title: Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)3] complexes.
abstract: The synthesis, electrochemical activity, and relative photodecomposition rate is reported for four new Mn(i) N-heterocyclic carbene complexes: [MnX(N-ethyl-N'-2-pyridylimidazol-2-ylidine)(CO)3] (X = Br, NCS, CN) and [MnCN(N-ethyl-N'-2-pyridylbenzimidazol-2-ylidine)(CO)3]. All compounds display an electrocatalytic current enhancement under CO2 at the potential of the first reduction, which ranges from -1.53 V to -1.96 V versus the saturated calomel electrode. Catalytic CO production is observed for all species during four-hour preparative-scale electrolysis, but substantial H2 is detected in compounds where X is not Br. All species eventually decompose under both 350 nm and 420 nm light, but cyanide substituted complexes (X = CN) last significantly longer (up to 5×) under 420 nm light as a result of a blue-shifted MLCT band.
authors.affiliation: Center for Computational Quantum Chemistry, University of Georgia, Athens, GA, USA. jagarwal@uga.edu.
authors.forename: Jay
authors.initials: J
authors.lastname: Agarwal
authors.forename: Charles J
authors.initials: CJ
authors.lastname: Stanton Iii
authors.forename: Travis W
authors.initials: TW
authors.lastname: Shaw
authors.forename: Jonathon E
authors.initials: JE
authors.lastname: Vandezande
authors.forename: George F
authors.initials: GF
authors.lastname: Majetich
authors.forename: Andrew B
authors.initials: AB
authors.lastname: Bocarsly
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer Iii