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Electrochemical and Computational Study of the Reactivity of a Diiron Azadithiolate Complex towards Protons in the Presence of Coordinating Anions

Abstract : In a continued effort to gain understanding of the impact of the second coordination sphere on the catalytic activity of the FeFe-H2ase models, we report the results of an electrochemical and computational study of the reactivity of [Fe2(μ-adtH)(CO)6] {1, adtH = (SCH2)2NH} towards protons in the presence of coordinating anions. The voltammetric behavior of 1 in the presence of HCl (pKa ≈ 9.5) in Bu4NPF6/MeCN is very similar to that of adtR derivatives in the presence of HBF4·Et2O (pKa ≈ 3), suggesting an effect of coordinating anion (i.e. Cl– or BF4–) rather than an effect of acid strength on the catalytic pathway. This hypothesis is supported by DFT calculations, which indicate a weak but significant interaction between Cl– and the proton of the amine group the closest to the metal center in the N-protonated and reduced form of 1.
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https://hal.univ-brest.fr/hal-01538594
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Submitted on : Tuesday, June 13, 2017 - 5:09:48 PM
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Marc Bourrez, Frederic Gloaguen. Electrochemical and Computational Study of the Reactivity of a Diiron Azadithiolate Complex towards Protons in the Presence of Coordinating Anions. European Journal of Inorganic Chemistry, Wiley-VCH Verlag, 2015, 2015 (30), pp.4986 - 4990. ⟨10.1002/ejic.201500675⟩. ⟨hal-01538594⟩

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