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Electrocatalytic O 2 Activation by Fe Tetrakis(pentafluorophenyl)porphyrin in Acidic Organic Media. Evidence of High-Valent Fe Oxo Species

Abstract : O2 activation under mild conditions remains a weighty challenge for chemists. Herein we report a study of electrochemical O2 reductive activation catalyzed by Fe III (F20 TPP)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.
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Nikolaos Kostopoulos, Ceĺia Achaibou, Jean-Marc Noel, Fredeŕic Kanoufi, Marc Robert, et al.. Electrocatalytic O 2 Activation by Fe Tetrakis(pentafluorophenyl)porphyrin in Acidic Organic Media. Evidence of High-Valent Fe Oxo Species. Inorganic Chemistry, American Chemical Society, 2020, 59 (16), pp.11577-11583. ⟨10.1021/acs.inorgchem.0c01379⟩. ⟨hal-02951618⟩

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