Novel bulky fluorinated ligands for homogeneous catalysis
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A series of novel monodentate and bidentate phosphine ligands substituted with bulky tert-butyl and fluorinated aryl groups have been synthesised. Borane protection has proved to be an excellent method for easy synthesis and purification of bidentate ligands in some cases. However, several of the bulky fluorinated ligands do not form stable borane complexes leading to complications in the synthesis and purification of these compounds. By reaction with transition metal platinum and palladium precursors, it was possible to form dichloride complexes from the synthesised ligands, which were characterised by X-ray crystallography. The complexes were found to be effective catalysts for the hydroxycarbonylation of vinyl arenes (yields of up to 95 % with 3 mol% catalyst). An unsymmetrical bidentate complex (3.18) in combination with paratoluenesulfonic acid and LiCl promoters has given exceptional (for a diphosphine ligand) regioselectivity for the branched acid (98.7 % branched) in the hydroxycarbonylation of styrene. The role of the promoters has been found to be crucial in deciding the activity and selectivity in this reaction.
Thesis, PhD Doctor of Philosophy
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