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

The two-electron oxidation reactions of the neutral [(C6F5) 2 M(μ-PR2)2M'(NCCH3) 2 ] (M = M' = Pt or Pd, M = Pt, M' = Pd) complexes using 12 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 C 6 F 5 takes place along the reaction pathway for all oxidized complexes. The most salient structural features of the [(C6F5) 2 Pt(μ-PR2)2Pd(C6F5)2]2-, [(C6F5) 2 Pd(μ-PR2)2Pd(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).