Trifluorophosphine complexes alkyls

Relatively few examples of metal trifluorophosphine complexes of formula [MRx(PF3)y are known (see Table XVI). 

Since the P—F bonds are labile in these complexes some mixed trifluorophosphine-fluorophosphite nitrosyl complexes have been prepared by reactions with either diisopropyl-water mixtures or barium hydroxide (method F) to give the (PF20) compounds which can be alkylated. 

Alkyltetrakis(trifluorophosphine)cobalt complexes can be prepared from the anion [Co(PF3)4] only with strong alkylating agents because of the low nucleophilicity of the anion (method A). Thus, treatment of [Co(PF3)4] with an oxonium salt yields [Me30] [Co(PF3)4], which on heating gives the desired product. 

Oxidation of trifluorophosphine by halogens is well known (282) and although corresponding reactions with alkyl or aryl fluorophosphines have received only little attention, it has become apparent that oxidation to the pentavalent phosphorus fluorides can be brought about by a wide variety of reagents. In certain cases the reducing property of the fluoro-phosphine has been utilized in the synthesis of zero-valent transition metal fluorophosphine complexes (Section IX). 

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