Journal of Biological Inorganic Chemistry vol. 9, no. 6, pp. 654 - 660
Oxoiron(IV) porphyrin π-cation radicals have been considered as the sole reactive species in the catalytic oxidation of organic substrates by cytochromes P450 and their iron porphyrin models over the past two decades. Recent studies from several laboratories, however, have provided experimental evidence that multiple oxidizing species are involved in the oxygen transfer reactions and that the mechanism of oxygen transfer is much more complex than initially believed. In this Commentary, reactive intermediates that have been shown or proposed to be involved in iron porphyrin complex-catalyzed oxidation reactions are reviewed. Particularly, the current controversy on the oxoiron(IV) porphyrin π-cation radical as a sole reactive species versus the involvement of multiple oxidizing species in oxygen transfer reactions is discussed.