Title
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Electrochemical formation and reactivity of a manganese peroxo complex : acid driven generation vs. O-O bond cleavage
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Author
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Abstract
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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. |
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Language
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English
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Source (journal)
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Chemical science. - Cambridge, 2010, currens
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Publication
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Cambridge
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Royal Society of Chemistry
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2014
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ISSN
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2041-6520
[print]
2041-6539
[online]
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DOI
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10.1039/C3SC53469C
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Volume/pages
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5
:6
(2014)
, p. 2304-2310
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Full text (Publisher's DOI)
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Full text (publisher's version - intranet only)
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