Extending the coordination chemistry of cobalt with the metalloligand [Pt2(μ-S)2(PPh3)4]: Synthesis of the first cobalt(III) derivatives

► Series of new cobalt(II) and cobalt(III) adducts of [Pt2(μ-S)2(PPh3)4] prepared. ► 8-Hydroxyquinolinate (Q), picolinate and dithiocarbamate promote oxidation of Co(II) to Co(III). ► ESI MS study indicates fragmentation of [Pt2(μ-S)2(PPh3)4CoQ2]+ to [Pt2(μ-S)2(PPh3)4]+. ► [Pt2(μ-S)2(PPh3)4]+ observed in ESI MS analysis of [Pt2(μ-S)2(PPh3)4] in alkaline solution. ► Structure of [Pt2(μ-S)2(PPh3)4CoQ2]PF6 is the first of a true six-coordinate adduct of this type.