Fluoroalkenyl, fluoroalkynyl and fluoroalkyl phosphines

A review of the methods available for the preparation of monodentate P(III) compounds containing fluoroalkenyl, fluoroalkynyl and fluoroalkyl groups is given. The synthesis, properties and coordination chemistry of some fluoroalkenyl- and fluoroalkynyl-containing phosphines derived from HFC-134a (CF3CH2F) and HFC-245fa (CF3CH2CH2F) is summarised. The development of the reaction between trimethylsilyl-containing phosphines and RfI which provides a general method by which bulky fluoroalkyl groups, such as i-C3F7, t-C4F9, c-C6F11, can be readily introduced into phosphorus(III) centres is reported. Together these methods provide a way of generating P(III) systems of the type R3−nP(Rf)n capable of possessing a wide range of steric and electronic properties.