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Submitted in fulfillment of the requirements for the award of the Degree of Master of Applied Science in Chemistry, Durban University of Technology, Durban, South Africa, 2016. / The 𝛼-aminophosphonates (APs) and dihydropyrimidinones (DHPMs) exhibit a wide range of important biological activities. The great potential of these compounds in biological applications prompted an increased interest in the development of efficient synthetic methods for their preparation. A novel rhodium supported boron nitride (RhBNT) material was synthesized by simply mixing boron nitride in a solution of rhodium acetate, under inert atmosphere for 7 days followed by filtration; the yield was 95 %. It exhibited excellent catalytic properties for the synthesis of 13 novel APs and 5 DHPMs. Characterization of RhBNT was performed by several techniques: the crystalline nature of RhBNT and nano size was confirmed by SEM spectroscopy, EDX pattern for RhBNT showed signals for rhodium metal, the Brumnauer-Emmett-Teller (BET) analysis showed the specific surface area of RhBNT to be 28.12 m2/g, pore volume 0.23cm3/g and pore size of 199.8Aº thereby suggesting RhBNT as a potentially effective catalyst for organic reactions; the mesoporous nature of the material was established by a type- IV adsorption isotherm; the DSC-TGA Profile indicates that RhBNT has good thermal stability and can be used adequately for catalysis. The DSC curve showed evidence of a broad exothermic peak. The RhBNT was subsequently used in the Kabachnik-Fields and Biginelli reaction in order to assess its catalytic potential. Herein Vilsmeier-Haack reagent was used to synthesize 4-oxo-chromene-3-carbaldehyde and 4-oxo-4H-benzo[h]chromene-3- carbaldehyde from 2-hydroxyacetophenone and 1-hydroxy-2-acetonaphthone, respectively. These two carbaldehydes were subsequently used to synthesize thirteen novels APs and five DHMPs using RhBNT as the catalyst The antimicrobial activities of the synthesized compounds were assessed against Escherichia coli, Bacillus cereus, Micrococcus luteus, Staphylococcus aureus and Candida albicans using the disc diffusion method. It was found that none of the compounds inhibited growth of bacteria or fungus. The assessment of toxicity was evaluated by using the brine shrimp lethal test. It was found that six of the novel compounds exhibited more than 50% brine shrimp death and were considered toxic against Artemia sp. and hence unsuitable as a potential drug whilst four compounds were found to be less toxic, exhibiting a brine shrimp death of less than 50%. Molecular docking studies were carried out for 13 APs to estimate their binding interactions with HIV-1 reverse transcriptase. Four APs showed good potential for the inhibition of HIV-1 reverse transcriptase. / M

by Kin Wah Mak. / Thesis (Ph.D.)--Chinese University of Hong Kong, 1998. / Includes bibliographical references (p. 180-195). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web.

*Please refer to dissertation for diagrams. / Part 1 describes the selective C(alpha)-(beta) bonds cleavage of a series of aliphatic ethers (RCH2OCH2R: R = Et, Pr, Bu, iBu and pentyl) by RhII(tmp) using PPh3 as the promoting ligand to give Rh(tmp)-alkyls bearing the C(beta)-substituent in 13-40% yields at 24°C. The rate and the yields of Rh(tmp)-alkyls decreased with increasing steric hindrance of ethers. Addition of bases such as KOtBu, CsOH.H2O and KOH as well as H2O further promoted the product yields of the reactions with n-butyl ether to 56-62%. The reaction between RhII(tmp) and the cyclic ether, oxepane, at 24°C for 1 day gave Rh(tmp)(CH2)5OCHO in 17% yield suggesting that Rh(tmp)OH is the key intermediate in the C-C cleavage step and presumably generated via the PPh3-, H2O-, and OH --assisted disproportionation of RhII(tmp).* / Secondly, the reductive dehydrogenation of Rh(tmp)H to RhII(tmp) was also observed. Rh(tmp)H reacted with KOH in benzene-d6 at 100°C for 1 hour to give RhII(tmp) in 30% yield. [Rh I(tmp)]- is proposed to form initially via the deprotonation of Rh(tmp)H with KOH and then reacts with the unreacted Rh(tmp)H to give Rh II(tmp) via electron transfer. Thirdly, the hydroxide-induced disproportionation of RhII(tmp) to RhIII(tmp)OH and [Rh I(tmp)]- has also been proposed.* / The objective of this thesis focuses on studies of selective, base-promoted aliphatic carbon(alpha)-carbon(beta) bond activation (CCA) of ethers with rhodium(II) and rhodium(III) meso-tetramesitylporphyrin complexes (Rh II(tmp) and Rh(tmp)I). The roles of potassium hydroxide in promoting the interconversions of rhodium porphyrin species (RhII(tmp), Rh(tmp)I, Rh(tmp)OH and Rh(tmp)H) will also be discussed. / Lai, Tsz Ho. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 72-04, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 161-172). / 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. / Abstract also in Chinese.

