Publication
Title
Electrochemical formation and reactivity of a manganese peroxo complex : acid driven generation vs. O-O bond cleavage
Author
Abstract
The formation of a side-on peroxo [MnIIIL(O2)] complex (L ¼ 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 MnO bond is broken, resulting in the release of H2O2, whereas in the presence of a weak acid the OO bond is cleaved via a concerted dissociative electron transfer. This dichotomy of M O versus OO bond cleavage is unprecedented for peroxomanganese(III) complexes and the latter offers a route for electrochemical O2 activation by a manganese(II) complex.
Language
English
Source (journal)
Chemical science. - Cambridge, 2010, currens
Publication
Cambridge : Royal Society of Chemistry , 2014
ISSN
2041-6520 [print]
2041-6539 [online]
DOI
10.1039/C3SC53469C
Volume/pages
5 :6 (2014) , p. 2304-2310
Full text (Publisher's DOI)
Full text (publisher's version - intranet only)
UAntwerpen
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Creation 25.10.2017
Last edited 22.08.2023
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