Chan, Chung Yin. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references (leaves 77-80). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.V / Abstract --- p.vi / Chapter Chapter 1 - --- Introduction --- p.1 / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- History of Carbon-Fluorine Bond Activation --- p.1 / Chapter 2.2.1 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1970s --- p.1 / Chapter 2.2.2 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1980s --- p.2 / Chapter 2.2.3 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 1990s --- p.3 / Chapter 2.2.4 --- Examples of Aromatic Carbon-Fluorine Bond Activation in 2000s --- p.6 / Chapter 1.3 --- Difficulties and Challenges in Aromatic Bond Activation Applications of Aromatic Carbon Fluorine Bond Activation --- p.6 / Chapter 2.2.1 --- Thermodynamic Estimations --- p.7 / Chapter 2.2.2 --- Competitive Aromatic Bond Activation --- p.9 / Chapter 1.3.2.1 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Halogen Bond Activation --- p.10 / Chapter 1.3.2.2 --- Competitive Aromatic Carbon-Hydrogen and Carbon-Fluorine Bond Activation --- p.15 / Chapter 1.4 --- Mechanistic Investigations of Aromatic CFA --- p.17 / Chapter 2.2.1 --- Oxidative Addition --- p.17 / Chapter 2.2.2 --- Nucleophilic Aromatic Substitution --- p.18 / Chapter 2.2.3 --- Fluorine Atom Abstraction --- p.19 / Chapter 2.2.4 --- "1,2-Addition" --- p.19 / Chapter 1.5 --- Mechanistic Investigations of Aromatic Carbon-Hydrogen Bond Activation --- p.20 / Chapter 2.2.1 --- Oxidative Addition --- p.20 / Chapter 2.2.2 --- Electrophilic Aromatic Substitution --- p.21 / Chapter 2.2.3 --- "1,2-Addition" --- p.21 / Chapter 1.6 --- Applications of Aromatic Carbon-Fluorine Bond Activation --- p.22 / Chapter 1.7 --- Applications of Aromatic Carbon-Hydrogen Bond Activation --- p.23 / Chapter 1.8 --- Structural Features of Iridium Porphyrins --- p.23 / Chapter 1.9 --- Obj ectives of the Work --- p.25 / Chapter Chapter 2 - --- Competitive Aromatic Carbon Fluorine and Carbon Hydrogen Bond Activation by Iridium(III) Porphyrins --- p.26 / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.26 / Chapter 2.2 --- Preparation of Starting Materials --- p.26 / Chapter 2.2.1 --- Preparation of Tetratolylporphyrin --- p.26 / Chapter 2.2.2 --- Preparation of Iridium(III) Porphyrin Carbonyl Chloride --- p.27 / Chapter 2.3 --- Base Effect of Carbon-Fluorine Bond Activation --- p.27 / Chapter 2.4 --- Solvent Effect of Carbon-Fluorine Bond Activation --- p.30 / Chapter 2.5 --- Temperature Effect --- p.31 / Chapter 2.6 --- Concentration Effect of Carbon-Fluorine Bond Activation --- p.33 / Chapter 2.7 --- Activations of Fluorobenzenes --- p.33 / Chapter 2.8 --- Electronic Effect --- p.36 / Chapter 2.9 --- Mechanistic Studies --- p.38 / Chapter 2.9.1 --- Activation of Fluorobenzene --- p.38 / Chapter 2.9.2 --- Reaction between Ir(ttp)H and Fluorobenzene --- p.40 / Chapter 2.9.3 --- Reaction between Ir2(ttp)2 and Fluorobenzene --- p.41 / Chapter 2.9.4 --- "Reaction between Ir(ttp)""K+ and Fluorobenzene" --- p.42 / Chapter 2.9.5 --- Reaction between Ir(ttp)Me and Fluorobenzene --- p.44 / Chapter 2.10 --- Proposed Mechanism for CFA --- p.45 / Chapter 2.11 --- Proposed Mechanism for CHA --- p.47 / Chapter 2.12 --- Kinetic and Thermodynamic CFA and CHA Products --- p.47 / Chapter 2.13 --- Summary --- p.48 / Chapter Chapter 3 - --- Experimental Section --- p.49 / Reference --- p.77 / Chapter Appendix I - --- Spectra --- p.81