Au, Ching Chi. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 83-89). / Abstracts in English and Chinese. / Table of contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Importance of Transition Metal Amido Complexes --- p.1 / Chapter 1.1.1 --- Transition Metal Amido Complexes as Catalysts --- p.1 / Chapter 1.1.2 --- Transition Metal Amido Complexes as Reaction Intermediates --- p.2 / Chapter 1.2 --- Bonding Nature of Late Transition Metal Amido Complexes --- p.4 / Chapter 1.2.1 --- Theory of π Conflict --- p.5 / Chapter 1.2.2 --- E-C Approach --- p.7 / Chapter 1.3 --- Synthesis of Transition Metal Amido Complexes --- p.8 / Chapter 1.3.1 --- Transmetallation --- p.9 / Chapter 1.3.2 --- Deprotonation of Coordinated Amine --- p.10 / Chapter 1.3.3 --- Hydride Addition across Organic Azide --- p.11 / Chapter 1.4 --- Reactivity of Transition Metal Amido Complexes --- p.12 / Chapter 1.4.1 --- β-Elimination --- p.12 / Chapter 1.4.2 --- Insertion --- p.13 / Chapter 1.4.3 --- Reductive Elimination --- p.16 / Chapter 1.4.4 --- Bond Activation --- p.17 / Chapter 1.5 --- Structural Features of Rhodium Porphyrin Complexes --- p.18 / Chapter 1.6 --- Examples of Metalloporphyrin Complexes Containing Nitrogen Ligands --- p.19 / Chapter 1.7 --- Bond Activation by Rhodium Porphyrins --- p.21 / Chapter 1.8 --- Objectives of the Work --- p.23 / Chapter Chapter 2 --- Synthesis and Reactivity Studies of Rhodium Porphyrin Amido Complexes --- p.24 / Chapter 2.1 --- Synthesis of Porphyrin and Rhodium Porphyrin Chloride --- p.24 / Chapter 2.2 --- Synthesis of Rhodium Porphyrin Amido Complexes from Rhodium Porphyrin Chloride --- p.24 / Chapter 2.2.1 --- By Transmetallation with Lithium Amide --- p.25 / Chapter 2.2.2 --- By Base-promoted Ligand Substitution Using Rh(ttp)Cl --- p.27 / Chapter 2.2.2.1 --- Optimization of Reaction Conditions --- p.27 / Chapter 2.2.2.2 --- Substrate Scope --- p.31 / Chapter 2.3 --- X-ray Structure of Rh(ttp)NHS02Ph --- p.33 / Chapter 2.4 --- Bond Activation Chemistry of Rh(ttp)NHS02Ph --- p.36 / Chapter 2.5 --- Conclusion --- p.37 / Chapter Chapter 3 --- Reactivity Studies of Rh(ttp)NHS02Ph --- p.39 / Chapter 3.1 --- Thermal Reaction of Rh(ttp)NHS02Ph in Benzene-d6 --- p.39 / Chapter 3.2 --- Mechanistic Studies of the Conversion from Rh(ttp)NHS02Ph to [Rh(ttp)]2 --- p.41 / Chapter 3.2.1 --- Mechansim A (Hydrolysis of Rh(ttp)NHS02Ph) --- p.42 / Chapter 3.2.2 --- Mechanism B (Rh-N Bond Homolysis - (PhS02NH)2 Hydrolysis) --- p.44 / Chapter 3.2.3 --- Mechanism C (Rh-N Bond Homolysis - (PhS02NH)2 Nitrogen-Hydrogen Bond Activation) --- p.45 / Chapter 3.3 --- Discussions --- p.52 / Chapter 3.3.1 --- Estimation of Rhodium-Nitrogen Bond Dissociation Energy --- p.52 / Chapter 3.3.2 --- Effect of Excess PhS02NH2 in the Synthesis of Rh(ttp)NHS02Ph --- p.58 / Chapter 3.4 --- Conclusion --- p.58 / Chapter Chapter 4 --- Experimental Section --- p.60 / References --- p.83 / Appendix I X ray data --- p.90 / Appendix I List of Spectra --- p.96

