Choi, Kwong Shing. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2011. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Song, Xu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 92-96). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Part I --- Carbon-Carbon Bonds Activation (CCA) of Ketones by Iridium(III) Porphyrins / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Carbon-Carbon Bonds Activation by Transition Metals --- p.1 / Chapter 1.2 --- Thermodynamic and Kinetic Considerations in CCA --- p.1 / Chapter 1.3 --- C-C Bonds Activation by Low Valent Transition Metal Complexes --- p.3 / Chapter 1.3.1 --- CCA in Strained System --- p.3 / Chapter 1.3.2 --- CCA Driven by Aromatization --- p.6 / Chapter 1.3.3 --- Chelation Assisted CCA --- p.8 / Chapter 1.4 --- C-C Bonds Activation by High Valent Transition Metal Complexes --- p.11 / Chapter 1.5 --- Previous Mechanistic Studies on CCA by High Valent Transition Metal Complexes --- p.14 / Chapter 1.6 --- Objective of the Work --- p.16 / Chapter Chapter 2 --- Carbon-Carbon Bonds Activation (CCA) of Ketones by Iridium(III) Porphyrins / Chapter 2.1 --- Introduction --- p.17 / Chapter 2.2 --- CCA of Aromatic Ketones with Iridium(III) Porphyrins --- p.17 / Chapter 2.2.1 --- CCA of Aromatic Ketones with Ir(III) Porphyrin Chloride --- p.17 / Chapter 2.2.2 --- CCA of Aromatic Ketones with Ir(III) Porphyrin Methyl --- p.20 / Chapter 2.2.3 --- Steric Effect on CCA with Ir(III) Porphyrins --- p.21 / Chapter 2.3 --- CCA of Aliphatic Ketones with Iridium(III) Porphyrins --- p.21 / Chapter 2.3.1 --- CCA of Unstrained Aliphatic Ketones with Ir(III) Porphyrins --- p.21 / Chapter 2.3.2 --- CCA of Cyclic Aliphatic Ketones with Ir(III) Porphyrins --- p.22 / Chapter 2.4 --- Summary --- p.23 / Chapter Chapter 3 --- Preliminary Mechanistic Studies of Carbon-Carbon Bonds Activation (CCA) / Chapter 3.1 --- Proposed Mechanism of CCA with Ir(III) Porphyrin Chloride --- p.24 / Chapter 3.2 --- Proposed Mechanism of CCA with Ir(III) Porphyrin Methyl --- p.27 / Chapter 3.3 --- Determination of CCA co-product in situ --- p.30 / Chapter 3.4 --- Summary --- p.31 / Experimental Section --- p.33 / References --- p.44 / List of Spectra I --- p.48 / Chapter Part II --- Supramolecular Chemistry of C6o with Ir(III) Porphyrin Methyl / Chapter Chapter 1 --- General Introduction / Chapter 1.1 --- Supramolecular Interactions --- p.62 / Chapter 1.2 --- Introduction of C6o --- p.67 / Chapter 1.3 --- Supramolecular Interactions between C6o and Metalloporphyrins --- p.70 / Chapter 1.3.1 --- Discovery of Supramolecular Interactions between C6o And Metalloporphyrins --- p.70 / Chapter 1.3.2 --- Development of C6o-Metalloporphyrin Supramolecular Structure and Application --- p.71 / Chapter 1.3.3 --- Investigation on C6o-Metalloporphyrin Bonding Nature --- p.73 / Chapter 1.4 --- Objective of the Work --- p.76 / Chapter Chapter 2 --- Supramolecular Interaction between C60 and Ir(III) Porphyrin Methyl / Chapter 2.1 --- Synthesis of C60-Ir(ttp)Me Complexes --- p.77 / Chapter 2.2 --- X-ray Structure Analysis of C60-Ir(ttp)Me Complexes --- p.78 / Chapter 2.3 --- 1H NMR Analysis of C60-Ir(ttp)Me Complexes --- p.83 / Chapter 2.4 --- 13C NMR Analysis of C60-Ir(ttp)Me Complexes --- p.84 / Chapter 2.5 --- Binding Constant of C60-Ir(ttp)Me Complexes Using UV-Vis Analysis --- p.85 / Chapter 2.6 --- Summary --- p.87 / Experimental Section --- p.88 / References --- p.92 / Appendix --- p.97 / List of Spectra II --- p.101 / Reprint of OM Paper --- p.112 / Supporting Information for Organometallics Paper --- p.118

