How axial ligands control the reactivity of high-valent iron(IV)–oxo porphyrin π-cation radicals in alkane hydroxylation: A computational study

Abstract

The push effect of anionic axial ligands of high-valent iron(IV)–oxo porphyrin π-cation radicals, (Porp) + Fe IV(O)(X) (X = OH −, AcO −, Cl −, and CF 3 SO 3 - ), in alkane hydroxylation is investigated by B3LYP DFT calculations. The electron-donating ability of anionic axial ligands influences the activation energy for the alkane hydroxylation by the iron(IV)–oxo intermediates and the Fe–O bond distance of the iron–oxo species in transition state.