Lam Chun Pong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.v / Abstracts --- p.vi / Abbreviations --- p.viii / Chapter CHAPTER 1. --- SYNTHESIS AND REACTIVITY STUDIES OF MODEL COMPLEXES FOR INTRADIOL DIOXYGENASES WITH BENZIMIDAZOLE- CONTAINING LIGAND / Chapter I.1 --- Introduction / Chapter I.1.1 --- General Background --- p.1 / Chapter I.1.2 --- A General Review on the Modeling Chemistry for Catechol Dioxygenases --- p.3 / Chapter I.1.3 --- Intradiol Dioxygenases --- p.3 / Chapter I.1.3.1 --- Early model studies for intradiol dioxygenases --- p.5 / Chapter I.1.3.2 --- Factors affecting enzymatic reactivity for intradiol dioxygenases --- p.6 / Chapter I.1.3.3 --- Other functional models for intradiol dioxygenases --- p.7 / Chapter I.1.3.4 --- Reactivity studies of model complexes --- p.8 / Chapter I.1.4 --- Extradiol Dioxygenases --- p.8 / Chapter I.1.4.1 --- Early model studies for extradiol dioxygenases --- p.11 / Chapter I.1.4.2 --- Iron(III) complexes with extradiol properties --- p.12 / Chapter I.1.5 --- Objective of This Work --- p.14 / Chapter I.2 --- Results and Discussion / Chapter I.2.1 --- Synthesis of the Ligand Ntb --- p.15 / Chapter I.2.2 --- Synthesis of the Model Complex [Fe(ntb)Cl2]Cl --- p.16 / Chapter I.2.3 --- Synthesis of Enzyme-Substrate Model Complexes --- p.16 / Chapter I.2.4 --- Oxygenation Reactivities of Enzyme-Substrate Model Complexes 2-4 --- p.18 / Chapter I.2.4.1 --- Oxygenation of [Fe(ntb)(dbc)](C104) (2) in DMF --- p.18 / Chapter I.2.4.2 --- Oxygenation of [Fe(ntb)(cat)](Cl04) (3) in DMF --- p.21 / Chapter I.2.4.3 --- Oxygenation of [Fe(ntb)(tcc)](ClO4) (4) in DMF --- p.23 / Chapter I.2.4.4 --- Comparison of the oxygenation reactivities of complexes2-4 --- p.25 / Chapter I.2.5 --- Identification of Oxidative Cleavage Products --- p.27 / Chapter I.2.5.1 --- Isolation of oxidative cleavage products of complex 2 --- p.27 / Chapter I.2.5.2 --- Identification of cleavage products --- p.27 / Chapter I.2.6 --- Physical Characterization of Complexes 1-4 --- p.29 / Chapter I.2.6.1 --- Melting-points --- p.29 / Chapter I.2.6.2 --- Cyclic Voltammograms --- p.30 / Chapter I.2.6.3 --- EPR spectra --- p.31 / Chapter I.2.7 --- Molecular Structures of Complexes 1-4 --- p.34 / Chapter I.2.7.1 --- Molecular structure of [Fe(ntb)Cl2]Cl-4H20 (1) --- p.34 / Chapter I.2.7.2 --- Molecular structure of [Fe(ntb)(dbc)](Cl04)-2Me0H-H20 (2) --- p.36 / Chapter I.2.7.3 --- Molecular structure of [Fe(ntb)(cat)](ClO4) H20 (3) --- p.38 / Chapter I.2.7.4 --- Molecular structure of [Fe(ntb)(tcc)](Cl04).Me2C(0).H20 (4) --- p.41 / Chapter I.2.7.5 --- Comparison of the molecular structures of complexes 1-4 --- p.43 / Chapter I.3 --- Experimentals for Chapter 1 --- p.45 / Chapter I.4 --- References for Chapter 1 --- p.49 / Chapter CHAPTER II --- iron(iii) complexes containing N202 and N3O type ligands as models for INTRADIOL DIOXYGENASES / Chapter II.1 --- Introduction / Chapter II.1.1 --- Brief Remarks on Model Studies of Intradiol Dioxygenases. --- p.53 / Chapter II.1.2 --- Objective of This Work --- p.53 / Chapter II.2 --- Results and Discussion / Chapter II.2.1 --- Synthesis of N202 and N30 Type Ligands --- p.55 / Chapter II.2.2 --- Synthesis of Model Complexes --- p.57 / Chapter II.2.2.1 --- Model complex with ligand L1H --- p.57 / Chapter II.2.2.2 --- Model complex with ligand L2H2 --- p.58 / Chapter II.2.3 --- Synthesis of Enzyme-Substrate Model Complexes --- p.59 / Chapter II.2.3.1 --- Synthesis of enzyme-substrate model complexes from 14.