Characterization and reactivity of triperoxo vanadium complexes in protic solvents

ESI-MS and V-51 NMR techniques have been used to detect the formation of va nadium triperoxo complexes in protic solvents. RHF/6-311++G(d,p) ab initio calculations were also carried out to address the structure and the energy requirements of vanadium peroxo species formed from vanadates and hydrogen peroxide. Such studies point to a step-by-step decomposition process involv ing the triperoxo vanadium complex, as highlighted by ESI-MSn experiments. The reactivity of the triperoxo compound has been examined in an alcohol/wa ter mixture with the aim of elucidating its oxidative behavior; evidence fo r the formation of the HOO- anion as an active oxidant in solution has been obtained.