Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 154-166).

Thesis (M. Sc.)--University of Canterbury, 2009. / Typescript (photocopy). "March 2009." Includes bibliographical references (leaves 92-94). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Washington, 1996. / Vita. Includes bibliographical references (leaves [165]-173).

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2007. / Includes bibliographical references. Also available in electronic version.

M.Sc. / The increasing number of individuals living with the HIV virus and the extensive use of antimicrobial medicines has resulted in an increase in opportunistic infections such as tuberculosis, pneumonia, fungal, and viral diseases. In addiction, the drugs currently in use have short comings such as limited efficacy, cell membrane penetration and side effects. The increasing number of opportunistic infections such as systemic fungal infections and the development of resistance to commonly used drugs have prompted the search for answers by producing new and novel ones. Dithiocarbamates (DTCs) have been a subject of major research in the past decade and a number of these compounds have been prepared. Dithiocarbamates are versatile 1,1-dithiolato ligands with broad pharmacological properties. Coordinating these ligands with metals such as copper and nickel may produce compounds with enhanced biological properties and this can be a basis for novel compounds. On the other hand, triphenylphosphine (PPh3) is a good binding ligand for transition metals. Further functionalization of the DTC metal complexes with triphenylphosphine should produce compounds with potential pharmaceutical applications. In this study, several bioactive starting compounds such as indole, imidazole, cyclopentylamine and cyclohexylamine were used to synthesize DTC ligands and their metal complexes of Ni, Co, Cu and Zn. The ligands were obtained in good yields of 55-87% with the complexes in yields of 35-66%. Triphenylphosphine adducts of the DTC metal complexes were also prepared and the yields obtained were between 35-71%. All the prepared complexes and ligands were characterized by Infrared, UV-Vis spectroscopy and NMR (1H, 13C and 31P) spectroscopy.

Due to the ever increasing necessity to reduce our dependence on fossil fuels as feedstocks for polymeric materials, the work presented herein describes the investigation of new metal complexes as initiators for the formation of polyesters and polycarbonates from renewable monomers. These polymers are regarded as biodegradable and have the properties required to replace traditional plastics in applications such as food packaging, electronic devices, and medical biomaterials. Chapter one introduces previous literature relevant to the research on which this study focuses; ligands based on alkoxides, phosphine oxides and N-heterocyclic carbenes with alkoxide or amino pendant groups, as well as the metal complexes in which they are used. Current methods of polymerisation and copolymerisation and the initiators utilised are also examined. Chapter two contains the design and synthesis of [M(LR n)]m metal complexes where LR is [(R)2P(O)CH2CH(tBu)O]– and R is Ph or tBu. Divalent metal centres such as CoII and ZnII have been used for the formation of the studied compounds. Studies on their reactivity as initiators for polymerisations are also described. Chapter three presents the utilisation of di- and tridentate ligands, with one or two NHC species respectively, for the synthesis of [Mx(LY n)], where M is CuI, ZnII or TiIII and LY is an alkoxy-tethered NHC species or a ‘CNC’ tridentate ligands with an amino derivative as bridge. Their reactivity and ability to act as initiators for polymerisation reactions was also examined. Chapter four comprises overall conclusions of this work and the impact of these investigations. Chapter five outlines the experimental details and data for the compounds presented.

published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

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