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Click-Derived Triazoles and Triazolylidenes of Manganese for Electrocatalytic Reduction of CO2

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Detalhes bibliográficos
Resumo:A series of new fac-[Mn(L)(CO)3 Br] complexes where L is a bidentate chelating ligand containing mixed mesoionic triazolylidene-pyridine (MICˆpy, 1), triazolylidene-triazole (MICˆtrz, 2), and triazole-pyridine (trzˆpy, 3) ligands have been prepared and fully characterized, including the single crystal X-ray diffraction studies of 1 and 2. The abilities of 1–3 and complex fac-[Mn(MICˆMIC)(CO)3 Br] (4) to catalyze the electroreduction of CO2 has been assessed for the first time. It was found that all complexes displayed a current increase under CO2 atmosphere, being 3 and 4 the most active complexes. Complex 3, bearing a NˆN-based ligand exhibited a good efficiency and an excellent selectivity for reducing CO2 to CO in the presence of 1.0 M of water, at low overpotential. Interestingly, complex 4 containing the strongly electron donating di-imidazolylidene ligand exhibited comparable activity to 3, when the experiments were performed in neat acetonitrile at slightly higher overpotential (−1.86 vs. −2.14 V).
Autores principais:Friães, Sofia
Outros Autores:Realista, Sara; Gomes, Clara S. B.; Martinho, Paulo N.; Royo, Beatriz
Assunto:Electrocatalytic CO reduction Manganese Mesoionic carbenes Analytical Chemistry Chemistry (miscellaneous) Molecular Medicine Pharmaceutical Science Drug Discovery Physical and Theoretical Chemistry Organic Chemistry
Ano:2021
País:Portugal
Tipo de documento:artigo
Tipo de acesso:acesso aberto
Instituição associada:Universidade Nova de Lisboa
Idioma:inglês
Origem:Repositório Institucional da UNL
Descrição
Resumo:A series of new fac-[Mn(L)(CO)3 Br] complexes where L is a bidentate chelating ligand containing mixed mesoionic triazolylidene-pyridine (MICˆpy, 1), triazolylidene-triazole (MICˆtrz, 2), and triazole-pyridine (trzˆpy, 3) ligands have been prepared and fully characterized, including the single crystal X-ray diffraction studies of 1 and 2. The abilities of 1–3 and complex fac-[Mn(MICˆMIC)(CO)3 Br] (4) to catalyze the electroreduction of CO2 has been assessed for the first time. It was found that all complexes displayed a current increase under CO2 atmosphere, being 3 and 4 the most active complexes. Complex 3, bearing a NˆN-based ligand exhibited a good efficiency and an excellent selectivity for reducing CO2 to CO in the presence of 1.0 M of water, at low overpotential. Interestingly, complex 4 containing the strongly electron donating di-imidazolylidene ligand exhibited comparable activity to 3, when the experiments were performed in neat acetonitrile at slightly higher overpotential (−1.86 vs. −2.14 V).