Trifluorophosphine synthesis

In our study of the fluorination of coordinated chlorophosphine ligands (23), we started out with tetrakis(trichlorophosphine)nickel-(0), which could previously be converted into tetrakis(trifluorophosphine)nickel-(0) by displacement of the coordinated phosphorus trichloride with excess phosphorus trifluoride in a sealed tube (32). The limitations of this method, requiring the use of phosphorus trifluoride, a low boiling gas, under pressure, and involving the mechanical separation of the fluorophosphine complex from phosphorus trichloride, are obvious, and the yield was low. A straightforward method for the synthesis of this interesting compound was found in the fluorination of the coordinated phosphorus trichloride with potassium fluorosulfinate ... 

An interesting synthesis of zero-valent ruthenium phosphine-trifluorophosphine complexes has been reported (2, 4) (method I) via reductive elimination of acetic acid from the ruthenium(II) hydrido acetato complex [RuH(C02Me)(PPh3)3]. 

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). 

Tetrakis (trifluorophosphine) nickel, Ni(PF3)4 and Pt(PF3)4 can be obtained by direct synthesis of the gas with metal powder at 100°C and 300 atm. The very stable nickel compound contains zero valent tetrahedral nickel since sufficient lone pairs are donated by the ligand PF3 groups to complete... 

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