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 R_fI 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 R_3−nP(R_f)_n capable of possessing a wide range of steric and electronic properties.