biostudies-literatureUnknown13(5)Hong WSelective reduction of CO₂ is an efficient solution for producing nonfossil-based chemical feedstocks and simultaneously alleviating the increasing atmospheric concentration of this greenhouse gas. With this aim, molecular electrocatalysts are being extensively studied, although selectivity remains an issue. In this work, a combined experimental-computational study explores how the molecular structure of Mn-based complexes determines the dominant product in the reduction of CO₂ to HCOOH, CO, and H₂. In contrast to previous Mn(bpy-R)(CO)₃Br catalysts containing alkyl amines in the vicinity of the Br ligand, here, we report that bpy-based macrocycles locking these amines at the side opposite to the Br ligand change the product selectivity from HCOOACS catalysis3109-3119https://www.ebi.ac.uk/biostudies/studies/S-EPMC9990071biostudies-literatureExploring the Parameters Controlling Product Selectivity in Electrochemical CO₂ Reduction in Competition with Hydrogen Evolution Employing Manganese Bipyridine Complexes.PMC9990071Nova AHammershoj HCDCastro ACSkrydstrup TLuthra MHong WPedersen SUBalcells DMadsen MRJakobsen JBDaasbjerg KfalseExploring the Parameters Controlling Product Selectivity in Electrochemical CO₂ Reduction in Competition with Hydrogen Evolution Employing Manganese Bipyridine Complexes.Selective reduction of CO₂ is an efficient solution for producing nonfossil-based chemical feedstocks and simultaneously alleviating the increasing atmospheric concentration of this greenhouse gas. With this aim, molecular electrocatalysts are being extensively studied, although selectivity remains an issue. In this work, a combined experimental-computational study explores how the molecular structure of Mn-based complexes determines the dominant product in the reduction of CO₂ to HCOOH, CO, and H₂. In contrast to previous Mn(bpy-R)(CO)₃Br catalysts containing alkyl amines in the vicinity of the Br ligand, here, we report that bpy-based macrocycles locking these amines at the side opposite to the Br ligand change the product selectivity from HCOO2023-01-01T00:00:00Z2023 Mar2025-04-19T16:36:49.76Z2025-04-19T16:36:49.76ZS-EPMC99900713691087510.1021/acscatal.2c05951