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New Systematic Route to Mixed-Valence Triiron Clusters Derived from Dinuclear Models of the Active Site of [Fe–Fe]-Hydrogenases

Abstract : A novel reaction pathway to synthesize the linear trinuclear clusters [Fe3(CO)5(κ2-diphosphine)(μ-dithiolate)2] via the direct reaction of the dinuclear hexacarbonyl precursor [Fe2(CO)6(μ-dithiolate)] with the mononuclear species [Fe(CO)2(κ2-diphosphine)(κ2-dithiolate)] has been developed with diphosphine (dppe) and dithiolate (pdt = propanedithiolate) (1) or adtBn ({SCH2}2NBn = azadithiolate) (2). A crystallographic study was carried out on 2 and Mössbauer spectroscopy, and DFT calculations have been used to describe the electronic and structural properties of 1. The electrochemical properties of 1 in the absence and in the presence of a weak acid have been the subject of a preliminary investigation.
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https://hal.univ-brest.fr/hal-01535887
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Submitted on : Friday, June 9, 2017 - 4:18:46 PM
Last modification on : Friday, July 10, 2020 - 7:58:46 AM

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Laetitia Beaume, Martin Clémancey, Geneviève Blondin, Claudio Greco, François Y. Pétillon, et al.. New Systematic Route to Mixed-Valence Triiron Clusters Derived from Dinuclear Models of the Active Site of [Fe–Fe]-Hydrogenases. Organometallics, American Chemical Society, 2014, 33 (22), pp.6290 - 6293. ⟨10.1021/om5010594⟩. ⟨hal-01535887⟩

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