Oxidation of dimethylplatinum(ii) complexes with a peroxyacid

Abstract

The complexes [PtMe₂(NN)], NN = 2,2′-bipyridine = bipy, 1a; NN = di-2-pyridylamine = dpa, 1b; NN = di-2-pyridyl ketone = dpk, 1c, NN = 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine, bebipy, react with m-chloroperoxybenzoic acid to give the platinum(IV) complexes [Pt(OH)(O₂C-3-C₆H₄Cl)Me₂(NN)], NN = bipy, 2, or [Pt(OH)(OH₂⋯O₂C-3-C₆H₄Cl)Me₂(NN)], NN = bipy, 3a; dpa, 3b; bebipy, 3d, or [Pt(OH)₂Me₂(dpkOH)]₃[Pt(OH)(OH₂)Me₂(dpkOH)][H(O₂C-3-C₆H₄Cl)₂]·2MeOH, 4₃·5·2MeOH. The reactions are proposed to occur by a polar oxidative addition mechanism, followed in most cases by the coordination of water. Complex 3a crystallises as a supramolecular polymer, the compound 4₃·5·2MeOH crystallises as a supramolecular sheet structure, and 3d easily forms a gel, all through strong intermolecular hydrogen bonding.