Oxygen substitution of the hexathiodiphosphate(IV) ion in aqueous solution

Abstract

Phosphorus-31 NMR and Raman analyses have been performed in order to check the stability of the hexathiodiphosphate(IV) anion [P₂S₆]^4– in aqueous solutions. This anion appears to be better stabilized in basic media than in acidic ones. Moreover, a gentle oxidation by a diluted solution of hydrogen peroxide allowed a partial substitution of sulfur by oxygen atoms that leads to mono- and di-substituted anions, respectively, [P₂S₅O]^4– and [P₂S₄O₂]^4–, with a total yield of 72% conversion, compared with the initial hexathiodiphosphate anion.