by Tam Tin Lok Timothy. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (leaves 75-81). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iv / Abbreviations --- p.vi / Structural Abbreviations for Porphyrin Complexes --- p.vii / Abstract --- p.viii / Chapter Chapter 1 --- GENERAL INTRODUCTION --- p.1 / Chapter 1.1 --- Carbon-Carbon Bonds Activation by Transition Metal Complexes --- p.1 / Chapter 1.1.1 --- Kinetic and Thermodynamic Considerations in CCA --- p.2 / Chapter 1.1.2 --- C-C Bond Activation in Strained System --- p.3 / Chapter 1.1.3 --- C-C Bond Activation Driven by Aromatization --- p.4 / Chapter 1.1.4 --- C-C Bond Activation of Carbonyl Compounds --- p.5 / Chapter 1.1.5 --- Intramolecular sp2-sp3 C-C Bond Activation in PCP system --- p.8 / Chapter 1.1.6 --- C-C Bond Activation in Homoallylic Alcohol by β-Allyl Elimination --- p.10 / Chapter 1.1.7 --- C-C Bond Activation by Metathesis of Alkanes --- p.11 / Chapter 1.1.8 --- C-C Bond Activation by Nucleophilic Attack of Rhodium Porphyrin Anion --- p.14 / Chapter 1.2 --- Objective of the work --- p.14 / Chapter CHAPTER 2 --- CARBON-CARBON BONDS ACTIVATION (CCA) BY RHODIUM PORPHYRIN RADICAL --- p.16 / Chapter 2.1 --- Serendipitous Discovery of CCA --- p.16 / Chapter 2.1.1 --- Proposed Mechanism of CCA --- p.16 / Chapter 2.2 --- CCA of Rhodium Porphyrin Radical witn Nitroxides --- p.17 / Chapter 2.2.1 --- Synthesis of Rhodium Porphyrins --- p.18 / Chapter 2.2.2 --- Synthesis of Rhodium(II) Porphyrin Radical --- p.19 / Chapter 2.2.3 --- "Synthesis of 1,1,3,3-Tetraalkylisoindolin-2-oxyls" --- p.19 / Chapter 2.2.4 --- Reactions between Rhodium(II) Porphyrin Radical and Nitroxides --- p.21 / Chapter 2.2.5 --- Independent Synthesis of Alkyl Rhodium(III) Porphyrins --- p.24 / Chapter 2.3 --- CCA of Rhodium Porphyrin Radical with Other Substrates --- p.26 / Chapter 2.3.1 --- Reactions between Rhodium(II) Porphyrin Radical and Non-enolizable Ketones --- p.26 / Chapter 2.3.2 --- Reactions between Rhodium(II) Porphyrin Radical and Diketones --- p.27 / Chapter 2.4 --- Ligand Effects on Carbon-Carbon Bonds Activation --- p.28 / Chapter 2.4.1 --- Ligand Coordination between Rhodium(II) Porphyrin Radical --- p.29 / Chapter 2.4.2 --- Phosphine Effects on CCA between Rhodium(II) Porphyrin Radical and Nitroxides --- p.31 / Chapter 2.5 --- Summary --- p.32 / Chapter CHAPTER 3 --- PRELIMINARY MECHANISTIC STUDIES OF CARBON- CARBON BONDS ACTIVATION (CCA) --- p.33 / Chapter 3.1 --- Attempted Mechanistic Studies of CCA --- p.33 / Chapter 3.1.1 --- Proposed Mechanism of CCA via SH2 Pathway --- p.33 / Chapter 3.1.2 --- Homolytic Bimolecular Substitution (Sr2) --- p.33 / Chapter 3.1.3 --- Literature Review on Sh2 Reaction --- p.34 / Chapter 3.1.4 --- Prerequisities on SH2 reactions at Carbon Center --- p.36 / Chapter 3.1.5 --- Kinetic Studies of CCA between Rh(tmp) and TEMPO…… --- p.37 / Chapter 3.2 --- Stereochemical Test for CCA --- p.39 / Chapter 3.2.1 --- Objective of the Stereochemical Test --- p.39 / Chapter 3.2.2 --- Synthesis of Alkyl Rhodium(III) Porphyrins --- p.42 / Chapter 3.2.3 --- Alkyl Exchange Reactions with Rh(por)R --- p.42 / Chapter 3.3 --- Summary --- p.43 / Chapter CHAPTER 4 --- EXPERIMENTAL SECTION --- p.45 / CONCLUSION --- p.74 / REFRENCES --- p.75 / LIST OF SPECTRA --- p.82 / SPECTRA --- p.83

