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Issue 6, 2014
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Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H2O2 generation vs. O–O bond cleavage

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Abstract

The formation of a side-on peroxo [MnIIIL(O2)] complex (L = phenolato-containing pentadentate ligand), resulting from the reaction of electrochemically reduced O2 and [MnIIL]+, is monitored in DMF using cyclic voltammetry, low temperature electronic absorption spectroscopy and electron paramagnetic resonance spectroscopy. Mechanistic studies based on cyclic voltammetry reveal that upon addition of a strong acid the Mn–O bond is broken, resulting in the release of H2O2, whereas in the presence of a weak acid the O–O bond is cleaved via a concerted dissociative electron transfer. This dichotomy of M–O versus O–O bond cleavage is unprecedented for peroxomanganese(III) complexes and the latter offers a route for electrochemical O2 activation by a manganese(II) complex.

Graphical abstract: Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H2O2 generation vs. O–O bond cleavage

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Publication details

The article was received on 17 Dec 2013, accepted on 14 Feb 2014 and first published on 14 Feb 2014


Article type: Edge Article
DOI: 10.1039/C3SC53469C
Citation: Chem. Sci., 2014,5, 2304-2310
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    Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H2O2 generation vs. O–O bond cleavage

    H. Y. V. Ching, E. Anxolabéhère-Mallart, H. E. Colmer, C. Costentin, P. Dorlet, T. A. Jackson, C. Policar and M. Robert, Chem. Sci., 2014, 5, 2304
    DOI: 10.1039/C3SC53469C

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