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We have established novel, aqueous 'Click' chemistry that is based on the thiophosphoryl group. Two systems for the creation of thiophosphoryl derivatives were involved: Thiophosphoramidate I and Bromoacetyl II. The first step in the Thiophosphoramidate system is our aqueous thiophosphorylation of amines using thiophosphoryl chloride. Through careful control of reaction conditions we have devised a method that allows us to prepare and alkylate the thiophosphoramidate group in aqueous media with high conversions, and thus provide a fast, clean and straightforward route to a number of products. The thiophosphoramidate system was, then, successfully applied towards the production of nucleoside monothiophosphoramidates. In addition, a number of quinoline-based thiophosphoramidates were generated as potential antileishmanials and in vivo assays were performed against Leishmania mexicana. The bromoacetyl system uses thiophosphorylated alcohols that we alkylated with a range of activated bromoacetate esters. Hydrolysis and aminolysis kinetic studies were employed on this system for a better understanding of the conditions required for facile production of amides on these thiophosphoryl acetate esters in water. Finally, we have combined the achievements from these two systems into the thiophosphoramidate-romoacetyl strategy III, expanding the scope for generating thiophosphoryl derivatives.

A review of the various means of catalyst immobilisation available to chemists is presented with particular emphasis on the areas of supported- and fluorous biphase-catalysis. Chapters 2 and 3 describe the design, development and realisation of a novel method of catalyst immobilisation, supported fluorous phase catalysis (SFPC). The efficacy of this approach is demonstrated via a series of rhodium-catalysed hydrogenation reactions using a perfluoroalkylated catalyst immobilised in a perfluorocarbon solvent physisorbed onto a variety of fluorine-containing support materials. The solid supports have been investigated by scanning electron microscopy, DRIFTS IR spectroscopy, CP MAS NMR spectroscopy and simultaneous thermal analysis (STA), whilst the catalyst activities and leaching levels have been determined by gas chromatography and AA/ICP spectroscopy. In Chapters 4 and 5 the synthesis of a number of novel perfluoroalkylated phosphorus(III) compounds, formulated for use in the SFPC system, is described. The compounds have been fully analysed by multinuclear NMR spectroscopy, mass spectroscopy and elemental analysis. The co-ordination chemistry of these ligands has been investigated using a range of late transition metals in order to evaluate the electronic properties of the various phosphorus centres. These novel co-ordination complexes have also been analysed by multinuclear NMR spectroscopy, mass spectroscopy, and elemental analysis. The solubilities of the various compounds in perfluorocarbon solvents have been determined in order to assess their suitability for use in perfluorocarbon-based catalytic technologies. Preliminary work is also described on the development of a novel range of perfluoroalkylated palladium complexes for use in carbon-carbon bond formation reactions. Chapter 6 describes the synthesis of two diphosphine compounds and a series of novel co-ordination complexes based on these ligands.

Selective alpha-olefin trimerisation catalysts are of substantial and increasing commercial significance. Novel chromium based catalyst systems, based on derivatives and analogues of the previously developed chromium III complexes of 1,3,5-triazacyclohexanes, have been investigated, with particular emphasis on the synthesis and reactivity of the potential ligand type RB(R’NCH2)2, and on the incorporation of weakly coordinating anionic functionalities into the active complexes.

The enzymes carbon monoxide dehydrogenase (CO dehydrogenase) and hydrogenase catalyse the release of energy from the simple diatomic molecules CO and H2. The ability of transition-metal centres to 1 harness the metabolic power of these compounds, which were highly prevalent in the early atmosphere of Earth, is thought to have been crucial to the development of primitive life.