biostudies-literatureRichter MLUniversitat Jaume IMinisterio de Ciencia e Innovacióne202401007https://www.ebi.ac.uk/biostudies/studies/S-EPMC11660741biostudies-literatureUnknown17(24)First row transition metal complexes have attracted attention as abundant and affordable electrocatalysts for CO₂ reduction. Manganese complexes bearing bis-N-heterocyclic carbene ligands defining 6-membered ring metallacycles have proven to reduce CO₂ 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 (C₂H₄-bis-mim) and a methylene-bis(N-methylimidazol-2-ylidene) ligand (CH₂-bis-miChemSusChemInfluence of the Bis-Carbene Ligand on Manganese Catalysts for CO<sub>2</sub> Electroreduction.PMC11660741UJI-A2021-09IJC2019-039982-IPID2021-127862NB-I00TED2021-130647B-I00TRANSUJI/2023/10Richter MLGonell SPeris EfalseInfluence of the Bis-Carbene Ligand on Manganese Catalysts for CO<sub>2</sub> Electroreduction.First row transition metal complexes have attracted attention as abundant and affordable electrocatalysts for CO₂ reduction. Manganese complexes bearing bis-N-heterocyclic carbene ligands defining 6-membered ring metallacycles have proven to reduce CO₂ 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 (C₂H₄-bis-mim) and a methylene-bis(N-methylimidazol-2-ylidene) ligand (CH₂-bis-mi2024-01-01T00:00:00Z2024 Dec2025-04-18T14:41:08.941Z2025-04-07T00:58:38.156ZS-EPMC116607413896294810.1002/cssc.202401007