本論文主要探討銠卟啉和銥卟啉絡合物，分別與酮類與醛類進行的鍵活化化學。 / 第一部分主要介紹由β-乙基羥基銠卟啉絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH)與酮類進行的羰基碳及α-碳(C(CO)-C(α)) 鍵活化(下稱碳碳鍵活化)。於室溫至50ºC時，在非溶劑的條件下，Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH選擇性地斷裂芳香酮和脂肪酮類的C(CO)-C(α)鍵，生成相對應的銠卟啉酰基絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)COR, R = 烷基或芳基)，產率最高可達80%。作為銠卟啉羥基絡合物(Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH)的前體，Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH的活性展示出Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH是碳碳鍵活化的重要中間體。 / 第二部分主要介紹由β-乙基羥基銥卟啉絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH)與芳香醛類進行，具選擇性的醛碳氫鍵活化。在160ºC和非溶劑的條件下，Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH與芳香醛類反應，生成相對應的銥卟啉酰基絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)COAr)作為碳氫鍵活化產物，產率最高可達72%。銥卟啉羥基絡合物(Ir{U+1D35}{U+1D35}{U+1D35}(ttp)OH)和乙烯配位銥卟啉絡合正離子((CH₂=CH₂)Ir{U+1D35}{U+1D35}{U+1D35}(ttp)⁺)被推斷為醛碳氫鍵活化的可能中間體。 / This research focuses on the bond activation chemistry by rhodium and iridium porphyrin complexes with ketones and aldehyde respectively. / Part 1 describes the C(CO)-C(α) bond activation (CCA) of ketones by Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH (ttp = 5,10,15,20-tetratolylporphyrinato dianion). Rh{U+1D35}{U+1D35}{U+1D35}(ttp)- CH₂CH₂OH selectively cleaved the C(CO)-C(α) bond of aromatic and aliphatic ketones in solvent-free conditions at room temperature to 50ºC, giving the corresponding rhodium(III) porphyrin acyls (Rh{U+1D35}{U+1D35}{U+1D35}(ttp)COR, R = alkyl or aryl) up to 80% yield. The activity of the Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH precursor, Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH, demonstrates Rh{U+1D35}{U+1D35}{U+1D35}(ttp)OH as the key intermediate in the CCA of ketones. / [With images]. / Part 2 describes the selective aldehydic carbon-hydrogen bond activation (CHA) of aryl aldehydes by Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH. Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH reacted with aryl aldehydes in solvent-free conditions at 160ºC to give the corresponding iridium(III) porphyrin acyls (Ir{U+1D35}{U+1D35}{U+1D35}(ttp)COAr) as the CHA products up to 72% yield. Ir{U+1D35}{U+1D35}{U+1D35}(ttp)OH and (CH₂=CH₂)Ir{U+1D35}{U+1D35}{U+1D35}(ttp)⁺ were proposed as the possible intermediate for the CHA reaction. / [With images]. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chan, Chung Sum. / "November 2012." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Abstracts also in Chinese. / Abstract --- p.i / Acknowledgement --- p.iii / Table of Contents --- p.iv / Abbreviations --- p.vii / Structural Abbreviations of Porphyrin --- p.viii / Chapter Part 1 --- Carbon-Carbon Bond Activation of Ketones with Rhodium(III) Porphyrin β-Hydroxyethyl --- p.1 / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Properties of Ketones --- p.1 / Chapter 1.2 --- Carbon(CO)-Carbon(α) Bond Activation (CCA) of Ketones --- p.2 / Chapter 1.2.1 --- CCA of Ketones by Transition Metal Complexes --- p.2 / Chapter 1.2.2 --- CCA of Ketones by Metalloporphyrins --- p.5 / Chapter 