chapter 1.1.2 --- General Considerations --- p.2 / Chapter 1.1.3 --- 8-Methylquinoline as Ligand Precursor --- p.8 / Chapter 1.1.4 --- Metallations by Organolithium Compounds --- p.9 / Chapter 1.1.5 --- Other Methods for Metallations --- p.16 / Chapter 1.1.6 --- Aim of the Present Work --- p.21 / Chapter 1.2 --- RESULTS AND DISCUSSION --- p.24 / Chapter 1.2.1 --- Reactions of 8-Methylquinoline with Organolithium Reagents --- p.26 / Chapter 1.2.2 --- Synthesis of Grignard Reagent --- p.35 / Chapter 1.2.3 --- Attempted Metal-Halogen Exchange Reaction at Low Temperature --- p.39 / Chapter 1.2.4 --- Metallation of 8-methylquinoline by Lithium Diisopropylamide --- p.40 / Chapter 1.3 --- EXPERIMENTAL FOR CHAPTER I --- p.43 / Chapter 1.4 --- REFERENCES FOR CHAPTER I --- p.53 / Chapter CHAPTER II --- SYNTHESIS AND CHARACTERISATION AND STRUCTURE OF SOME MAIN GROUP 14 ALKYLS / Chapter 2.1 --- INTRODUCTION --- p.58 / Chapter 2.1.1 --- General Aspects of Group 14 Organometallic Compounds --- p.58 / Chapter 2.1.2 --- Group 14 Organometallic Confounds --- p.59 / Chapter 2.1.3 --- Subvalent Group 14 Metal Alkyls --- p.63 / Chapter 2.2 --- RESULTS AND DISCUSSION --- p.67 / Chapter 2.2.1 --- Synthesis of Five Co-ordinated Tin (IV) Compound --- p.67 / Chapter 2.2.2 --- Molecular Structure of [Sn{8-(CHSiMe3)C9H6N}Ph2Cl] --- p.70 / Chapter 2.2.3 --- Synthesis of Group 14 Subvalent Metal Complexes --- p.74 / Chapter 2.3 --- EXPERIMENTAL FOR CHAPTER II --- p.76 / Chapter 2.4 --- REFERENCES FOR CHAPTER II --- p.79 / Chapter CHAPTER III --- SYNTHESIS AND CHARACTERISATION OF SOME GROUP 12 (ZINC AND CADMIUM) METAL DIALKYLS / Chapter 3.1 --- INTRODUCTION --- p.81 / Chapter 3.1.1 --- A General Aspect of Group 12 Organometallics --- p.81 / Chapter 3.2 --- RESULTS AND DISCUSSION --- p.88 / Chapter 3.2.1 --- Synthesis of Group 12 Organometallic Confounds --- p.88 / Chapter 3.2.2 --- Molecular Structure of [Cd{8-(CHSiMe3)C9H6N}(tmeda)Cl] --- p.91 / Chapter 3.3 --- EXPERIMENTAL FOR CHAPTER III --- p.93 / Chapter 3.4 --- REFERENCES FOR CHAPTER III / APPENDIX I / Chapter 1. --- GENERAL PROCEDURES --- p.97 / Chapter 2. --- PHYSICAL AND ANALYTICAL MEASUREMENTS --- p.100 / APPENDIX II / LIST OF SELECTED 1H NMR SPECTRA --- p.101

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