Oxidative addition of mercury(II) halides and carboxylates to platinum(II): formation of Pt–Hg covalent and donor–acceptor bonds

Abstract

The complex [PtMe 2(bu 2bpy)], 1, bu 2bpy = 4,4′-di- t-butyl-2,2′-bipyridine reacts with mercury(II) halides HgX 2 (X = Cl, Br, O 2CCF 3, O 2CMe) to give the corresponding complexes [PtMe 2X(HgX)(bu 2bpy)], 2, by trans oxidative addition followed, when X = O 2CCF 3, O 2CMe only, by easy isomerization to the cis isomers 3. The complexes 2 or 3 react with complex 1 to give the corresponding adducts [PtMe 2X(bu 2bpy)(μ-HgX)PtMe 2X(bu 2bpy)], 4, which are shown to contain both covalent and donor–acceptor Pt–Hg bonds in the solid state, and which exhibit very easy fluxionality in solution.