Electrochemical and Theoretical Investigations of the Oxidatively induced reactivity of the complex [Fe2(CO)4(κ2-dmpe)(µ-adtBn)] related to the Active Site of [FeFe]-Hydrogenases - Université de Bretagne Occidentale Access content directly
Journal Articles Chemistry - A European Journal Year : 2018

Electrochemical and Theoretical Investigations of the Oxidatively induced reactivity of the complex [Fe2(CO)4(κ2-dmpe)(µ-adtBn)] related to the Active Site of [FeFe]-Hydrogenases

Abstract

Electrochemical oxidation of the complex [Fe2(CO)4(κ2‐dmpe)(µ‐adtBn)] (adtBn = (SCH2)2NCH2C6H5, dmpe = Me2PCH2CH2PMe2) (1) has been studied by cyclic voltammetry (CV) in acetonitrile and in dichloromethane in presence of various substrates L (L =MeCN, trimethylphosphite, isocyanide). The oxidized species, [1‐MeCN](PF6)2, [1‐(P(OMe)3)2](PF6)2 and [1‐(RNC)4](PF6)2 (R = tButyl, Xylyl), have been prepared and characterized by IR, NMR spectroscopies and, excepted [1‐MeCN](PF6)2, by X‐ray diffraction analysis. The crystallographic structures of the new FeIIFeII complexes reveal in any case that the association of one additional ligand (P(OMe)3 or RNC) occurs and, according to the nature of the substrates, further substitutions of one or three carbonyl groups, by P(OMe)3 or RNC, respectively, arise. Density functional theory (DFT) calculations have been performed for elucidating and discriminating, in each case, the mechanisms leading to the corresponding oxidized species. Moreover, the different degree of ligand substitution in the diiron core has been theoretically rationalized.
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hal-01845050 , version 1 (20-07-2018)

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Federica Arrigoni, Salma Mohamed Bouh, Catherine Elleouet, Philippe P. Schollhammer, François Pétillon, et al.. Electrochemical and Theoretical Investigations of the Oxidatively induced reactivity of the complex [Fe2(CO)4(κ2-dmpe)(µ-adtBn)] related to the Active Site of [FeFe]-Hydrogenases. Chemistry - A European Journal, In press, ⟨10.1002/chem.201802980⟩. ⟨hal-01845050⟩
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