Silicon-Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures

Abstract : To learn from Nature how to create an efficient hydrogen-producing catalyst, much attention has been paid to the investigation of structural and functional biomimics of the active site of [FeFe]-hydrogenase. To understand their catalytic activities, the μ-S atoms of the dithiolate bridge have been considered as possible basic sites during the catalytic processes. For this reason, a series of [FeFe]-H2ase mimics have been synthesized and characterized. Different [FeFe]-hydrogenase model complexes containing bulky Si–heteroaromatic systems or fluorene directly attached to the dithiolate moiety as well as their mono-PPh3-substituted derivatives have been prepared and investigated in detail by spectroscopic, electrochemical, X-ray diffraction, and computational methods. The assembly of the herein reported series of complexes shows that the μ-S atoms can be a favored basic site in the catalytic process. Small changes in the (hetero)-aromatic system of the dithiolate moiety are responsible for large differences in their structures. This was elucidated in detail by DFT calculations, which were consistent with the experimental results.
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Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (13), pp.5061 - 5073. 〈http://onlinelibrary.wiley.com/doi/10.1002/chem.201406087/abstract〉. 〈10.1002/chem.201406087〉
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http://hal.univ-brest.fr/hal-01538589
Contributeur : Nicolas Renard <>
Soumis le : mardi 13 juin 2017 - 17:00:32
Dernière modification le : mercredi 11 avril 2018 - 10:56:01

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Roman Goy, Luca Bertini, Helmar Gorls, Luca De Gioia, Jean Talarmin, et al.. Silicon-Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures. Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (13), pp.5061 - 5073. 〈http://onlinelibrary.wiley.com/doi/10.1002/chem.201406087/abstract〉. 〈10.1002/chem.201406087〉. 〈hal-01538589〉

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