… --- p.59 / Chapter II.2.3.2 --- Attempted synthesis of enzyme-substrate model complexes starting from 15 --- p.61 / Chapter II.2.4 --- Reaction of Complex 16 with Dioxygen --- p.61 / Chapter II.2.4.1 --- Oxygenation of [Fe(L1)(dbc)] (16) in DMF --- p.65 / Chapter II.2.5 --- Identification of Oxidative Cleavage Products --- p.64 / Chapter II.2.5.1 --- Isolation of oxidative cleavage products of complex 16 --- p.64 / Chapter II.2.5.2 --- Identification of cleavage products --- p.65 / Chapter II.2.6 --- "Physical Characterization of L1H, L2H2, Complexes 14-18" --- p.66 / Chapter II.2.6.1 --- NMR spectra --- p.67 / Chapter II.2.6.2 --- Melting-points --- p.69 / Chapter II.2.6.3 --- Mass spectra --- p.69 / Chapter II.2.6.4 --- Cyclic voltammogram --- p.69 / Chapter II.2.6.4 --- EPR spectra --- p.70 / Chapter II.2.7 --- "Molecular Structures of Complexes 14,15 and 18" --- p.71 / Chapter II.2.7.1 --- Molecular structure of [Fe(L1)(MeOH)Cl][BPh4].MeOH (14) --- p.72 / Chapter II.2.7.2 --- Molecular structure of [Fe(L2)Cl].MeOH (15) --- p.75 / Chapter II.2.7.3 --- Molecular structure of [Et3 Nh]3［Fe(tcc)3］.H2O(18) --- p.78 / Chapter II.3 --- Experimentals for Chapter 2 --- p.80 / Chapter II.4 --- References for Chapter 2 --- p.87 / APPENDIX 1 General Procedures and Physical Measurements --- p.89 / "APPENDIX 2 Selected Crystallographic Data for Complexes 1-4, 15,16 and 18.…" --- p.90 / Table A-l.Selected crystallographic data for complexes 1-4 --- p.91 / "Table A-2.Selected crystallographic data for complexes 15, 16 and 18" --- p.92 / "APPENDIX 3 Other Physical Data for Ligand L1H L2H2, Complexes 2 and 16" --- p.93 / Figure A-l.1H NMR spectrum of ligand L1H --- p.94 / Figure A-2.13C NMR spectrum of ligand L1H --- p.94 / Figure A-3.1H NMR spectrum of ligand L2H2 --- p.95 / Figure A-4.13C NMR spectrum of ligand L2H2 --- p.95 / Figure A-5.GC spectrum of the oxidative cleavage products of complex 2 --- p.96 / Figure A-6.- A-l 1.Mass spectra of the oxidative cleavage products of Complex 2 --- p.96 / Figure A-12.GC spectrum of the oxidative cleavage products of complex 16 --- p.99 / Figure A-13.- A-23.Mass spectra of the oxidative cleavage products of Complex 16 --- p.99 / Figure A-24.GC spectrum of dbcH2 standard --- p.105 / Figure A-25.Mass spectrum of dbcH2 standard --- p.106 / Figure A-26.GC spectrum of dbcq standard --- p.106 / Figure A-27.Mass spectrum of dbcq standard --- p.107
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_323576 |
| Date | January 2001 |
| Contributors | Lam, Chun Pong., Chinese University of Hong Kong Graduate School. Division of Environmental Science. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, bibliography |
| Format | print, ix, 107 leaves : ill. ; 30 cm. |
| Rights | Use 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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