No description available.

M.Sc. / Since the discovery of Ni(CO)4 by Mond in 1890, many chemists became interested in organometallic chemistry. This field of research expanded after the synthesis of ferrocene in 1951. organometallic complexes are widely used in organic synthesis, especially as catalysts ...

by Chi-Shing Chan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1993. / Includes bibliographical references (leaves 62-65). / Acknowledgements --- p.i / Contents --- p.ii / Abbreviations --- p.iii / Abstract --- p.1 / Introduction --- p.2-8 / Synthetic Strategy --- p.9-12 / Results and Discussion / Chapter A. --- Synthesis of the aryl triflate substituted and aryl bromide substituted porphyrins --- p.13-15 / Chapter B. --- Synthesis of the (alkynyl)phenyl substituted porphyrins --- p.16-19 / Chapter C --- Benzannulation of Fischer carbene complexes with (alkynyl)phenyl substituted porphyrins --- p.20-23 / Chapter D. --- "Palladium-catalysed cross coupling reaction of 2,5-dimethoxyphenyl boronic acid with aryl triflate or aryl bromide substituted porphyrins" --- p.24-28 / Chapter E. --- Synthesis of the meso-tetrakis(benzoquinonyl) porphyrin --- p.29 / Chapter F. --- Metalation of the quinone-linked porphyrins --- p.30 / Chapter G. --- Preliminary study on the electrocatalytic activity of the quinone-linked metalloporphyrin complexes of cobalt and palladium for the electrochemical reduction of carbon dioxide --- p.31 / Conclusion --- p.32 / Experimental --- p.33-61 / References --- p.62-65 / List of spectra / Porphyrin aryl triflate4 --- p.66 / (Alkynyl)phenyl porphyrin 9 d --- p.67 / Tetra(quinonyl)phenyl porphyrin 12a --- p.68 / (Naphthoquinonyl)phenyl porphyrin 13b --- p.69 / "2,5 -dimethoxyphenyl boronic acid 16" --- p.70 / (Benzoquinonyl)phenyl porphyrin19 --- p.71 / Tetra(quinonyl)phenyl porphyrin 23 --- p.72

