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

Reductive activation of O2 is achieved by using the [FeIII(F20TPP)­Cl] (F20TPP = 5,10,15,20-tetrakis­(pentafluorophenyl) porphyrinate) porphyrin through electrochemical reduction of the [FeIII(F20TPP)­(O2 •–)] superoxo complex. Formation of the [FeIII(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 [FeIII(F20TPP)­(OOH)] hydroperoxo intermediate is probed using low-temperature electronic absorption spectroscopy and electron paramagnetic resonance.