Electrochemical study of the role of a H-bridged, unsymmetrically disubstituted diiron complex in proton reduction catalysis

Abstract : The electrochemical behaviour of the unsymmetrically disubstituted [Fe2(CO)4(κ2-dppe)(μ-pdt)(μ-H)]+ (1μH+) complex was studied by cyclic voltammetry (CV) in MeCN– and CH2Cl2–[NBu4][PF6] both in the absence and in the presence of acid (HBF4 · Et2O or HOTs). In the absence of acid, 1μH+ undergoes a reversible one-electron oxidation and two-successive one-electron reductions, the first of which is partially reversible. In contrast to symmetrical analogues, 1μH+ does not regenerate its neutral precursor 1 upon reduction on the CV timescale. When acid is present, the reduction leads to catalytic proton reduction at a mild potential (ca. −1.3 V vs. Fc+/Fc) according to an original mechanism where 1μH+ is the catalyst. A second proton reduction process at −1.5 V is also observed for both HBF4 · Et2O and HOTs. The latter is proposed to be catalysed by the one-electron reduced form of the H-bridged complex, 1μH.
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Journal of Electroanalytical Chemistry, Elsevier 2009, 626 (1-2), pp.161 - 170. 〈http://www.sciencedirect.com/science/article/pii/S0022072808004695〉. 〈10.1016/j.jelechem.2008.12.005〉
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http://hal.univ-brest.fr/hal-01578082
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Soumis le : lundi 28 août 2017 - 16:17:36
Dernière modification le : jeudi 11 janvier 2018 - 06:17:06

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Salah Ezzaher, Jean-François Capon, Nicolas Dumontet, Frederic Gloaguen, François Y. Pétillon, et al.. Electrochemical study of the role of a H-bridged, unsymmetrically disubstituted diiron complex in proton reduction catalysis. Journal of Electroanalytical Chemistry, Elsevier 2009, 626 (1-2), pp.161 - 170. 〈http://www.sciencedirect.com/science/article/pii/S0022072808004695〉. 〈10.1016/j.jelechem.2008.12.005〉. 〈hal-01578082〉

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