Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H2O2 generation vs. O-O bond cleavage - Archive ouverte HAL Access content directly
Journal Articles Chemical Science Year : 2014

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

Abstract

The formation of a side-on peroxo [(MnL)-L-III(O-2)] complex (L = phenolato-containing pentadentate ligand), resulting from the reaction of electrochemically reduced O-2 and [(MnL)-L-II](+), 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 MO versus O-O bond cleavage is unprecedented for peroxomanganese(III) complexes and the latter offers a route for electrochemical O-2 activation by a manganese(II) complex.
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hal-01362708 , version 1 (09-09-2016)

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H. Y. Vincent Ching, Elodie Anxolabéhère-Mallart, Hannah E. Colmer, Cyrille Costentin, Pierre Dorlet, et al.. Electrochemical formation and reactivity of a manganese peroxo complex: acid driven H2O2 generation vs. O-O bond cleavage. Chemical Science, 2014, 5 (6), pp.2304-2310. ⟨10.1039/c3sc53469c⟩. ⟨hal-01362708⟩
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