Silicon–Heteroaromatic [FeFe] Hydrogenase Model Complexes: Insight into Protonation, Electrochemical Properties, and Molecular Structures. Issue 13 (17th February 2015)

• Record Type: Journal Article
• Authors: Goy, Roman; Bertini, Luca; Görls, Helmar; De Gioia, Luca; Talarmin, Jean; Zampella, Giuseppe; Schollhammer, Philippe; Weigand, Wolfgang
• Is Part Of: Chemistry. Volume 21:Issue 13(2015)
• Page Start: 5061
• Page End: 5073
• Publication Date: 2015-02-17
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201406087
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>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.</p> </abstract>