Trifluorophosphine complexes

Trifluorophosphine complexes of transition metals. J. F. Nixon, Adv. Inorg, Chem. Radiochem., 1985,29,1 (368). 

Iridium(O).—The first dinuclear trifluorophosphine complex of Ir has been prepared by elimination of H from IrH(PF3)4 ... 

IR spectra, 22 177-179 Raman spectra, 22 178, 179 triazole and triazolate complexes, 32 180 trifluoride, structure, 27 90, 91, 92, 95, 97 trifluorophosphine complexes cyclopentadienyl, 29 103 hexakis anion, 29 53-54 [Ni4(0CH3)4(acac)4(CH3OH4)l, 43 323 Nitramide, reaction mechanisms, 22 138, 139 acid catalysis, 22 139... 

Trifluorophosphine complexes of the dimercury(I) ion Hg + in liquid S02 have been detected by 19F NMR.69,70 Cations such as (Hg2PF3)2+ or Hg2P(CF3)Ph2 2+ in these solutions are also... 

There are many similarities in the behavior of PF3 and CO as ligands. This is manifested by the existence of a large number of PF3 complexes of the transition metals (197, 226). Several UPS studies of such complexes have now appeared in the literature (20, 152, 169, 182, 221, 227). As pointed out in Section II, it is difficult to arrive at a completely unequivocal set of assignments for these compounds other than for the predominantly metal MOs. It is seen below, however, that one of the advantages of studying the UPS of the PF3 complexes is that many more ionizations pertinent to bonding discussions are discernible. Furthermore, trifluorophosphine complexes tend to be more thermally stable than their carbonyl counterparts. 

Structural and/or spectroscopic investigations have shown that the local symmetries around the metal atoms in the M(PF3)4 (189,215), M(PF3)5(2), and M(PF3)6 compounds are Td, D3h, and Oh, respectively. Unfortunately theoretical studies on trifluorophosphine complexes are confined to CNDO/2 calculations on Ni(PF3)4, Fe(PF3)5, and Cr(PF3)6 (251). In view of the discussion of relaxation effects and basis set dependences presented in Section II the CNDO/2 results (Table XXVI) should be used only as a qualitative guide to spectral assignment. 

The pentacoordinate trifluorophosphine complexes behave similarly. Thus the difference in energy between the 2E and 2E" states, Ae e"> increases markedly in going from Fe(PF3)s to Ru(PF3)s. This increase is caused by the change in energy of the 2E state, which, in turn, results from changing from a 3d to a 4d metal orbital. 

Trifluorophosphine Complexes of Transition Metals John F. Nixon... 

In some cases H2 can interact directly with binary metal-trifluorophosphine complexes under mild conditions with or without addition of PF3 or UV irradiation (method B), and group IV hydrides have also been utilized (method C). 

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