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Article Dans Une Revue Bioelectrochemistry Année : 2023

Electrochemical reduction and protonation of a biomimetic diiron azadithiolate hexacarbonyl complex: Mechanistic insights

Résumé

The electrochemical reduction and protonation of [Fe2(adtH)(CO)6] (1, adtH = SCH2N(H)CH2S) and [Fe2(pdt)(CO)6] (2, pdt = SCH2CH2CH2S) in the presence of moderately strong acid in acetonitrile was investigated by cyclic voltammetry (CV), focusing on the catalysis of hydrogen evolution reaction (HER) by a {2e−,2H+} pathway. The turnover frequencies at zero overpotential (TOF0) of the N-protonated product 1(H)+ and 2 for the HER were estimated from simulations of the catalytic CV responses at low acid concentration using a simple ECEC mechanism (two electrochemical and chemical steps). This approach confirmed that 1(H)+ is clearly a better catalyst than 2, pointing to a possible role of the protonable and biologically relevant adtH ligand in the enhancement of the catalytic performances. Density functional theory (DFT) calculations further suggested that, owing to a strong structural rearrangement in the course of the catalytic cycle, the HER catalysis by 1(H)+ only involves the iron center adjacent to the amine group in adtH and not the two iron centers as in 2. Since terminal hydride species (FeFe−H) are known to more easily undergo protonolyse to H2 than their bridging hydride isomers (Fe−H−Fe), this may explain here the enhanced activity of 1(H)+ over 2 for the HER.
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hal-04132478 , version 1 (14-02-2024)

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Marc Bourrez, Frédéric Gloaguen. Electrochemical reduction and protonation of a biomimetic diiron azadithiolate hexacarbonyl complex: Mechanistic insights. Bioelectrochemistry, 2023, 153, pp.108488. ⟨10.1016/j.bioelechem.2023.108488⟩. ⟨hal-04132478⟩
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