Influence of the Bis-Carbene Ligand on Manganese Catalysts for CO 2 Electroreduction.

Autor: Richter ML; Institute of Advanced Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I, Av. Vicente Sos Baynat s/n., E-12071, Castellón, Spain., Peris E; Institute of Advanced Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I, Av. Vicente Sos Baynat s/n., E-12071, Castellón, Spain., Gonell S; Institute of Advanced Materials (INAM), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Jaume I, Av. Vicente Sos Baynat s/n., E-12071, Castellón, Spain.
Jazyk: angličtina
Zdroj: ChemSusChem [ChemSusChem] 2024 Jul 04, pp. e202401007. Date of Electronic Publication: 2024 Jul 04.
DOI: 10.1002/cssc.202401007
Abstrakt: First row transition metal complexes have attracted attention as abundant and affordable electrocatalysts for CO 2 reduction. Manganese complexes bearing bis-N-heterocyclic carbene ligands defining 6-membered ring metallacycles have proven to reduce CO 2 to CO selectively at very high rates. Herein, we report the synthesis of manganese carbonyl complexes supported by a rigid ortho-phenylene bridged bis-N-heterocyclic carbene ligand (ortho-phenylene-bis(N-methylimidazol-2-ylidene), Ph-bis-mim), which defines a 7-membered ring metallacycle. We performed a comparative study with the analogues complexes bearing an ethylene-bis(N-methylimidazol-2-ylidene) ligand (C 2 H 4 -bis-mim) and a methylene-bis(N-methylimidazol-2-ylidene) ligand (CH 2 -bis-mim), and found that catalysts comprising a seven-membered metallacycle retain similar selectivity and activity as those with six-membered metallacycles, while reducing the overpotential by 120-190 mV. Our findings reveal general design principles for manganese bis-N-heterocyclic carbene electrocatalysts, which can guide further designs of affordable, fast and low overpotential catalysts for CO 2 electroreduction.
(© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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