Oxidation of organic substrates is achieved in nature under mild conditions thanks to metalloenzymes but remains a challenge for chemists. Herein we show by UV-Vis spectroelectrochemistry that when MnIIITPPCl is electrochemically reduced to MnII in CH2Cl2 under O2, a MnIIO2˙ species is generated. Benzoic anhydride reacts with the latter triggering a catalytic current in cyclic voltammetry. Electrolysis on the catalytic wave in the presence of cyclooctene leads to its oxygenation or halogenation depending on the axial ligand present as reported here for the first time.
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