This study aimed to demonstrate the behavior of different complexes using IR spectroelectrochemistry (SEC), a technique that combines IR spectroscopy with electrochemistry. Four different Mn and Re catalysts for electrochemical CO2 reduction were studied in dry acetonitrile. In the case of Mn(apbpy)(CO)3Br (apbpy = 4(4-aminophenyl)-2,2'-bipyridine), SEC suggested that a very slow catalytic reduction of CO2 also occurs in acetonitrile in the absence of proton donors, but at rather negative potentials. In contrast, the corresponding Re(apbpy)(CO)3Br clearly demonstrated slow catalytic conversion at the first reduction potential. Switching to saturated CO2 solutions in a mixture of acetonitrile and 5% water as a proton donor, the SEC of Mn(apbpy)(CO)3Br displayed a faster catalytic behavior.

Chemistry Division Brookhaven National Laboratory Upton NY 11973 5000 USA

CIRCC Via Celso Ulpiani 27 70126 Bari Italy

Department of Chemistry University of Torino Via P Giuria 7 10125 Torino Italy

J Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences Dolejškova 3 18223 Prague Czech Republic

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