Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N-C)(CO)3] complexes

Jay Agarwal, Charles J. Stanton, Travis W. Shaw, Jonathon E. Vandezande, George F. Majetich, Andrew Bruce Bocarsly, Henry F. Schaefer

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38 Scopus citations

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 5x) under 420 nm light as a result of a blue-shifted MLCT band.

Original languageEnglish (US)
Pages (from-to)2122-2131
Number of pages10
JournalDalton Transactions
Volume44
Issue number5
DOIs
StatePublished - Feb 7 2015

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry

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