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

The push effect of anionic axial ligands of high-valent iron(IV)–oxo porphyrin π-cation radicals, (Porp)+FeIV(O)(X) (X = OH−, AcO−, Cl−, and CF3SO3-), 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.