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Synthesis and reactivity study of rhodium porphyrin amido complexes.

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

Identiferoai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_327259
Date January 2010
ContributorsAu, Ching Chi., Chinese University of Hong Kong Graduate School. Division of Chemistry.
Source SetsThe Chinese University of Hong Kong
LanguageEnglish, Chinese
Detected LanguageEnglish
TypeText, bibliography
Formatprint, vi, 100 leaves : ill. ; 30 cm.
RightsUse of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/)

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