No description available.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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.

No description available.

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

An NMR spectroscopy study of trimethylsilylmethyllilthium, TMSM-Li, indicates that TMSM-Li exists as two different aggregates in cyclopentane solution. Using previously reported colligative properties of TMSM-Li in different solutions in connection with new 13C and 6Li NMR data collected in this study, aggregation states were assigned as octamer and hexamer. Low temperature 13C and 6Li NMR peak intensities indicated an equilibrium exists between the two aggregates that shifts toward the octamer as the temperature decreases. ΔH was calculated to be 5.23 + 0.15 kcal/mol and ΔS was calculated to be 17.9 + 0.6 eu for the hexamer/octamer equilibrium system. Samples of TMSM-Li were mixed with TMSM-OH in attempts to form mixed alkyllithium/lithium alkoxide aggregates. 13C NMR data for these mixtures gave inconclusive results whether or not these compounds formed, which is different from other primary alkyllithium compounds studied in the past. A study of neopentyllithium, NpLi, indicates only one aggregate in solution with the aggregation state unknown using low temperature 13C NMR spectroscopy.

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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.