by Kui Chi Fai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Acknowledgements --- p.i / Abstracts --- p.ii / Table of Contents --- p.v / Abbreviations --- p.viii / Chapter CHAPTER 1. --- METALLATION OF AMINOPYRIDINE AND AMINOQUINOLINE / Chapter 1.1 --- INTRODUCTION --- p.1 / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- A Brief Review on Sodium and Potassium Amides --- p.3 / Chapter 1.1.3 --- Preparation of Sodium and Potassium Amides --- p.8 / Chapter 1.2 --- RESULTS AND DISCUSSION --- p.10 / Chapter 1.2.1 --- "Synthesis of [NH(SiButMe2)(R)] [ R = 2-C5H3N-6-Me, 8-C9H6N ] as Ligand Precursors" --- p.10 / Chapter 1.2.2 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Pyridine-Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]- --- p.11 / Chapter 1.2.2.1 --- Sodium Pyridyl Amido Complexes --- p.11 / Chapter 1.2.2.2 --- Potassium Pyridyl Amido Complexes --- p.12 / Chapter 1.2.3 --- Synthesis of Sodium and Potassium Amido Complexes Containing the Quinoline-Functionalized Amido Ligand [N(SiButMe2)(8-C9H6N)]- --- p.15 / Chapter 1.2.3.1 --- Sodium Quinolyl Amido Complexes --- p.15 / Chapter 1.2.3.2 --- Potassium Quinolyl Amido Complexes --- p.16 / Chapter 1.2.4 --- Physical Characterization of Compounds 3-9 --- p.17 / Chapter 1.2.5 --- "Molecular Structures of Compounds 3, 5 and 7" --- p.20 / Chapter 1.3 --- EXPERIMENTALS FOR CHAPTER 1 --- p.30 / Chapter 1.3 --- REFERENCES FOR CHAPTER 1 --- p.36 / Chapter CHAPTER 2. --- "Synthesis,Structures, and Catalytic Properties of Lanthanide Metal Amides Containing the Pyridine - Functionalized Amido Ligand [N(SiButMe2)(2-C5H3N-6-Me)]-" / Chapter 2.1 --- INTRODUCTION --- p.39 / Chapter 2.1.1 --- General Background --- p.39 / Chapter 2.1.2 --- A Brief Review on Rare Earth Amido Complexes --- p.40 / Chapter 2.1.3 --- General Preparation Methods to Lanthanide Metal Amides --- p.44 / Chapter 2.1.4 --- Ring-Opening Polymerization of Lactones --- p.45 / Chapter 2.1.5 --- Objectives of This Work --- p.48 / Chapter 2.2 --- RESULTS AND DISCUSSION --- p.49 / Chapter 2.2.1 --- Synthesis and Physical Properties --- p.49 / Chapter 2.2.1.1 --- Homoleptic Lanthanide Metal Amides 10-18 --- p.49 / Chapter 2.2.1.2 --- Heteroleptic Lanthanide Metal Amides 19-22 --- p.53 / Chapter 2.2.2 --- Molecular Structures --- p.56 / Chapter 2.2.2.1 --- Molecular Structures of Homoleptic Lanthanide Metal Amides 10-18 --- p.56 / Chapter 2.2.2.2 --- Molecular Structures of Heteroleptic Lanthanide Metal Amides 19-22..… --- p.76 / Chapter 2.2.3 --- Reactivity Studies --- p.89 / Chapter 2.2.3.1 --- "Reaction with 3,5-di-tert-butylcatechol (dbcH2)" --- p.89 / Chapter 2.2.3.2 --- Ring-Opening Polymerization of s-Caprolactone --- p.95 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.100 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.108 / Chapter CHAPTER 3. --- Preparation of Pyridine Adducts of Zinc(II) Chloride and Low-coordinate Zinc(II) Dithiolate and Bis(aryloxide) Compounds / Chapter 3.1 --- INTRODUCTION --- p.111 / Chapter 3.1.1 --- General Background --- p.111 / Chapter 3.2 --- RESULTS AND DISCUSSION --- p.115 / Chapter 3.2.1 --- Synthesis of Pyridine Adducts of Zinc(II) Chloride --- p.115 / Chapter 3.2.2 --- Synthesis of Novel Three-Coordinate Zinc(II) Dithiolate and Bis(aryloxide) --- p.116 / Chapter 3.2.3 --- Physical Characterization of Compounds 23-26 --- p.118 / Chapter 3.2.4 --- Molecular Structures of Compounds 23-25 --- p.122 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.129 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.133 / Chapter CHAPTER 4. --- Summary of this Research Work --- p.135 / Appendix 1 General Procedures and Physical Measurements --- p.137 / "Appendix 2 Table A-l. Selected Crystallographic Data for Compounds 3, 5，7，10 and 11" --- p.139 / Table A-2. Selected Crystallographic Data for Compounds12-16 --- p.140 / Table A-3. Selected Crystallographic Data for Compounds17-21 --- p.141 / Table A-4. Selected Crystallographic Data for Compounds22-25 --- p.142

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE / Vita. / Includes bibliographical references. / by Scott M. Rocklage. / Ph.D.