Peng Yu. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.iv / Abstract --- p.v / Abbreviations --- p.ix / Chapter CHAPTER 1. --- METALLATION OF AMINOPYRIDINE AND AMINOQUINOLINE / Chapter 1.1 --- INTRODUCTION / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- Synthesis of Metal Amides --- p.2 / Chapter 1.1.3 --- General Review of Lithium Amido Complexes --- p.4 / Chapter 1.1.4 --- Structures of Some Potassium and Sodium Amido Complexes --- p.8 / Chapter 1.1.5 --- A Brief Review of TV-functionalized Amido Metal Complexes --- p.9 / Chapter 1.1.6 --- Objective of This Work --- p.13 / Chapter 1.2 --- RESULTS AND DISCUSSION / Chapter 1.2.1 --- Synthesis of N-functionalized Amido Ligands --- p.14 / Chapter 1.2.2 --- Lithiation of Aminopyridine --- p.15 / Chapter 1.2.3 --- Lithiation of Aminoquinoline --- p.17 / Chapter 1.2.4 --- Attempted Synthesis of Sodium Amido Complexes --- p.19 / Chapter 1.2.5 --- Attempted Synthesis of Potassium Amido Complexes --- p.19 / Chapter 1.2.6 --- Physical Characterizations of and Compounds 1-10 --- p.20 / Chapter 1.2.7 --- "Molecular Structures of Compounds 3，4, 7, 8, and10" --- p.24 / Chapter 1.3 --- EXPERIMENTALS FOR CHAPTER 1 --- p.37 / Chapter 1.4 --- REFERENCES FOR CHAPTER 1 --- p.44 / Chapter CHAPTER 2. --- SYNTHESIS AND STRUCTURES OF GROUP12 AMIDO COMPLEXES / Chapter 2.1 --- INTRODUCTION / Chapter 2.1.1 --- General Review of Zinc(II) Amido Complexes --- p.49 / Chapter 2.1.2 --- General Review of Cadmium(II) Amido Complexes --- p.53 / Chapter 2.1.3 --- General Review of Mercury(II) Amido Complexes --- p.56 / Chapter 2.2 --- RESULTS AND DISCUSSION / Chapter 2.2.1 --- Synthesis of Homoleptic Zinc(II) Amido Complexes --- p.58 / Chapter 2.2.2 --- Attempted Reaction of Compounds [Zn(L1)2] and [Zn(L3)2] (11) with ArSH and S --- p.59 / Chapter 2.2.3 --- Attempted Reaction of [Zn(L1)Cl] with ArSLi and ArMe OLi --- p.59 / Chapter 2.2.4 --- Synthesis of Cadmium(II) Amido Complexes --- p.61 / Chapter 2.2.5 --- "Attempted Reaction of [{Cd(L3)2}2(tmeda)] (16) with S， Se, and ArSH" --- p.63 / Chapter 2.2.6 --- "Attempted Reaction of [Cd(L3)2] (15) with 4,4'- bipyridine" --- p.64 / Chapter 2.2.7 --- Synthesis of Mercury(II) Amido Complexes --- p.65 / Chapter 2.2.8 --- "Reaction of [Hg(L3)2] (21) with S, Se, and ArSH " --- p.67 / Chapter 2.2.9 --- Physical Characterizations of Compounds 11-23 --- p.68 / Chapter 2.2.10 --- "Molecular Structures of Compounds 11, 13, 