Transition metal dioxygen complexes as intermediates in homogeneous catalytic oxidations

The formation and main structural properties of superoxo and peroxo complexes are briefly described. These complexes are involved in catalytic oxidations (oxygenations) by dioxygen occurring under mild conditions in the presence of iron, cobalt, manganese, rhodium and other transition metal complexes. Examples of catalytic systems are taken from cytochrome P-450 models with specific reference to the mechanisms involved. Metalloporphyrin-catalysed oxidations of hydrocarbons involve free-radical chain processes in most cases. Added reducing agents modify the mechanism of oxidation by pumping electrons into key intermediates. They help the formation of oxometal species, which may transfer oxygen atoms to substrates, thereby improving the selectivity. Olefin oxidation is a difficult task for the homogeneous catalysts described: only a few working systems are available, based mainly on rhodium phosphine complexes. Peroxometalacycles are presumably formed, whose decomposition involves co-oxidation of a phosphine molecule. The oxidation of hindered phenols catalysed by cobalt (II) Schiff-base complexes points to the involvement of superoxocobalt species abstracting a H-atom from the phenol. Complex reaction patterns emerge from the oxidation of o-disubstituted phenols. The synthetic potential of homogeneous catalytic oxidation is illustrated on examples including various types of organic compounds.