om0508029_si_002.pdf (536.21 kB)
Formation of PPh2C6F5 through Phosphido Platinum and/or Palladium(III) Intermediates‖,⊥
journal contributionposted on 2006-02-27, 00:00 authored by Irene Ara, Naima Chaouche, Juan Forniés, Consuelo Fortuño, Abdelaziz Kribii, Athanassios C. Tsipis
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).