Oxidative addition of E–E bonds (E = Group 16 element) to platinum(<scp>II</scp>): a route to platinum(<scp>IV</scp>) thiolate and selenolate complexes

Abstract

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, l41/a, a=b= 13.918(2), c= 25.432(5)Å, Z= 8, R= 0.0677, R′= 0.0705]. In the reaction with PhSSPh, a sparingly soluble, black intermediate formulated as [{PtMe2(phen)}2(PhSSPh)] was formed.