1.3 --- Porphyrin Ligands and Rhodium(III) Porphyrins --- p.7 / Chapter 1.3.1 --- Porphyrin Ligands --- p.7 / Chapter 1.3.2 --- Rhodium(III) Porphyrins --- p.8 / Chapter 1.4 --- Rhodium(III) Porphyrin Hydroxide --- p.10 / Chapter 1.4.1 --- Nature of Bonding in Late Transition Metal Hydroxides --- p.10 / Chapter 1.4.1.1 --- Hard-Soft Acid-Base principle --- p.11 / Chapter 1.4.1.2 --- dπ-pπ Interaction Model --- p.11 / Chapter 1.4.1.3 --- E-C Model --- p.12 / Chapter 1.4.2 --- Attempted Preparation of Rhodium(III) Porphyrin Hydroxides --- p.13 / Chapter 1.4.3 --- Chemistry of Rhodium(III) Porphyrin Hydroxides --- p.15 / Chapter 1.5 --- Rhodium(III) Porphyrin β-hydroxyethyl as Rhodium(III) Hydroxide Precursor --- p.18 / Chapter 1.6 --- Objective --- p.20 / Chapter Chapter 2 --- Carbon-Carbon Bond Activation of Ketones with Rhodium(III) Porphyrin β-Hydroxyethyl --- p.21 / Chapter 2.1 --- Preparation of Starting Materials --- p.21 / Chapter 2.1.1 --- Synthesis of Porphyrin --- p.21 / Chapter 2.1.2 --- Synthesis of Rhodium(III) Porphyrins --- p.21 / Chapter 2.2 --- CCA of Diisopropyl Ketone by Rh{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.22 / Chapter 2.3 --- Optimization of Reaction Conditions --- p.22 / Chapter 2.3.1 --- Atmosphere Effect --- p.22 / Chapter 2.3.2 --- PPh3 Effect --- p.23 / Chapter 2.3.3 --- Solvent Effect --- p.24 / Chapter 2.4 --- Substrate Scope --- p.26 / Chapter 2.4.1 --- CCA of Isopropyl Ketones --- p.26 / Chapter 2.4.2 --- CCA of Non-Isopropyl Ketones --- p.28 / Chapter 2.5 --- Proposed Mechanism --- p.29 / Chapter 2.6 --- Comparison on CCA of Ketones by Different Rh{U+1D35}{U+1D35}{U+1D35}(por)OH Sources --- p.31 / Chapter 2.6.1 --- Reaction Conditions --- p.31 / Chapter 2.6.2 --- Substrate Scope --- p.32 / Chapter 2.6.3 --- Regioselectivity --- p.33 / Chapter 2.7 --- Comparison on Bond Activation of Carbonyl Compounds by Rhodium Porphyrin β-Hydroxyethyl --- p.34 / Chapter 2.8 --- CCA of Ketones with Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.36 / Chapter 2.9 --- Conclusion --- p.37 / Chapter Chapter 3 --- Experimental Sections --- p.39 / References --- p.54 / List of Spectra I --- p.59 / Spectra --- p.60 / Chapter Part 2 --- Aldehydic Carbon-Hydrogen Bond Activation with Iridium(III) Porphyrin β-Hydroxyethyl --- p.63 / Chapter Chapter 1 --- Introduction --- p.63 / Chapter 1.1 --- Properties of Aldehydes --- p.63 / Chapter 1.2 --- Carbon-Hydrogen Bond Activation (CHA) of Aldehydes --- p.64 / Chapter 1.2.1 --- CHA of Aldehydes by Transition Metal Complexes --- p.64 / Chapter 1.2.2 --- Aldehydic CHA by Metalloporphyrins --- p.74 / Chapter 1.3 --- Iridium(III) Porphyrins --- p.77 / Chapter 1.4 --- Iridium(III) Porphyrin Hydroxide --- p.78 / Chapter 1.4.1 --- Attempted Preparation of Iridium(III) Porphyrin Hydroxides --- p.78 / Chapter 1.4.2 --- Chemistry of Iridium(III) Porphyrin Hydroxides --- p.81 / Chapter 1.5 --- Iridium(III) Porphyrin β-hydroxyethyl as Iridium(III) Hydroxide Precursor --- p.83 / Chapter 1.6 --- Objective --- p.85 / Chapter Chapter 2 --- Aldehydic Carbon-Hydrogen Bond Activation with Iridium(III) Porphyrin β-Hydroxyethyl --- p.86 / Chapter 2.1 --- Preparation of Iridium(III) Porphyrins --- p.86 / Chapter 2.2 --- Aldehydic CHA of Benzaldehyde by Ir{U+1D35}{U+1D35}{U+1D35}(ttp)CH₂CH₂OH --- p.87 / Chapter 2.3 --- Optimization of Reaction Conditions --- p.87 / Chapter 2.3.1 --- Temperature Effect --- p.87 / Chapter 2.3.2 --- Solvent Effect --- p.88 / Chapter 2.3.3 --- PPh₃ Effect --- p.90 / Chapter 2.4 --- Substrate Scope --- p.93 / Chapter 2.5 --- Proposed Mechanism --- p.94 / Chapter 2.6 --- Conclusion --- p.96 / Chapter Chapter 3 --- Experimental Sections --- p.97 / References --- p.108 / List of Spectra II --- p.112 / Spectra --- p.112

