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Reactivity of the Excited States of the H-Cluster of FeFe Hydrogenases

Abstract : FeFe hydrogenases catalyze H-2 oxidation and formation at an inorganic active site (the "H-cluster"), which consists of a [Fe-2(CO)(3)(CN)(2)(dithiomethylamine)] subcluster covalently attached to a Fe4S4 subcluster. This active site is photosensitive: visible light has been shown to induce the release of exogenous CO (a reversible inhibitor of the enzyme), shuffle the intrinsic CO ligands, and even destroy the H-cluster. These reactions must be understood because they may negatively impact the Use of hydrogenase for the photoproduction of H-2. Here, we explore in great detail the reactivity of the excited states of the H-duster under catalytic conditions by examining, both experimentally and using TDDFT calculations, the simplest photochemical reaction: the binding and release of exogenous CO. A simple dyad model can be used to predict which excitations are active. This could be used for probing other, aspects of the photoreactivity of the H-cluster.
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Matteo Sensi, Carole Baffert, Claudio Greco, Giorgio Caserta, Charles Gauquelin, et al.. Reactivity of the Excited States of the H-Cluster of FeFe Hydrogenases. Journal of the American Chemical Society, American Chemical Society, 2016, 138 (41), pp.13612-13618. ⟨10.1021/jacs.6b06603⟩. ⟨hal-01400732⟩



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