Discovery of cisplatin as an effective anticancer agent has stimulated the development of metal based medicine. The recent advances in research on platinum, ruthenium and gold complexes have received much attention in medicinal chemistry, and studies of other less explored metal complexes may reveal alternative mode of mechanism as novel therapeutic agents. A series of dirhodium(II,II) complexes with carboxylate and carboxamidate ligands and thiourea complexes of coinage metals have been prepared in this study. Their biological activities and mechanisms of action have been studied. Dirhodium(II,II) carboxylate complexes with variations of alkyl and benzoyl side chains were synthesized and displayed remarkable cytotoxicities to cancer cells with potency down to submicromolar level. The cytotoxicities of rhodium complexes were found to significantly correlate with the cellular uptake of the rhodium complexes. As revealed by oligonucleotide microarray and bioinformatic analysis, the mode of action of the rhodium carboxylate complexes are highly similar to that of a proteasome inhibitor. Further cellular and biochemical studies showed that rhodium carboxylate complexes induced an accumulation of ubiquitinated proteins, inhibited the proteolytic activities of purified 20S proteasome and proteasomal deubiquitinating enzyme. These results corroborate that the impairment of the ubiquitin-proteasome system is linked to the cytotoxic action of rhodium carboxylate complexes. Silver is known to be an anti-inflammatory agent for topical treatment. A silver complex of N, N’-disubstituted cyclic thiourea that is reasonably stable towards reduced glutathionewas found to potently inhibit the NF-B transcriptional activity. Treatment of cells with silver thiourea inhibited TNF-α-stimulated IκB kinase activity, IκBα phosphorylation and degradation, nuclear translocation of NF-κB p65 and eventually the stimulated gene expression of inflammatory cytokines. Suppression of IκB kinase activity was associated with modification of sensitive cysteine residues and disruption of IκB kinase assembly. These data demonstrated that the inhibitory properties of Ag+ ions on an anti-inflammatory and anti-cancer drug target could be effectively delivered via the thiourea ligand. Silver is also an antimicrobial metal, and this study was also extended to understand the silver-bacteria interaction using a silver resistant bacteria as a model. Many silver resistant bacteria often produce considerable amount of silver particles when exposed to high concentrations of silver salts but the mechanism of biosynthesis is not well understood. A silver resistant E. coli that displays active silver efflux was shown to synthesize zero-valent silver nanoparticles in the periplasmic space through reduction of silver ions under anaerobic conditions. As the microbial c-type cytochromes are known to mediate respiratory metal reduction, their role in the biosynthesis of silver nanoparticles was examined. A deletion mutant of the cytoplasmic membrane-anchored tetra-heme c-type cytochrome subunit of periplasmic nitrate reductase (NapC) showed marked reduction of accumulation of silver nanoparticles. This study identified a molecular mechanism of biosynthesis of silver nanoparticles that may have implication in bioenvironmental processes and synthetic biology of metal nanomaterials. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

