Synthesis of diorganoplatinum(IV) complexes by the SS bond cleavage with platinum(II) complexes

•Oxidative addition of MeSSMe to organoplatinum(II) complexes is studied.•New organoplatinum(IV) complexes are prepared.•The structures of organoplatinum(IV) complexes containing PtS bonds are theoretically investigated.

Reaction of [PtR2(NN)] (R = Me, p-MeC6H4 or p-MeOC6H4; NN = 2,2′−bipyridine, 4,4′−dimethyl−2,2′−bipyridine, 1,10−phenanthroline or 2,9−dimethyl−1,10−phenanthroline) with MeSSMe gives the platinum(IV) complexes cis,trans−[PtR2(SMe)2(NN)]. They are characterized by NMR spectroscopy and elemental analysis. The geometries and the nature of the frontier molecular orbitals of Pt(IV) complexes containing PtS bonds are studied by means of the density functional theory.