16, and 21" --- p.73 / Chapter 2.3 --- EXPERIMENTALS FOR CHAPTER 2 --- p.84 / Chapter 2.4 --- REFERENCES FOR CHAPTER 2 --- p.94 / Chapter CHAPTER 3. --- SYNTHESIS AND STRUCTURES OF COPPER AND SILVER(I) AMIDO COMPLEXES / Chapter 3.1 --- INTRODUCTION / Chapter 3.1.1 --- Overview of Transition Metal Amides --- p.99 / Chapter 3.1.2 --- General Review of Copper Amido Complexes --- p.101 / Chapter 3.1.3 --- General Review of Silver(I) Amido Complexes and their Derivatives --- p.105 / Chapter 3.2 --- RESULTS AND DISCUSSION / Chapter 3.2.1 --- Synthesis of Homoleptic Copper(I) Amido Complexes --- p.108 / Chapter 3.2.2 --- Reaction of [{Cu(L3)}2] (24) with ArSH and Dioxygen --- p.110 / Chapter 3.2.3 --- Synthesis of Homoleptic Copper(II) Amido Complexes --- p.111 / Chapter 3.2.4 --- Attempted Reaction of CuCl2 with [{Li(L4)}3] (8) --- p.112 / Chapter 3.2.5 --- Attempted Reaction of [Cu(L3)2] (24) with ArSH --- p.112 / Chapter 3.2.6 --- Synthesis of Silver(I) Amido Complexes --- p.113 / Chapter 3.2.7 --- Attempted Reaction of AgN03 with [{Li(L4)}3] (8) --- p.114 / Chapter 3.2.8 --- Physical Characterizations of Compounds 24-29 --- p.115 / Chapter 3.2.9 --- "Molecular Structures of Compounds 24, 25, 26, and28" --- p.119 / Chapter 3.3 --- EXPERIMENTALS FOR CHAPTER 3 --- p.131 / Chapter 3.4 --- REFERENCES FOR CHAPTER 3 --- p.138 / Chapter CHAPTER 4. --- SYNTHESIS AND STRUCTURES OF NICKEL(II) AMIDO COMPLEXES / Chapter 4.1 --- INTRODUCTION / Chapter 4.1.1 --- General Review of Nickel Derivatives --- p.139 / Chapter 4.2 --- RESULTS AND DISCUSSION / Chapter 4.2.1 --- Synthesis of Homoleptic Nickel(II) Amido Complexes --- p.144 / Chapter 4.2.2 --- Attempted Reaction of NiCl2 with [Li(L3)(tmeda)] (3) --- p.145 / Chapter 4.2.3 --- Physical Characterizations of Compounds 30-32 --- p.145 / Chapter 4.2.4 --- Molecular Structures of Compounds 31 and 32 --- p.147 / Chapter 4.3 --- EXPERIMENTALS FOR CHAPTER 4 --- p.153 / Chapter 4.4 --- REFERENCES FOR CHAPTER 4 --- p.155 / Chapter APPENDIX 1 --- General Procedures and Physical Measurements --- p.157 / Chapter APPENDIX 2 --- "Table A-1. Selected Crystallographic Data for Compounds 3, 4, 7, and 8" --- p.160 / "Table A-2. Selected Crystallographic Data for Compounds 10, 11, 13，and 16" --- p.161 / "Table A-3. Selected Crystallographic Data for Compounds 21, 24, 25, and 26" --- p.162 / "Table A-4. Selected Crystallographic Data for Compounds 28，31, and 32" --- p.163