by Chiu Peng Fai. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references (leaves 82-87). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abbreviations --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Definition of Carbon Hydrogen Bond Activation (CHA) by Transition Metal Comple --- p.1 x / Chapter 1.2 --- The Importance of Alkane CHA and its Potential Use --- p.1 / Chapter 1.3 --- Difficulties in Alkane CHA --- p.3 / Chapter 1.4 --- The Use of Transition Metal Complexes in CHA Reactions --- p.4 / Chapter 1.5 --- Classification of CHA Reactions --- p.6 / Chapter 1.6 --- The Importance of Toluene and Benzene CHA --- p.11 / Chapter 1.7 --- Difficulties and Challenges in CHA of Toluene --- p.11 / Chapter 1.8 --- Selectivity Control and Rate Promotion --- p.12 / Chapter 1.9 --- Structural Features of Rhodium Porphyrins --- p.17 / Chapter 1.10 --- CHA by Rhodium Porphyrins --- p.19 / Chapter 1.11 --- Objective of Work --- p.21 / Chapter Chapter 2 --- CHA Reactions of Toluenes by Rhodium Porphyrin Chlorides / Chapter 2.1 --- Synthesis of Rhodium Porphyrin Chlorides --- p.22 / Chapter 2.2 --- Temperature Effects of CHA in Toluene --- p.22 / Chapter 2.3 --- Inter and Intra Molecular Exchange of Alkyl Rhodium Porphyrin Complexes --- p.24 / Chapter 2.4 --- Electronic Effect of Rhodium Porphyrin Chlorides --- p.24 / Chapter 2.5 --- Electronic Effect of Toluene Towards CHA --- p.25 / Chapter 2.6 --- X-Ray Data --- p.26 / Chapter 2.7 --- Mechanistic Studies --- p.30 / Chapter 2.8 --- Ligand and Base Effects --- p.32 / Chapter 2.9 --- Optimization of Reaction Conditions --- p.35 / Chapter 2.10 --- Electronic Effect of Toluenes --- p.36 / Chapter 2.11 --- Concentraction Effects of Toluenes (Reactions in Benzene) --- p.38 / Chapter 2.12 --- Porphyrin Effects in CHA of Toluene --- p.39 / Chapter 2.13 --- Mechanistic Studies --- p.40 / Chapter 2.14 --- Conclusion --- p.42 / Chapter 2.15 --- Reaction between Rh(ttp)Me and Toluenes --- p.42 / Chapter 2.16 --- Selective Benzylic CHA --- p.42 / Chapter 2.17 --- Isotope Effect --- p.44 / Chapter 2.18 --- Discussion --- p.44 / Chapter 2.19 --- Exploratory Studies of Other Base-Promoted Reactions --- p.45 / Chapter 2.20 --- Benzylic CHA and Aromatic Carbon Halogen Bond Activation (CXA) Reactions --- p.45 / Chapter 2.21 --- Base-Enhanced Aromatic CXA --- p.48 / Chapter 2.22 --- X-Ray Data --- p.49 / Chapter 2.23 --- Base-Enhanced Benzylic Carbon Carbon Bond Activation (CCA) Reactions --- p.51 / Chapter 2.24 --- Summary --- p.52 / Chapter Chapter 3 --- Experimental Sections --- p.53 / References --- p.82 / Appendix I Crystal Data and Processing Parameters --- p.88 / Appendix II List of Spectra --- p.123 / Spectra --- p.125

