REACTIONS OF HYDROPEROXIDES WITH IRON(III) PORPHYRINS - HETEROLYTIC CLEAVAGE FOLLOWED BY HYDROPEROXIDE OXIDATION

Reaction of alpha,alpha-dimethylphenethyl hydroperoxide with iron(III) tetramesitylporphyrin in protic solvent gives alkoxy-radical products and little epoxide. Such observations are usually interpreted as evid ence for homolysis of the O-O bond in the catalytic process. Yet the s ame products are now obtained under similar conditions from the reacti on of this hydroperoxide with the high-valent oxene (Fe+=0), generated unambiguously. Therefore such products are not necessarily evidence f or homolysis but are consistent with heterolysis. Nevertheless, the so lvent can affect the nature of O-O cleavage. (C) 1998 Elsevier Science Ltd. All rights reserved.