Issue 37, 2016

A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution

Abstract

Cobalt dithiolene complexes are a new class of H2-evolving catalysts. Here we describe the preparation, the structure and the catalytic activity of an original cobalt complex using a bioinspired ligand, a quinoxaline–pyran-fused dithiolene derivative (qpdt2−) that mimics the molybdopterin cofactor present in the active sites of formate dehydrogenases. This complex displays very good activity for electrochemical proton reduction under weak acid conditions in terms of turnover frequency, faradic yields and stability. Density functional theory calculations show that protonation of a nitrogen atom of the ligand decreases overpotentials by 520 mV and H2 formation proceeds via protonation of an intermediate Co–H hydride, with an adjacent S atom of the dithiolene ligand serving as a proton relay.

Graphical abstract: A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution

Supplementary files

Article information

Article type
Paper
Submitted
09 mei 2016
Accepted
03 jul 2016
First published
04 jul 2016

Dalton Trans., 2016,45, 14754-14763

A cobalt complex with a bioinspired molybdopterin-like ligand: a catalyst for hydrogen evolution

T. Fogeron, J. Porcher, M. Gomez-Mingot, T. K. Todorova, L. Chamoreau, C. Mellot-Draznieks, Y. Li and M. Fontecave, Dalton Trans., 2016, 45, 14754 DOI: 10.1039/C6DT01824F

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