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Hydrogen Evolution Reactions Catalyzed by a Bis(thiosemicarbazone) Cobalt Complex: An Experimental and Theoretical Study
Author(s) -
Straistari Tatiana,
Hardré Renaud,
Fize Jennifer,
Shova Sergiu,
Giorgi Michel,
Réglier Marius,
Artero Vincent,
Orio Maylis
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201801155
Subject(s) - cobalt , semicarbazone , catalysis , chemistry , hydrogen , inorganic chemistry , stereochemistry , organic chemistry
The synthesis and characterization of a dinuclear bis(thiosemicarbazone) cobalt complex [Co 2 L 2 (NCS) 2 ] is reported. This complex exhibits significant catalytic activity for hydrogen production in DMF by using triethylammonium (Et 3 NHBF 4 ) 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.