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

Phosphorus-31 NMR and Raman analyses have been performed in order to check the stability of the hexathiodiphosphate(IV) anion [P2S6](4-) in aqueous so lutions. 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 lea ds to mono- and di-substituted anions, respectively, [P2S5O](4-) and [P2S4O 2](4-), with a total yield of 72% conversion, compared with the initial hex athiodiphosphate anion.