*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.

The oxidative addition of amino acids and other biologically interesting molecules to iridium{(I) complexes was studied and the reactivity of the resulting hydrido chelate complexes was investigated. Oxidative addition of amino acids to [Ir(COD)(PMe₃)₃]Cl resulted in the formation of meridional tris trimethylphosphine Ir(III) hydride complexes, with the amino acid chelated to the metal center forming 5 membered rings. The majority of the naturally occurring amino acids were studied as potential oxidative addition reactants. The amino acids with reactive side chains did not form clean products. The amino acids without reactive side chains did form clean products which were characterized by ¹H NMR, ³¹P NMR, ¹³C NMR spectroscopy, C,H analyses, and single crystal X-ray diffraction. The studies went on to investigate other 𝛂 amino acid compounds and attempts were made to form 6 membered ring complexes with 𝛃 amino acids. The reactivity of these complexes was also studied. A number of reaction conditions were used in attempts to induce the iridium amino acid complexes and various unsaturates, but the stability of the 5 membered ring system did not allow for insertion of unsaturates. An attempt was made to synthesize coordinately unsaturated complexes of iridium with amino acids. A variety of reactions were tried with the coordinately unsaturated compound, [Ir(COD)(DMPE)]Cl, but amino acid products were not produced in these reactions. Rather, an interesting rearrangement product of [Ir(COD)(DMPE)]Cl was formed and the crystal structure of [Ir (µ¹, µ³ - COD)DMPE]Cl complex was solved. Other attempts to induce reactivity of hydrido amino acid - Ir complexes involved synthesizing N-methyl amino acid complexes. The treatment of [Ir(COD)(PMe₃)₃]Cl with N-methylphenylalanine or N-methylglycine formed the respective chelate hydrido complexes. The reactivity studies of these complexes were negative. The insertion of an unsaturate was observed with 2-amino-4- pentenoic acid. This compound is an a-amino acid with a tethered olefin and when treated with Ir(COD)(PMe₃)₃]Cl binds through three sites (O, N, C) to the metal center. The Ir-C bond formed supports the fact that the olefin has inserted into the Ir-H bond. The crystal structure of this complex was solved. Several amino acid iridium complexes were tested for biological activity in NCI cancer and HIV assays. The complexes had no activity against cancer, but the phenylalanine complex did show moderate activity against HIV. The results prompted studies with other biologically interesting molecules and a number of sulfur containing compounds were studied. The formation of 4 membered ring systems was observed resulting from reactions of thiourea and analogs with [Ir(COD)(PMe₃)₃]Cl. These compounds are to be studied for their reactivity with unsaturates. / Ph. D.