Regioselective Arene Hydroxylation Mediated by a (μ-Peroxo)diiron(III) Complex: A Functional Model for Toluene Monooxygenase

Diiron(II) complexes, [Fe 2 (L Ph4 )(RCO 2 )] 2+ (R = Ph 3 C or Ph), react with dioxygen to generate peroxodiiron(III) complexes [Fe 2 (L Ph4 )(RCO 2 )(O 2 )] 2+ . Their reactivities can be greatly controlled by the stereochemistry of the bridging carboxylates. Thermal decomposition of a peroxo complex with Ph 3 CCO 2 resulted in regioselective hydroxylation of one of phenyl groups of the supporting ligand, which mimics toluene monooxygenase hydroxylase activity, whereas a peroxo complex with PhCO 2 exhibited reversible deoxygenation.