Reactivity of primary amines co-ordinated to palladium and platinum. Part II. Cyclometallation and rearrangement of the co-ordinated ligands

Abstract

Reaction of trans-[PdCl₂(NH₂X)₂](X = NPhR or PhCH₂; R = Ph, Me, or H) with acetophenone gives the cyclo-palladated dimer [{PdCl(C₆H₄CMeNX)}₂], the acetophenone phenyl ring being orthometallated. Reaction of [PtCl₄]^2– and [Pd₂Cl₆]^2– with 2-aminothiazoline and 2-aminothiazole (L) affords in acid media the cyclic N-co-ordinated monosubstituted [NBu₄][PdCl₃L] and disubstituted cis-[PtCl₂L₂] and trans-[PdCl₂L₂] complexes. In basic solution, the monomeric [PdCl₂L′₂] and dimeric [{MCl₂L′}₂] species are obtained [M = Pt^II or Pd^II; L′= HS·CH₂·CH₂·NH·C⋮N and HS·CH:CH·NH⋮N. The combined presence of the metal and hydroxide ions appears to induce the ring opening and rearrangement of the amine ligands.