Lau Cheuk Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2005. / Includes bibliographical references (leaves 93-98). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Structural Abbreviations for Porphyrin Complexes --- p.v / Abstract --- p.vi / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- General Introduction --- p.1 / Chapter 1.2 --- Activation of Carbon-Hydrogen Bond (CHA) by Transition Metal --- p.2 / Chapter 1.2.1 --- Application of CHA by Transition Metals --- p.3 / Chapter 1.2.2 --- Thermodynamic in CHA by Transition Metals --- p.5 / Chapter 1.2.3 --- Types of Carbon-Hydrogen Activations --- p.6 / Chapter 1.3 --- Carbon-Hydrogen Bond Activation of Aldehydes --- p.14 / Chapter 1.3.1 --- Catalytic Application of CHA of Aldehydes by Transition Metals --- p.14 / Chapter 1.3.2 --- Stability of Intermediate M(COR) --- p.15 / Chapter 1.3.3 --- Issue in Selectivity --- p.16 / Chapter 1.4 --- Structural Features of Rhodium Porphyrins --- p.23 / Chapter 1.5 --- Objective of the work --- p.24 / Chapter Chapter 2 --- Carbon-Hydrogen Activation of Aldehydes by Rh(ttp)Cl and Rh(ttp)Me / Chapter 2.1 --- Introduction --- p.26 / Chapter 2.2 --- CHA of Aldehydes by Rh(ttp)Cl --- p.27 / Chapter 2.2.1 --- Preparation of Rh(ttp)Cl --- p.27 / Chapter 2.2.2 --- Solvents Screening --- p.27 / Chapter 2.2.3 --- Results and Discussion --- p.30 / Chapter 2.3 --- CHA of Aldehydes by Rh(ttp)Me --- p.33 / Chapter 2.3.1 --- Preparation of Rh(ttp)Me --- p.34 / Chapter 2.3.2 --- Results and Discussion --- p.35 / Chapter 2.4 --- Mechanistic Studies --- p.37 / Chapter 2.4.1 --- CHA of Aldehydes by Rh(ttp)Cl --- p.37 / Chapter 2.4.2 --- CHA of Aldehydes by Rh(ttp)R --- p.42 / Chapter 2.5 --- Comparison of the u(C=0) --- p.48 / Chapter 2.6 --- X-ray Data --- p.49 / Chapter 2.7 --- Summary --- p.50 / Chapter Chapter 3 --- CHA of Aldehydes by Rh(ttp)CH2CH2OH and Rh(ttp)+X- / Chapter 3.1 --- Introduction --- p.52 / Chapter 3.2 --- CHA of Aldehydes by Rh(ttp)CH2CH2OH --- p.53 / Chapter 3.2.1 --- Results and Discussion --- p.53 / Chapter 3.2.2 --- Mechanistic Studies --- p.61 / Chapter 3.3 --- CHA of Aldehydes by Rh(ttp)+X- --- p.65 / Chapter 3.4 --- Summary --- p.67 / Conclusion --- p.68 / Experimental --- p.69 / Reference --- p.93 / Appendix I Crystal Data and Processing Parameters --- p.99 / List of Spectra --- p.141 / Spectra --- p.143

Base-promoted CHA of unstrained alkanes with 5,10,15,20-tetratolylporphyrinatorhodium complexes, Rh(ttp)X (X = Cl, H, Rh(ttp)), has been achieved. Rh(ttp)Cl, reacted with n-pentane, n-hexane, n-heptane, c-pentane and c-hexane in the presence of potassium carbonate at 120 °C in 6 to 24 h to give rhodium porphyrin alkyls, Rh(ttp)R, in 29--76% yields. Mechanistic investigations suggested that Rh 2(ttp)2 and Rh(ttp)H are key intermediates for the parallel CHA step. The roles of base are (i) to facilitate the formation of Rh(ttp)Y (Y- = OH-, KCO3 -), (ii) to enhance the CHA rate with alkane and generate Rh(ttp)H by a Rh(ttp)Y species which is more reactive than Rh(ttp)Cl, and (iii) to provide a parallel CHA pathway by Rh2(ttp)2. / c-Octane reacted with Rh(ttp)Cl at 120 °C in 7.5 h in the presence of K2CO3 to yield Rh(ttp)( n-octyl) and Rh(ttp)H in 33% and 58% yields, respectively. Mechanistic investigations indicate that the CCA product is generated from the Rh II(ttp)-catalyzed 1,2-addition of c-octane with Rh(ttp)H. Reaction of c-octane and Rh(ttp)H/Rh2(ttp) 2 (10:1) selectively yielded Rh(ttp)(n-octyl) in 