Terminal platinum(II) perfluoroacyl phosphido complexes: Synthesis and dynamic processes

The Pt(II) phosphido methyl complexes Pt(dppe)(Me)(PPhR) (dppe = Ph2PCH2CH2 PPh2, R = i-Bu, 1; R = Is = 2,4,6-(i-Pr)(3)C6H2, 2) have been prepared by p roton transfer from secondary phosphines to the methoxide ligand of Pt(dppe )(Me)(OMe). Oxidative addition of ClC(O)C3F7 to Pt(PPh2Me)(4) gives trans-P t(PPh2Me)(2)(COC3F7)(Cl) (3); treatment of 3 with dppe yields Pt(dppe)(COC3 F7)(Cl) (4). Complexes 3.0.5CH(2)Cl(2) and 4 were structurally characterize d by X-ray crystallography. Reaction of 4 with AgBF4 and a secondary phosph ine or treatment of [Pt(dppe)(COC3F7)(NCMe)][BF4] (5) with a secondary phos phine gives the cations [Pt(dppe)(COC3F7)(PHPhAr)][BF4] (Ar = Mes = 2,4,6-M e3C6H2, 6; Ar = o-anisyl, 7; Ar = Is, 8; Ar = Mes-F-9 = 2,4,6-(CF3)(3)C6H2, 9; Ar = Ph, 10). Deprotonation of the cations with LiN(SiMe3)(2) affords t he phosphido complexes Pt(dppe)(COC3F7)(PPhAr) (Ar = Mes, 11; Ar = o-anisyl , 12; Ar = Is, 13; Ar = Mes-F-9, 14; Ar = Ph, 15). Fluxional processes in c omplexes 11-15 were studied by variable-temperature multinuclear NMR spectr oscopy; the spectra are consistent with rapid phosphorus inversion on the N MR time scale at room temperature.