Journal
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
Volume 626, Issue 1-2, Pages 161-170Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jelechem.2008.12.005
Keywords
Electrochemistry; Di-iron complexes; Bridging hydride; Proton reduction; Bioinorganic chemistry; [FeFe]hydrogenases
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Funding
- CNRS (Centre National de la Recherche Scientifique)
- ANR (Programme PhotoBioH2 and CatH2)
- Universite de Bretagne Occidentale
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The electrochemical behaviour of the unsymmetrically disubstituted [Fe-2(CO)(4)(kappa(2)-dppe)(mu-pdt)(mu-H)](+) (1 mu H+) complex was studied by cyclic voltammetry (CV) in MeCN- and CH2Cl2-[NBu4][PF6] both in the absence and in the presence of acid (HBF4 center dot Et2O or HOTs). In the absence of acid, 1 mu H+ undergoes a reversible one-electron oxidation and two-successive one-electron reductions, the first of which is partially reversible. In contrast to symmetrical analogues, 1 mu H+ 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 1 mu H+ is the catalyst. A second proton reduction process at 1.5 V is also observed for both HBF4 center dot Et2O and HOTs. The latter is proposed to be catalysed by the one-electron reduced form of the H-bridged complex, 1 mu H. (C) 2008 Elsevier B.V. All rights reserved.
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