This thesis describes the synthesis and catalytic testing of new bis(diphenylphosphino)amine 'PNP' ligands for use in chromium catalysed trimerisation, rhodium catalysed asymmetric hydrogenation and palladium catalysed telomerisation. Chapter 1 presents an overview of catalysis with particular emphasis on the importance of ligand design, homogeneous and heterogeneous asymmetric catalysis, oligomerisation, concluding with future prospects . Chapter 2 investigates the application of bis(diarylphosphino)amine ligands in telomerisation catalysis, comparison of PNP ligands with the benchmark ligand triphenylphosphine, optimization of the telomerisation of carbon dioxide with l,3-butadiene to give a highly active and selective novel catalyst system. Chapter 3 describes the synthesis of soft donor PNP ligands, their complexation with chromium precursors and their application in oligomerisation and co-oligomerisation catalysis with ethene, carbon dioxide, heterodienes and alkynes. Chapter 4 introduces bis(diarylphosphino) amino acid ester based ligands, their synthesis, and complexation to transition metals. The application of these ligands in asymmetric hydrogenation catalysis of methylamino cinnamic methyl ester (MAC) and methylamino methyl ester (MAA). Chapter 5 extends the synthesis of amino acid ester ligand to tripeptide backbone bis(diarylphosphino)amine ligands, development of synthetic methodology, complexation to platinum, palladium and rhodium precursors, characterisation and application in asymmetric catalysis. Chapter 6 contains the experimental details for the preceeding chapters.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:681562 |
| Date | January 2014 |
| Creators | Pritchard-Smith, Helen Deborah |
| Publisher | University of Bristol |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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