*Please refer to dissertation for diagrams. / Part I describes the silicon-hydrogen bond activation (SiHA) of silanes with both electron-deficient iridium porphyrin carbonyl chloride (Ir(ttp)Cl(CO)) and electron-rich iridium porphyrin methyl (Ir(ttp)Me) to give iridium(III) porphyrin silyls (Ir(ttp)SiR3). Firstly, Ir(ttp)SiR3 were synthesized in moderate to good yields conveniently from the reactions of Ir(ttp)Cl(CO) and Ir(ttp)Me with silanes, via SiHA in solvent-free conditions and non-polar solvents at 200°C. Base facilitated the SiHA reaction even at lower temperature of 140°C. Specifically, K3PO4 accelerated the SiHA with Ir(ttp)Cl(CO), while KOAc promoted the SiHA by Ir(ttp)Me. Mechanistic experiments suggest that Ir(ttp)Cl(CO) initially forms iridium porphyin cation (Ir(ttp)+), which then reacts with silanes likely via heterolysis to give iridium porphyrin hydride (Ir(ttp)H). Ir(ttp)H further reacts with silanes to yield Ir(ttp)SiR3. On the other hand, Ir(ttp)Me and Ir(ttp)SiR3 undergo either oxidative addition (OA) or sigma-bond metathesis (SBM) to form the products. In the presence of base, a penta-coordinated silicon hydride species likely forms and reacts with Ir(ttp)Me to form iridium porphyrin anion (Ir(ttp) -) that can further react with silane to yield Ir(ttp)H after protonation. Ir(ttp)H finally reacts with excess silane to give Ir(ttp)SiR 3.* / Part II describes successful base promoted aromatic carbon-fluorine (C-F) and carbon-hydrogen (C-H) bond activation of fluorobenzenes in neat conditions to give the corresponding iridium(III) porphyrin aryls (Ir(ttp)Ar) at 200°C in up to 95% yield. Mechanistic studies suggested that Ir(ttp)SiEt3 is firstly converted to Ir(ttp)- in the presence of KOH. Ir(ttp)- cleaves the aromatic C-F bond via an S NAr process. As the reaction proceeds, a hydroxide anion can coordinate to the iridium center of Ir(ttp)Ar to form an iridium porphyrin trans aryl hydroxyl anion (trans-[ArIr(ttp)OH]-). In the presence of water, trans-[ArIr(ttp)OH]- can give Ir(ttp)OH and ArH. Ir(ttp)OH then undergoes aromatic C-H bond activation reaction to give Ir(ttp)Ar'. Furthermore, the aromatic C-F bond activation products were found as the kinetic products, and aromatic C-H bond activation products were the thermodynamic ones.* / Part III describes the successful C(C=O)-C(alpha) bond activation of acetophenones by high-valent iridium porphyrin complexes (Ir(ttp)X, X = Cl(CO), (BF4)(CO), Me) in solvent-free conditions at 200°C to give the corresponding iridium porphyrin benzoyls (Ir(ttp)COAr) in up to 92% yield. Mechanistic studies suggest that Ir(ttp)X reacts with acetophenones to give alpha-CHA product as the primary product, which can re-convert back to the active intermediate Ir(ttp)OH or Ir(ttp)H in the presence of water formed from the concurrent iridium-catalyzed aldol condensation of acetophenones. Then Ir(ttp)OH cleaves the aromatic C-H bonds to produce the aromatic CHA products, which are more thermally stable than the alpha-CHA product. Both Ir(ttp)H and Ir(ttp)OH were the possible intermediates to cleave the C(C=O)-C(alpha) bond to give thermodynamic products of Ir(ttp)COAr. On the other hand, only Ir(ttp)(BF 4)(CO) can react with the aliphatic ketones, likely due to the stronger Lewis acidity and the HBF4 generated in catalyzing the aldol condensation of aliphatic ketones to facilitate the formation of Ir(ttp)OH and Ir(ttp)H.* / The objectives of the research focus on the bond activation chemistry by iridium porphyrin complexes with three organic substrates, (1) hydrosilanes (HSiR3), (2) fluorobenzenes (C6HnF6-n , n = 0--6), and (3) aromatic or aliphatic ketones (RCOR, R = alkyl or aryl). / Li, Baozhu. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 72-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. Ann Arbor, MI : ProQuest Information and Learning Company, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese.

