Electrocatalytic O<sub>2</sub> Activation by Fe Tetrakis(pentafluorophenyl)porphyrin in Acidic Organic Media. Evidence of High-Valent Fe Oxo Species
Nikolaos Kostopoulos, Célia Achaibou, Jean‐Marc Noël, Frédéric Kanoufi, Marc Robert, Claire Fave, Elodie Anxolabéhère‐Mallart
Abstract
O2 activation under mild conditions remains a weighty challenge for chemists. Herein we report a study of electrochemical O2 reductive activation catalyzed by FeIII(F20TPP)Cl, by means of cyclic voltammetry and UV–vis spectroelectrochemistry in acidic solutions of N,N-dimethylformamide. Two parallel catalytic pathways have been evidenced occurring at different overpotentials. At high overpotential a classical electron–proton (EPT) pathway where protonation of Fe peroxo ultimately leads to the formation of high-valent Fe oxo species dominates. At low overpotential a proton–electron (PET) pathway involving a hydrosuperoxo species has been identified.