Use of the Asymmetrical Chelating N-Donor 2-Imino-Pyridine as a Redox [Fe$_4$S$_4$] Cubane Surrogate at a Di-Iron Site Related to [FeFe]-Hydrogenases - Chimie Electrochimie Moléculaires et Chimie Analytique
Journal Articles Inorganics Year : 2023

Use of the Asymmetrical Chelating N-Donor 2-Imino-Pyridine as a Redox [Fe$_4$S$_4$] Cubane Surrogate at a Di-Iron Site Related to [FeFe]-Hydrogenases

Abstract

Two complexes, related to the active site of [FeFe]-hydrogenases, [Fe$_2$(CO)$_4$($κ^2$-pma)(µ-bdt)] (1) and [Fe$_2$(CO)$_4$($κ^2$-pma)(µ-pdt)] (2) (bdt = benzene-1,2-dithiolate, pdt = propane-1,2-dithiolate) featuring the diaza chelate ligand trans-N-(2-pyridylmethylene)aniline (pma) were prepared, in order to study the influence of such a redox ligand, potentially non-innocent, on their redox behaviours. Both complexes were synthesized by photolysis in moderate yields, and they were characterized by IR, $^1$H and $^{13}$C{1H} NMR spectroscopies, elemental analyses and X-ray diffraction. Their electrochemical study by cyclic voltammetry, in the presence and in the absence of protons, revealed different behaviours depending on the aliphatic or aromatic nature of the dithiolate bridge. Density functional theory (DFT) calculations showed the role of the pma ligand as an electron reservoir, allowing the rationalization of the proton reduction process of complex 1.
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Dates and versions

hal-04373319 , version 1 (13-09-2024)

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Andrea Mele, Federica Arrigoni, Luca de Gioia, Catherine Elleouet, François Pétillon, et al.. Use of the Asymmetrical Chelating N-Donor 2-Imino-Pyridine as a Redox [Fe$_4$S$_4$] Cubane Surrogate at a Di-Iron Site Related to [FeFe]-Hydrogenases. Inorganics, 2023, 11 (12), pp.463. ⟨10.3390/inorganics11120463⟩. ⟨hal-04373319⟩
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