73% at 120 °C in 15 h. The catalyst RhII(ttp) radical cleaves the C-C bond of c-octane to form to a Rh(ttp)-alkyl radical, which then abstracts a hydrogen atom from Rh(ttp)H to generate the Rh(ttp)( n-octyl), and subsequently leading to regeneration of the Rh II(ttp) radical. (Abstract shortened by UMI.) / K2CO3-promoted CHA of the ring-strained cycloheptane with Rh(ttp)Cl at 120 °C in 6 h gave the CHA product Rh(ttp)( c-heptyl) and together with, unexpectedly, the CCA product Rh(ttp)Bn, in 30% and 24% yields, respectively. Mechanistic studies revealed that Rh(ttp)( c-heptyl) undergoes beta-hydride elimination in neutral condition or beta-proton elimination in basic condition followed by reprotonation to give rhodium(III) porphyrin hydride, Rh(ttp)H, and c-heptene. Successive base-promoted CHA of c-heptene with Rh(ttp)H, followed by beta-proton elimination, generates cycloheptatriene. The CHA of cycloheptatriene with Rh(ttp)H formed Rh(ttp)(c-heptatrienyl), which underwent rearrangement with carbon-carbon cleavage at 120 °C in 16 d to yield Rh(ttp)Bn in 96% yield. / The objectives of this research focus on the investigation of carbon-hydrogen bond activation (CHA) and carbon-carbon bond activation (CCA) of alkanes by rhodium porphyrin complexes as well as the mechanistic understanding. / Chan, Yun Wai. / Adviser: Kin Shing Chan. / Source: Dissertation Abstracts International, Volume: 73-02, 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, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

by Fung Chun-wah. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references (leaves 117-119). / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.v / Abbreviations --- p.vi / Abstract --- p.vii / Chapter PART I: --- ACTIVATION OF CARBON-CARBON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL / Chapter CHAPTER 1 --- General Introduction --- p.1 / Chapter 1.1.1 --- Activation of Carbon-Carbon Bond (CCA) by Transitional Metals --- p.1 / Chapter 1.1.1.1 --- Potential Application of C-C Bond Activation --- p.1 / Chapter 1.1.1.1.1 --- Cracking --- p.1 / Chapter 1.1.1.1.2 --- Depolymerization --- p.2 / Chapter 1.1.1.2 --- Thermodynamic and Kinetic Considerations in CCA --- p.3 / Chapter 1.1.1.3 --- C-C Bond Activation in Strained System --- p.3 / Chapter 1.1.1.4 --- C-C Bond Activation facilitated by Aromatization --- p.7 / Chapter 1.1.1.5 --- C-C Bond Activation of Carbonyl Compounds --- p.9 / Chapter 1.1.1.6 --- C-C Bond Activation of the Nitriles --- p.13 / Chapter 1.1.1.7 --- Selective C-C Bond Activation on a Multimetallic Site --- p.16 / Chapter 1.1.1.8 --- Intramolecular sp2 -sp3 C-C Bond Activation in PCP System --- p.17 / Chapter 1.1.1.9 --- CCA in N-Heterocyclic Carbene --- p.18 / Chapter 1.1.1.10 --- CCA in Pt(0) complexes bearing Chelating P´ةN- and P´ةP- Ligands --- p.19 / Chapter 1. 