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

Abstract

The two-electron oxidation reactions of the neutral [(C 6 F 5 ) 2 M(μ-PR 2 ) 2 M‘(NCCH 3 ) 2 ] (M = M‘ = Pt or Pd, M = Pt, M‘ = Pd) complexes using I 2 as oxidant have been investigated by experimental (R = Ph) and electronic structure calculation methods (R = H). It was found that a reductive coupling of PR 2 and C 6 F 5 takes place along the reaction pathway for all oxidized complexes. The most salient structural features of the [(C 6 F 5 ) 2 Pt(μ-PR 2 ) 2 Pd(C 6 F 5 ) 2 ] 2 -, [(C 6 F 5 ) 2 Pd(μ-PR 2 ) 2 Pd(acac)] -, and [(C 6 F 5 ) 2 Pt(μ-PR 2 ) 2 PtI 2 ] complexes (experimental R = Ph) are reproduced very well by the B3LYP/lanl2dz calculations (R = H).