OXIDATIVE ADDITION OF E-E BONDS (E= GROUP 16 ELEMENT) TO PLATINUM(II) - A ROUTE TO PLATINUM(IV) THIOLATE AND SELENOLATE COMPLEXES

Reaction of [PtMe2(phen)] 1 (phen=1,10-phenanthroline) with RE-ER gives the complexes [PtMe2(ER)2(phen)] [2, ER = OH; 3, ER = OC(=O)Ph; 4, ER = SMe; 5, ER = SPh; 6, ER = SePh]. These contain predominantly isomer a in which the ER groups are trans but, in most cases, there is a minor product b in which the ER groups are cis; complexes 4-6 appear to be the first bis(thiolato) or bis(selenolato) complexes of platinum(IV). The structures were determined by NMR spectroscopy and, in the case of complex 6a, by an X-ray structure determination [tetragonal, I4(1)/a, a = b = 13.918(2), c = 25.432(5) angstrom, Z = 8, R = 0.0677, R' = 0.07051. In the reaction with PhSSPh, a sparingly soluble, black intermediate formulated as [{PtMe2(phen)}2(PhSSPh)] was formed.