Unconventional Phosphorus Ligands for Catalysis

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Phosphorus(III) ligands are pre-eminent in important areas of homogeneous catalysis (e.g. hydroformylation, hydrocyanation, C-C and C-N coupling reactions, olefin oligomerisation and metathesis, asymmetric hydrogenation) and many of these processes have found industrial applications. The facility and finesse with which P-ligands can be modified is one of the reasons for their popularity. Conventional P-ligands contain P-C, P-O or P-N bonds but the aims of this project are to stretch the boundaries of P-ligand space by exploring the use in homogeneous catalysis of ligands containing P-F, P-B and P=C bonds. The synthesis of these compounds has been developed recently but their applications in catalysis remains largely unexplored. The catalytic processes that will be investigated include hydroformylation using fluorophosphite ligands and dehydrogenation using pincer-ligand complexes. Phospha-alkene ligands have been extensively studied for academic interest but not as ligands for catalysis despite the great interest in the applications of N analogues (imines). Bis(phospha-alkenes) will be screened for a variety of catalytic reactions including methoxy-carbonylation.