Transfer of tertiary phosphine between rhodium and either platinum or palladium

Abstract

Biheterometallic chloro-bridged hydrido-species of type [L₂HClRh(µ-Cl)₂MClL′](L = PBu^tPr₂ or PPrBu^t₂, M = Pd or Pt, L′= PEt₃, PBu₃, or PPr₂Bu^t) are formed on mixing toluene solutions of square-pyramidal [RhHCl₂L₂]²(L = PPr₂Bu^t or PPrBu^t₂) and a chloro-bridged dimeric palladium or platinum complex, [M₂Cl₄L′₂](M = Pt, L′= PEt₃, PBu₃, or PPr₂Bu^t; M = Pd, L′= PBu₃). On standing, in solution, at ambient temperature these biheterometallic complexes decompose, giving rise to mixed tertiary-phosphine complexes of type trans-[MCl₂LL′]. The rate of this reaction is strongly dependent on the nature of both M and L. The ¹H and ³¹P n.m.r. data of the com-plexes are reported.