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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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https://hal.univ-brest.fr/hal-01845050
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Submitted on : Friday, July 20, 2018 - 9:29:13 AM
Last modification on : Thursday, October 3, 2019 - 8:50:02 AM

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Federica Arrigoni, Salma Mohamed Bouh, Catherine Elleouet, Philippe 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, Wiley-VCH Verlag, In press, ⟨10.1002/chem.201802980⟩. ⟨hal-01845050⟩

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