Trifluorophosphine oxide

R. Middleton, J. R. Hull, S. R. Simpson, C. H. Tomlinson, and P. L. Timms, Formation of Complexes with Arenes, Trifluorophosphine, and Nitric Oxide, J. Chem. Soc., Dalton Trans. 1973, 120-124. 

The dihalogenotetrakis(trifluorophosphine)iron complexes can readily be obtained by direct oxidation of [Fe(PF3)5] with the appropriate halogen under mild conditions (method D). NMR studies establish that the halogens lie in cis-positions of the octahedron. 

Oxidative addition of an allyl halide to a zero-valent complex (method D) or treatment of a trifluorophosphine metal late complex with an allylic halide followed by loss of PF3 (method E) have also been briefly reported. 

Good yields of certain rhodium(III) perfluoroalkyl derivatives have been obtained in oxidative addition reactions of perfluoroalkyl iodides (R I) with rhodium (I) trifluorophosphine complexes (method C). 

The parent TMM complex (190 R = H) undergoes photochemical ligand substitution with trifluorophosphine or trimethylamine Al-oxide assisted substitution with tertiary phosphines or t-butyl isocyanide (Scheme 5A) Trimethylamine A-oxide assisted substitution using isoprene as the incoming ligand results in C-C bond formation to afford the bis-TT-allyl complex (197). An intramolecular version of this reaction is also known.The parent complex (190 R = H) reacts with electrophiles. Addition of HCl or Br2 gives the methallyl complexes (192) and (198), respectively. Tetrafluoroethylene adds across the Fe bond to afford (199) under photochemical conditions. Complex (190) undergoes Friedel-Crafts-type acylation with... 

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). 

When manganese vapour and a mixture of nitric oxide, trifluorophosphine and boron trifluoride are co-condensed the compound Mn(PF3)(NO)3 is produced [280]. Co-condensation of nickel and carbon dioxide results in the formation of some nickel tetracarbonyl [280]. Burdett and Turner [298] showed that co-condensation of nickel and nitrogen at 20°K resulted in a nickel—nitrogen complex. Moskovits and Ozin [299] have recently repeated the experiment and have shown from the infrared spectrum of the matrix that the major product is NiN2, with the nickel atom bonded to the end of the nitrogen molecule. 

---