Platinum(II)‐mediated disulfide/thiolate interconversion in organic disulfides: Density functional theory thermodynamic study

Abstract

We present a complete Density Functional Theory (DFT) study of the thermodynamics of the reactions of disulfides (L-cystine, cystamine, DL-homocystine, and 3,3 0dithiodipropionic acid) with Pt(II) ions in aqueous media. SMD solvation model was fitted to take into account the solvation effects of the medium. DFT calculations predict the oxidative addition reaction with the formation of thiolate complexes of Pt(IV)-[PtCl 4 (S-R) 2 ] which is consistent with experimental data. We propose a theoretical model that rationalizes the experimental data on Pt(II) interactions with homological disulfides. The role of explicit solvation in reactions is also investigated. We propose that the stability of S,S 0 -binuclear disulfide complexes correlates with the redistribution of charges on sulfur atoms. We compared MN15 and PBE0 functionals for the calculation of equilibrium constants.