Characterization and Subsequent Reactivity of an Fe-Peroxo Porphyrin Generated by Electrochemical Reductive Activation of O2

Reductive activation of O-2 is achieved by using the [Fe-III(F20TPP)Cl] (F20TPP = 5,10,15,20-tetrakis-(pentafluorophenyl) porphyrinate) porphyrin through electrochemical reduction of the [Fe-III(F20TPP)(O-2(center dot-))] superoxo complex. Formation of the [Fe-III(F20TPP)(OO)](-) peroxo species is monitored by using low-temperature electronic absorption spectroscopy, electron paramagnetic resonance, and cyclic voltammetry. Its subsequent protonation to yield the [Fe-III(F20TPP)(OOH)] hydroperoxo intermediate is probed using low-temperature electronic absorption spectroscopy and electron paramagnetic resonance.