Insertion of Elemental Sulfur and SO2 into the Metal−Hydride and Metal−Carbon Bonds of Platinum Compounds

Elemental sulfur (S 8 ) has been found to insert only one sulfur atom into the metal−hydride bonds of the platinum alkyl and aryl hydride complexes [(dcpe)PtRH] (dcpe = Cy 2 PC 2 H 4 PCy 2 ). Unlike the parent compounds, the S-inserted complexes do not undergo reductive elimination to form the corresponding alkane- or arenethiols. Methane is lost from the methyl sulfhydryl complex. Sulfur dioxide was also found to insert into a platinum−methyl bond to form the corresponding S-bound sulfinate, which upon reacting with mineral acids generates methylsulfinic acid.