Formation of PPh₂C₆F₅ through Phosphido Platinum and/or Palladium(III) Intermediates^‖,⊥

The two-electron oxidation reactions of the neutral [(C₆F₅)₂M(μ-PR₂)₂M‘(NCCH₃)₂] (M = M‘ = Pt or Pd, M = Pt, M‘ = Pd) complexes using I₂ as oxidant have been investigated by experimental (R = Ph) and electronic structure calculation methods (R = H). It was found that a reductive coupling of PR₂ and C₆F₅ takes place along the reaction pathway for all oxidized complexes. The most salient structural features of the [(C₆F₅)₂Pt(μ-PR₂)₂Pd(C₆F₅)₂]^2-, [(C₆F₅)₂Pd(μ-PR₂)₂Pd(acac)]^-, and [(C₆F₅)₂Pt(μ-PR₂)₂PtI₂] complexes (experimental R = Ph) are reproduced very well by the B3LYP/lanl2dz calculations (R = H).