Iron(III) corrole complexes catalyze the highly chemoselective oxidation of sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc) 2 ] as a mild oxygen source. Various substituted thioanisoles, vinyl sulfides, and hydroxyl sulfides can be efficiently oxidized to sulfoxides with quantitative conversions (up to 5000 TONs) and excellent selectivies without over-oxidation to sulfones. The remarkably enhanced catalytic activity and stability against degradation is ascribed to the slow and steady-state formation of PhIO from highly soluble PhI(OAc) 2 in the presence of a small amount of water. On the basis of Hammett correlation and mixing UV-vis spectral studies, a putative high-valent iron(V)-oxo species is likely generated as a short-lived active intermediate.
Depending on the structure of the porphyrin ligands, the visible light photolysis of porphyrin–iron(iii) bromates produced iron(iv)-oxo radical cations or iron(iv)-oxo porphyrins, permitting direct kinetic studies of their oxidation reactions.
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