The versatile chemistry of peroxo complexes of vanadium, molybdenum and tungsten as oxidants of organic compounds

The oxidation of organic compounds by hydrogen peroxide, catalysed by transition metal derivatives, e.g. V(V), Mo(VI) and W(VI) complexes, involves the formation of peroxometal complexes. These are much more efficient oxidants than hydrogen peroxide so that the catalysed reactions are of remarkable synthetic significance. Several peroxometal complexes can be isolated and used as stoichiometric oxidants. An appealing feature of these oxidants is their versatility, as demonstrated by the fact that they are able to oxidize substrates such as alkenes, alcohols, ketones, sulphur, phosphorus and nitrogen derivatives and even aromatic and aliphatic hydrocarbons. Either polar or radical oxidations may take place. The reactivity depends on the nature of the metal and especially on the nature of the ligands coordinated to the metal. Therefore, an important goal consists in predicting the reactivity of peroxometal complexes on the basis of their structural features. Examples presented demonstrate that structure-reactivity correlations may be established. However, the effect of the ligands appears to be complex so that care must be exercized in drawing general conclusions. © 1996 by John Wiley & Sons, Ltd.