Some new hydrido-complexes of platinum(II) and their reactions with electrophiles

Abstract

The solvolysis of zerovalent platinum complexes of alkyl diphenylphosphinites in aqueous ethanol leads to the formation of hydridoplatinum(II) complexes. The compounds obtained from n-butyl diphenylphosphinite, isopropyl diphenylphosphinite, and methyl diphenylphosphinite have the respective stoicheiometries corresponding to PtH(OPPh₂)(HOPPh₂)(BuⁿOPPh₂), PtH(OPPh₂)(HOPPh₂)(PrⁱOPPh₂), and PtH(OPPh₂)(HOPPh₂)₂. PtH(OPPh₂)(HOPPh₂)₂ reacts with HCl to give PtCl(OPPh₂)(HOPPh₂)₂. PtHCN(PPh₃)₂ reacts with HBr, HCl, and CF₃CO₂H to give PtBrCN(PPh₃)₂, PtClCN(PPh₃)₂, and Pt(OCOCF₃)CN(PPh₃)₂ respectively. The solvolysis of Pd(BuⁿOPPh₂)⁴ in BuⁿOPPh₂, N₂H₄, and EtOH gives Pd₂(OPPh₂)₄(HOPPh₂)₂ which gives Pd₂Cl₂(OPPh₂)₂(HOPPh₂)₂ with HCl.