Mechanisms of hydrogen evolution by six-coordinate cobalt complexes: a density functional study on the role of a redox-active pyridinyl-substituted diaminotriazine benzamidine ligand as a proton relay.
Dalton Trans
; 53(13): 6006-6019, 2024 Mar 26.
Article
em En
| MEDLINE
| ID: mdl-38469898
ABSTRACT
The hydrogen evolution reaction is an important process for energy storage. The six-coordinate cobalt complex [CoIII(L1-)(LH)]2+ (LH = N-(4-amino-6-(pyridin-2-yl)-1,3,5-triazin-2-yl)benzamidine) was found to catalyze photocatalytic hydrogen evolution. In this work, we performed density functional calculations to obtain the reduction potentials and the proton-transfer free energy of possible intermediates to determine the preferred pathways for proton reduction. The mechanism involves the metal-based reduction of Co(III) to Co(II) before the protonation at the amidinate N on the pyridinyl-substituted diaminotriazine benzamidinate ligand L1- to form [CoII(LH)(LH)]2+. Essentially, the subsequent electron transfer is not metal-based reduction, but rather ligand-based reduction to form [CoII(LH)(LHË1-)]1+. Through a proton-coupled electron transfer process, the cobalt hydride [CoIIH(LH)(LH2Ë)]1+ is formed as the key intermediate for hydrogen evolution. As the cobalt hydride complex is coordinatively saturated, a structural change is required when the hydride on Co is coupled with the proton on pyridine. Notably, the redox-active nature of the ligand results in the low acidity of the protonated pyridine moiety of LH2Ë, which impedes its function as a proton relay. Our findings suggest that separating the proton relay fragment from the electron reservoir fragment of the redox-active ligand is preferred for fully utilizing both features in catalytic H2 evolution.
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01-internacional
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MEDLINE
Idioma:
En
Ano de publicação:
2024
Tipo de documento:
Article