1.1.11 --- CCA of Alkyne via Hydroiminoacylation by Rh(I) Catalyst --- p.20 / Chapter I. 1.1.12 --- CCA in Homoallylic Alcohol by β-Allyl Elimination --- p.21 / Chapter I. 1.1.13 --- C-C Bond Activation by Metathesis of Alkanes --- p.23 / Chapter I.1.2 --- Structural Features of Rhodium Porphyrins --- p.25 / Chapter I.1.3 --- Objective of the Work --- p.27 / Chapter CHAPTER 2 --- Carbon-Carbon Bond Activation (CCA) of Nitriles by Rhodium Porphyrin Radical --- p.28 / Chapter I.2.1 --- Introduction --- p.28 / Chapter I.2.1.1 --- CCA of Nitroxides by Rhodium(II) Porphyrin Radical Rh(por) --- p.28 / Chapter I.2.2 --- CCA of Nitriles by Rh(tmp) Radical --- p.29 / Chapter I.2.2.1 --- Synthesis of Rh(tmp)Me --- p.29 / Chapter I.2.2.2 --- Synthesis of Rh(tmp) Radical --- p.30 / Chapter I.2.2.3 --- Ligand effect on CCA --- p.31 / Chapter I.2.2.3.1 --- Synthesis of Phosphines --- p.31 / Chapter I.2.2.3.2 --- Reactions between Rh(tmp) and Phosphines --- p.32 / Chapter I.2.2.3.3 --- Synthesis of Alkyl Rh(tmp) --- p.35 / Chapter I.2.2.4 --- CCA of Nitriles by Rh(tmp) with PPh3 added --- p.36 / Chapter I.2.2.4.1 --- Synthesis of Nitrile --- p.36 / Chapter I.2.2.4.2 --- Reactions between Rh(tmp) and Nitriles --- p.37 / Chapter I.2.3.4 --- Proposed Mechanism of CCA --- p.44 / Chapter CHAPTER 3 --- Experimental Section --- p.46 / Conclusion --- p.63 / References --- p.64 / Chapter PART II --- ACTIVATION OF CARBON-SILICON BONDS OF NITRILES BY RHODIUM PORPHYRIN RADICAL --- p.71 / Chapter CHAPTER 1 --- General Introduction --- p.71 / Chapter II. 1.1 --- Carbon-Silicon Bond Activation by Transitional Metals --- p.71 / Chapter II. 1.1.1 --- Potential Application of C-Si Bond Activation --- p.72 / Chapter II.l. l.2 --- C(sp3)-Si Bond Activation --- p.73 / Chapter II. 1.1.2.1 --- Intermolecular C(sp3)-Si Bond Activation in Strained System --- p.73 / Chapter II. 1.1.2.2 --- Intermolecular C(sp3)-Si Bond Activation in Unstrained System --- p.76 / Chapter II. 1.1.3 --- C(sp2)-Si Bond Activation --- p.78 / Chapter II. 1.1.3.1 --- Intermolecular C(aryl)-Si Bond Activation --- p.78 / Chapter II. 1.1.3.2 --- Intramolecular C(aryl)-Si Bond Activation --- p.84 / Chapter II. 1.1.3.3 --- C(vinyl)-Si Bond Activation --- p.87 / Chapter II. 1.1.4 --- C(sp)-Si Bond Activation --- p.89 / Chapter II. 1.2 --- Objective of the Work --- p.92 / Chapter CHAPTER 2 --- Carbon-Silicon Bond Activation (CSA) of Nitriles --- p.93 / Chapter II.2.1 --- Introduction --- p.93 / Chapter II.2.2 --- Reactions between Rh(tmp) Radical and Silylnitriles --- p.93 / Chapter II.2.2.1 --- Investigation the CSA of Trimethylsilylcyanide by Rh(tmp) --- p.93 / Chapter II.2.2.1.1 --- Synthesis of Rh(tmp)SiMe3 --- p.93 / Chapter II.2.2.1.2 --- Synthesis of Rh(tmp)CN --- p.94 / Chapter II.2.2.1.3 --- Reactions between Rh(tmp) and Trimethylsilylcyanide --- p.95 / Chapter II.2.2.1.4 --- Ligands effect on CSA of Trimethylsilylcyanide by Rh(tmp) --- p.98 / Chapter II.2.2.1.5 --- Temperature effect on CSA --- p.101 / Chapter II.2.2.2 --- Reactions between Rh(tmp) and other Silylnitriles --- p.102 / Chapter II.2.3 --- Mechanism of CSA of Trimethylsilylcyanide --- p.103 / Chapter II.2.3.1 --- Proposed Mechanism of CSA of Trimethylsilylcyanide by Rh(tmp) --- p.104 / Chapter II.2.4 --- A Comparison of CSA and CCA of Nitriles --- p.105 / Chapter CHAPTER 3 --- Experimental Section --- p.107 / Conclusion --- p.116 / References --- p.117 / List of Spectra --- p.120 / Spectra --- p.121