Fluoroalkyl-containing phosphines

This review describes recent advances in the synthesis, chemistry and applications of phosphine ligands containing one or more perfluoroalkyl, Rf, substituent. The methods reviewed are capable of generating a wide variety of monodentate, bidentate and PCP-pincer ligands containing Rf groups. Based on the chemistry of complexes containing these ligands, and compilations of their spectroscopic data and structural parameters it is shown that fluoroalkyl-containing phosphines have a distinct combination of steric and electronic properties, often quite different to fluoroaryl analogues. The catalytic activities displayed by complexes of these ligands are described.

► Comprehensive survey of monodenate, bidentate and pincer perfluoroalkyl-phosphines. ► A review of recently published methods of synthesizing Rf-containing phosphines. ► Summaries of structures and spectroscopic data available, upto 2011, for fluoroalkyl-phosphines. ► Applications in catalysis.