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Complexes and applications of substituted bidentate P, S ligands

Koursarou, Despina. 2006. Complexes and applications of substituted bidentate P, S ligands. PhD Thesis, Cardiff University.

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In recent years there has been great interest in developing bidentate systems where only one of the atoms is phosphorus. Mixed P, O- and P, N- donor ligands have been extensively applied in catalysis and there is growing interest with respect to potential applications of P, S-ligands. This thesis reports on the synthesis and application of a range of substituted P, S-ligands and the catalytic results obtained are discussed. Chapter 2 describes the synthesis of several bidentate phosphinothiolate and -thioether (P, S) ligands. The P, S ligand l-(diphenylphosphino)butane-2-thiol (L1) was derived from a thiirane which was synthesised by the ring-opening reaction of an epoxide. The thioether tertiary-butyl derivative (L2) was also synthesised along with the thioether methyl (L3), thioether benzyl (L4), thioether xylene (L5), thioether naphthalene (L6) and thioether anthracene (L7). The ligands were subsequently coordinated to palladium and the resulting complexes (1-12) exhibit a monomelic or dimeric geometry. Chapters 3 and 4 detail the application of the palladium complexes in catalytic reactions. The palladium phosphinothiolate and -thioether complexes have been tested as pre- catalysts in the Heck and Suzuki cross-coupling reactions which were performed under aerobic conditions. The Heck couplings with styrene and butyl acrylate were investigated along with a variety of haloarenes, and the Suzuki reactions have explored the cross-couplings of various haloarenes with benzene boronic acid. The complexes tested were highly efficient catalysts in the coupling reactions. Turnover numbers (TONs) of up to 1 million have been achieved for Heck couplings and 1.98 x 1010 for the Suzuki coupling reactions.

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
ISBN: 9781303207709
Date of First Compliant Deposit: 30 March 2016
Last Modified: 12 Feb 2016 23:15

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