Lee, Man Ho. / Thesis submitted in: October 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 78-83). / Abstracts in English and Chinese. / Table of Contents --- p.ii / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Aromatic Bond Activation --- p.1 / Chapter 1.2 --- Application of Aromatic Carbon Fluorine Bond Activation --- p.1 / Chapter 1.3 --- Mechanistic Schemes Involved in Aromatic Bond Activation --- p.2 / Chapter 1.4 --- Difficulties in Aromatic Bond Activation --- p.7 / Chapter 1.5 --- Competitive Bond Activations --- p.20 / Chapter 1.6 --- Structural Features of Rhodium Porphyrins --- p.27 / Chapter 1.7 --- Objective of the Work --- p.28 / Chapter Chapter 2 --- Competitive C-F and C-H Activation of Fluorobenzenes by Rhodium(III) Porphyrins / Chapter 2.1 --- C-F Activation of Fluorobenzene by Rhodium(III) Porphyrins --- p.29 / Chapter 2.2 --- Preparation of Starting Materials --- p.29 / Chapter 2.3 --- Base Effect of CFA --- p.30 / Chapter 2.4 --- Solvent Effect of CFA --- p.32 / Chapter 2.5 --- Temperature Effect of CFA Reaction --- p.34 / Chapter 2.6 --- Activations of Fluorobenzene --- p.35 / Chapter 2.7 --- Electronic Effect of Carbon-Fluorine Bond Activations --- p.38 / Chapter 2.8 --- Preliminary Mechanistic Studies --- p.39 / Chapter 2.9 --- Proposed C-F Activation Mechanism --- p.44 / Chapter 2.10 --- Proposed C-H Activation Mechanism --- p.48 / Chapter 2.11 --- Summary --- p.51 / Chapter Chapter 3 --- Experimental Section --- p.56 / References --- p.78 / Table of Content of Appendix --- p.83 / Appendix I Crystal Data and Processing Parameters --- p.85 / Appendix II Spectra --- p.91

No description available.

Diquinoline molecules have been shown previously to have interesting inclusion properties. Of the nine new, targeted molecules produced for this work, seven formed inclusion compounds, and their solid-state structures are discussed herein. Chapter 2 shows the effect that substituting a hydrogen atom with a chlorine atom has on the inclusion properties. This comes about because of the additional intermolecular attractions that are now possible, and a wider range of guest molecules is included as a result. A new homochiral aromatic 'swivel offset face-face (OFF)' interaction is observed. Chapters 3 and 4 deal with the effect of adding extra aromatic planes to the target molecules, two or four planes, respectively. Each of these host molecules formed dimeric host-host units that are extremely similar across all crystal structures. These dimers mainly employed aromatic edgeface (EF) interactions. Chapter 5 looks at the effect of combining the modifications described in Chapters 2-4, namely additional aromatic surfaces and atom substitution. The resulting host molecule specifically includes polyhalomethane guests. In addition, this host molecule formed two concomitant pseudo-dimorph compounds with chloroform-d. The diquinoline host molecule presented in Chapter 6 incorporated an isomeric central linker ring to the other compounds. Although only a single crystal structure could be obtained, 1H NMR spectroscopy experiments show other small aromatics may be included. The effect of electron donating chemical substituents was examined in Chapter 7. These compounds were found to be quite insoluble, and did not produce crystals suitable for X-ray analysis. The host molecules in Chapter 8 contain electron withdrawing nitro groups. The two isomeric compounds that act as inclusion hosts show quite different properties. One of these hosts forms a series of inclusion compounds with water, in which the site occupancy of the guest can range from 0-100% without change to the overall structure. All the X-ray structures described have been analysed in crystal engineering terms, and their supramolecular interactions described in detail.

Abstract not available

Hydrogen gas is the cleanest and most cost-effective reductant available to mankind, and the use of hydrogen gas in catalytic hydrogenation reactions is one of the oldest and most utilized organic reactions. Although catalytic hydrogenation has been practiced in industry on enormous scale, the use of hydrogen gas as a terminal reductant in C-C bond forming reactions has been limited to processes involving the migratory insertion of carbon monoxide such as: alkene hydroformylation and the Fischer-Tropsch reaction. A significant advance to the field of synthetic organic chemistry would be the expansion of C-C bond forming reactions beyond reductive coupling via carbon monoxide insertion. Herein, related metal catalyzed reductive couplings to [alpha],[beta]-unsaturated compounds in the presence of reducing agents such as: silane, borane, and hydrogen are reviewed. The following chapters discuss the development of hydrogen-mediated reductive aldol and Mannich reactions. The results from this body of work clearly demonstrate that hydrogen-mediated C-C bond forming reactions are emerging as a powerful tool for synthetic chemists.