Oxidative addition of functional disulfides to platinum(II): Formation of chelating and bridging thiolate–carboxylate complexes of platinum(IV)

An unusual type of oxidative addition of disulfides containing a carboxylic acid group to platinum(II) is established, giving the first thiolate–carboxylate complexes of platinum(IV). The disulfide R2S2 with R = CH2CH2CO2H reacts with [PtMe2(2,2′-bipyridine)] to give RSH and the chelating thiolate–carboxylate complex [PtMe2(κ2-S,O–SCH2CH2CO2)(bipy)]. However, the disulfide R2S2 with R = C6H3–4–NO2–3–CO2H reacts to give first the product of trans oxidative addition [PtMe2(SR)2(bipy)], which slowly reacts further to give RSH and the bridging thiolate–carboxylate complex [Pt2Me4(κ2–S,O–SC6H3–4–NO2–3–CO2)2(bipy)2].