Mechanistic Insight into the Aromatic Hydroxylation by High-Valent Iron(IV)-oxo Porphyrin -Cation Radical Complexes

摘要

Mechanistic studies of the aromatic hydroxylation by high-valent iron(IV)-oxo porphyrin -cation radicals revealed that the aromatic oxidation involves an initial electrophilic attack on the -system of the aromatic ring to produce a tetrahedral radical or cationic -complex. The mechanism was proposed on the basis of experimental results such as a large negative Hammett value and an inverse kinetic isotope effect. By carrying out isotope labeling studies, the oxygen in oxygenated products was found to derive from the iron-oxo porphyrin intermediates.