Solvent effects on the catalytic activity of manganese(III) corroles

Abstract

Four Mn ( III ) corroles that differ in their electronic environments based on meso-substitution by pentafluorophenyl and phenyl groups were synthesized and characterized by spectroscopic techniques. Utilization of these Mn ( III ) corroles for styrene oxidation using iodosylbenzene (PhIO) as oxygen source in toluene, dichloromethane (DCM), DMF, DMAc, THF and DMSO revealed a remarkable effect of solvent on the catalytic activity. Furthermore, the transformation of Mn ( III ) corroles into their corresponding Mn ( V )-oxo corroles, and subsequent treatment with styrene also indicated that more electron-deficient Mn ( V )-oxo corroles exhibit higher reactivity in toluene and DCM, while less electron-deficient Mn ( V )-oxo corroles exhibit higher reactivity in DMF and DMAc. A significant difference in the observed rates of reaction suggest that the catalytic oxidation of styrene by manganese corroles may proceed through different pathways, and is strongly solvent-dependent.