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Issue 5, 2015
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Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes

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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.

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

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Publication details

The article was received on 07 Oct 2014, accepted on 04 Dec 2014 and first published on 04 Dec 2014


Article type: Paper
DOI: 10.1039/C4DT03079F
Citation: Dalton Trans., 2015,44, 2122-2131
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    Exploring the effect of axial ligand substitution (X = Br, NCS, CN) on the photodecomposition and electrochemical activity of [MnX(N–C)(CO)3] complexes

    J. Agarwal, C. J. Stanton III, T. W. Shaw, J. E. Vandezande, G. F. Majetich, A. B. Bocarsly and H. F. Schaefer III, Dalton Trans., 2015, 44, 2122
    DOI: 10.1039/C4DT03079F

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