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.

Goy, R., Bertini, L., Görls, H., DE GIOIA, L., Talarmin, J., Zampella, G., et al. (2015). Silicon-Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures. CHEMISTRY-A EUROPEAN JOURNAL, 21(13), 5061-5073 [10.1002/chem.201406087].

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

BERTINI, LUCA
;
DE GIOIA, LUCA;ZAMPELLA, GIUSEPPE
;
2015

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.
Articolo in rivista - Articolo scientifico
density functional calculations; enzyme models; hydrogen; protonation; sulfur; Chemistry (all)
English
2015
21
13
5061
5073
none
Goy, R., Bertini, L., Görls, H., DE GIOIA, L., Talarmin, J., Zampella, G., et al. (2015). Silicon-Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures. CHEMISTRY-A EUROPEAN JOURNAL, 21(13), 5061-5073 [10.1002/chem.201406087].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/97057
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