Cheuk Wai So. / "June 2003." / Thesis (Ph.D.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references. / 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. / Abstracts in English and Chinese.

No description available.

This thesis describes the synthesis and properties of some extended donor-acceptor dyads with the donor being a ferrocenyl moiety and a fluorescent naphthalimide group as the acceptor. Two series of extended ferrocenyl-naphthalimide dyads were prepared in reasonable yield depending on the synthetic route. The first are a series of three ferrocenyl-CH=CH-spacer-C[triple bond]C-naphthalimide dyads in which the spacers are phenyl, biphenyl and anthryl and the second are a series of three ferrocenyl-C[triple bond]C-spacer-C[triple bond]C-naphthalimide dyads in which the spacers are 2,2� -bithiophene, 2,5-dimethoxybenzene and tetrafluorobenzene groups. The molecular structures of some compounds have been determined by X-ray diffraction although with many challenges because of the extensive [pi]-[pi] stacking of molecules that leads to ready aggregation in the solid state, particularly for the ferrocenyl-CH=CH-spacer-C[triple bond]C-naphthalimide dyads, in which the naphthalimide bears a methyl head group. In order to reduce the [pi]-[pi] stacking effect between the molecules and also to produce chiral molecules for the potential nonlinear optical applications, a chiral α-methylbenzylamine was introduced as the head group of naphthalimide for the ferrocenyl-C[triple bond]C-spacer-C[triple bond]C-naphthalimide dyads. The resulting comounds successfully gave crystals of sufficient quality for X-ray structural investigation. While the oxidative electrochemistry of the ferrocenyl compound in the two series of dyads was largely predictable (E� ~ 0.55 V for ferrocenyl-CH=CH- and ~ 0.72 V for ferrocenyl-C[triple bond]C-), the presence of spacers in the dyads appeared to afford stability to the reduced naphthalimide species. This was exhibited by the appearance of chemically reversible one-electron reduction processes for each of the compounds investigated. Similar unusual chemical reversibility was also shown by the spacer-C[triple bond]C-naphthalimide precursor systems. For the ferrocenyl-CH=CH-spacer-C[triple bond]C-naphthalimide dyads, the oxidation and reduction potentials closely resembled those of the simple ferrocenyl-CH=CH-spacer systems. This suggested that augmentation of the simple ferrocenyl-CH=CH-phenyl, -biphenyl and -anthryl systems with an alkyne linked naphthalimide unit showed little influence on the oxidation of the ferrocenyl moiety or the reduction of the naphthalimide unit. However, for the ferrocenyl-C[triple bond]C-spacer-C[triple bond]C-naphthalimide dyads, the oxidation and reduction potentials are influenced by the inductive effects of the spacers. While an anodic shift was observed for the dyad with the electron-withdrawing spacer tetrafluorobenzene, a cathodic shift was displayed for the dyads with the electron-donating spacers 2,2�-bithiophene and 2,5-dimethoxybenzene compared to that in the simple ferrocenyl-C[triple bond]C-naphthalimide system. The spectroscopic properties of the ferrocenyl-CH=CH-spacer-C[triple bond]C-naphthalimide dyads showed that interpolation of the aromatic spacers does not interfere with the internal charge separation. Oxidation of the ferrocenyl moiety resulted in bleaching of the metal-to-ligand charge transfer band at ~ 500 nm and the growth of a new band in the near infrared region at ~ 1000 nm. This new band can be assigned to a ligand-to-metal charge transfer transition, where the ferrocenium now acts as an acceptor to the naphthalimide donor. For the ferrocenyl-C[triple bond]C-spacer-C[triple bond]C-naphthalimide dyads, the spectroscopic properties showed that the mutually electron-withdrawing tetrafluorobenzene and naphthalimide units had little interaction despite their connection by a conductive alkyne link. In contrast, the dyads containing the electron-donating 2,2�-bithiophene and 2,5-dimethoxybenzene showed some degree of interaction between the spacer and the naphthalimide fragments. This was evidenced by the appearance of a broad absorption band in the range 410 - 440 nm, which is associated with an orbital that is delocalised between the spacer and the naphthalimide fragments. Again, the roles of donor and acceptor were reversed on oxidation of the ferrocenyl moiety. This resulted in the growth of a new near infrared band at ~750 mn for the dyad containing the tetrafluorobenzene spacer and at ~ 1000 nm for the dyads with 2,2�-bithiophene and 2,5 -dimethoxybenzene spacers. The ferrocenyl unit went from being a net donor to ferrocenium, which was acting as an acceptor, with the tetrafluorobenzene spacer adopting the donor role more reluctantly than the delocalised 2,2�-bithiophene-C[triple bond]C-naphthalimide and 2,5-dimethoxybenzene-C[triple bond]C-naphthalimide moieties. 1,3,5-Tri- and 1,2,4,5-tetra-substituted benzene cores were also used as spacers for the preparation of extended arrays of ferrocenyl-naphthalimide dyads. Utilisation of the 1,3,5 -tri-substituted benzene core enabled the core to be embellished in three directions, resulting in Y-motif extended arrays containing either one ferrocenyl unit [(ethenylferrocenyl)-C₆H₃-(C[triple bond]C-C₆H₅)₂] or one naphthalimide moiety [(4-piperidino-N-propargyl-naphthalimide)-C₆H₃-(Br)₂]. With the 1,2,4,5-tetra-substituted benzene core, the extension of the core was possible in four directions and gave extended arrays in an X-motif. Again, these systems contained either ferrocenyl units [bis(alkoxyferrocenyl)-C₆H₂-(C[triple bond]C-C₆H₅)₂] or naphthalimide moieties [(tetrakis-naphthalimide)-C₆H₂]. Attempts to incorporate both ferrocenyl and naphthalimide fragments into the X- or Y-motif extended arrays were unsuccessful. By adding C₂Co₂(CO)₆dppm across the triple bonds of two of the four alkyne groups in the X-motif naphthalimide system [(tetrakis-naphthalimide)-C₆H₂], it was possible to incorporate two oxidisable C₂Co₂(CO)₄dppm cluster units into the molecule. The electrochemistry of the resulting system showed two discrete oxidation processes, suggesting the possibility of some interaction between the dicobalt cluster redox centres.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references. Available also from UMI/Dissertation Abstracts International.

Thesis (Ph. D.)--University of Texas at Austin, 2002. / Vita. Includes bibliographical references.

Includes bibliographical references.