Home > Articles > Published articles > Unravelling the Mechanistic Pathway of the Hydrogen Evolution Reaction Driven by a Cobalt Catalyst |
Date: | 2022 |
Abstract: | A cobalt complex bearing a κ-NP ligand is presented (1 or Co(L), where L is (1E,1'E)-1,1'-(pyridine-2,6-diyl)bis(N-(3-(diphenylphosphanyl)propyl)ethan-1-imine). Complex 1 is stable under air at oxidation state Co thanks to the π-acceptor character of the phosphine groups. Electrochemical behavior of 1 reveals a two-electron Co/Co oxidation process and an additional one-electron reduction, which leads to an enhancement in the current due to hydrogen evolution reaction (HER) at E=−1. 6 V vs Fc/Fc. In the presence of 1 equiv of bis(trifluoromethane)sulfonimide, 1 forms the cobalt hydride derivative Co(L)-H (2), which has been fully characterized. Further addition of 1 equiv of CoCp* (Cp* is pentamethylcyclopentadienyl) affords the reduced Co(L)-H (2) species, which rapidly forms hydrogen and regenerates the initial Co(L) (1). The spectroscopic characterization of catalytic intermediates together with DFT calculations support an unusual bimolecular homolytic mechanism in the catalytic HER with 1. |
Grants: | Agencia Estatal de Investigación PID2019-111617RB-I00 Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-1631 Ministerio de Ciencia e Innovación CEX2019-000925-S Agencia Estatal de Investigación PID2019-104171-RB-I00 |
Note: | Altres ajuts: acords transformatius de la UAB |
Rights: | Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades. |
Language: | Anglès |
Document: | Article ; recerca ; Versió publicada |
Subject: | Catalysis ; Hydrogen Evolution Reaction ; Ligands ; Molecular Catalysis ; Reaction Mechanism |
Published in: | Angewandte Chemie (International ed. Internet), Vol. 61, Issue 40 (October 2022) , art. e20220905, ISSN 1521-3773 |
9 p, 984.7 KB |