title: Mn-NHC Electrocatalysts: Increasing π Acidity Lowers the Reduction Potential and Increases the Turnover Frequency for CO2Reduction.
abstract: A new manganese(I) N-heterocyclic carbene electrocatalyst containing a benzimidazole-pyrimidine-based ligand is reported for the two-electron conversion of CO2. The increased π acidity of pyrimidine shifts the two-electron reduction to -1.77 V vs Fc/Fc+, 70 mV more positive than that for MnBr(2,2'-bipyridine)(CO)3; increased catalytic current enhancement is also observed (5.2× vs 2.1×). Theoretical analyses suggest that this heightened activity may follow from the preference for a reduction-first dehydroxylation mechanism.
authors.affiliation: Department of Chemistry and ‡Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Charles J
authors.initials: CJ
authors.lastname: Stanton
authors.affiliation: Department of Chemistry and ‡Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Jonathon E
authors.initials: JE
authors.lastname: Vandezande
authors.affiliation: Department of Chemistry and ‡Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: George F
authors.initials: GF
authors.lastname: Majetich
authors.affiliation: Department of Chemistry and ‡Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
authors.affiliation: Department of Chemistry and ‡Center for Computational Quantum Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Jay
authors.initials: J
authors.lastname: Agarwal