Electrocatalytic CO(2) Reduction with a Binuclear Bis‐Terpyridine Pyrazole‐Bridged Cobalt Complex

A pyrazole‐based ligand substituted with terpyridine groups at the 3 and 5 positions has been synthesized to form the dinuclear cobalt complex 1, that electrocatalytically reduces carbon dioxide (CO(2)) to carbon monoxide (CO) in the presence of Brønsted acids in DMF. Chemical, electrochemical and UV‐vis spectro‐electrochemical studies under inert atmosphere indicate pairwise reduction processes of complex 1. Infrared spectro‐electrochemical studies under CO(2) and CO atmosphere are consistent with a reduced CO‐containing dicobalt complex which results from the electroreduction of CO(2). In the presence of trifluoroethanol (TFE), electrocatalytic studies revealed single‐site mechanism with up to 94 % selectivity towards CO formation when 1.47 M TFE were present, at −1.35 V vs. Saturated Calomel Electrode in DMF (0.39 V overpotential). The low faradaic efficiencies obtained (<50 %) are attributed to the generation of CO‐containing species formed during the electrocatalytic process, which inhibit the reduction of CO(2).