Bioinspired Tungsten Dithiolene Catalysts for Hydrogen Evolution: A Combined Electrochemical, Photochemical, and Computational Study

Bis­(dithiolene)­tungsten complexes, WVIO2 (L = dithiolene)2 and WIVO (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduct...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2015-10, Vol.119 (43), p.13524-13533
Main Authors: Gomez-Mingot, Maria, Porcher, Jean-Philippe, Todorova, Tanya K, Fogeron, Thibault, Mellot-Draznieks, Caroline, Li, Yun, Fontecave, Marc
Format: Article
Language:English
Subjects:
Biomimetics
Catalysis
Electrochemical Techniques
Formate Dehydrogenases - chemistry
Formate Dehydrogenases - metabolism
Hydrogen - chemistry
Molecular Structure
Organometallic Compounds - chemistry
Photochemical Processes
Protons
Quantum Theory
Sulfhydryl Compounds - chemistry
Tungsten - chemistry
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Summary:Bis­(dithiolene)­tungsten complexes, WVIO2 (L = dithiolene)2 and WIVO (L = dithiolene)2, which mimic the active site of formate dehydrogenases, have been characterized by cyclic voltammetry and controlled potential electrolysis in acetonitrile. They are shown to be able to catalyze the electroreduction of protons into hydrogen in acidic organic media, with good Faradaic yields (75–95%) and good activity (rate constants of 100 s–1), with relatively high overpotentials (700 mV). They also catalyze proton reduction into hydrogen upon visible light irradiation, in combination with [Ru­(bipyridine)3]2+ as a photosensitizer and ascorbic acid as a sacrificial electron donor. On the basis of detailed DFT calculations, a reaction mechanism is proposed in which the starting WVIO2 (L = dithiolene)2 complex acts as a precatalyst and hydrogen is further formed from a key reduced W–hydroxo–hydride intermediate.
ISSN:1520-6106
1520-5207
DOI:10.1021/acs.jpcb.5b01615