Palladium(II) Ion Mediated Disulfide/Thiolate Interconversion: Predicting the Disulfide Group State from First Principles.

Different reactivity of homologous disulfides toward Pd was previously reported: stepwise complexation to Pd for l-cystine and cystamine ligands, while for dl-homocystine and 3,3'-dithiodipropionic acid, disulfide's disproportionation toward thiolate and sulfinic acid complexes is observed. The disulfide/thiolate interconversion of four different disulfide ligands in the presence of nonredox metal cation Pd in aqueous solution has been computationally investigated. We see this different reactivity in different capacities of considered homologous disulfides to stabilize forming S,S'-binuclear complexes, which are believed to be key intermediates toward interconversion products. We thus devise a theoretical model that rationalizes experimentally observed phenomenon of disulfides different reactivity toward nonredox transition metal cation Pd.