Hydrogen Evolution Reactions Catalyzed by a Bis(thiosemicarbazone) Cobalt Complex: An Experimental and Theoretical Study

The synthesis and characterization of a dinuclear bis(thiosemicarbazone) cobalt complex [Co2L2(NCS)2] is reported. This complex exhibits significant catalytic activity for hydrogen production in DMF by using triethylammonium (Et3NHBF4) as the proton source. Cyclic voltammetry data allowed a maximum...

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Bibliographic Details
Published in:Chemistry : a European journal 2018-06, Vol.24 (35), p.8779-8786
Main Authors: Straistari, Tatiana, Hardré, Renaud, Fize, Jennifer, Shova, Sergiu, Giorgi, Michel, Réglier, Marius, Artero, Vincent, Orio, Maylis
Format: Article
Language:English
Subjects:
Catalysis
Catalytic activity
Chemistry
Cobalt
Cobalt compounds
Coordination compounds
electrocatalysts
Electrolysis
Gas analysis
hydrogen evolution reaction
Hydrogen evolution reactions
Hydrogen production
Ligands
Metals
Organic chemistry
Protonation
Quantum chemistry
redox-active ligands
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Summary:The synthesis and characterization of a dinuclear bis(thiosemicarbazone) cobalt complex [Co2L2(NCS)2] is reported. This complex exhibits significant catalytic activity for hydrogen production in DMF by using triethylammonium (Et3NHBF4) as the proton source. Cyclic voltammetry data allowed a maximum turnover frequency of 130 s−1 for 1 m proton concentration to be determined. The catalytic nature of the process and the production of dihydrogen were confirmed by gas analysis during controlled potential electrolysis experiments. Quantum chemical calculations show that the complex displays a ligand‐assisted metal‐centered reactivity and supports a catalytic mechanism involving ligand‐based reduction and protonation steps followed by metal‐centered processes. Center of attraction: A dinuclear cobalt complex based on a thiosemicarbazone ligand is an efficient electrocatalyst for hydrogen evolution reactions. The catalytic mechanism involves ligand‐based reductions alternating with protonation steps consistent with an unusual ligand‐assisted metal‐centered reactivity (see scheme).
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201801155