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In this work, we have prepared and characterized some gold compounds wearing a N-heterocyclic carbene (NHC) ligand as well as alkynyl derivatives with different substituents. The study of their electrochemical behavior reveals that these complexes show an irreversible wave at potentials ranging between −2.79 and −2.91 V, referenced to the ferrocenium/ferrocene pair. DFT calculations indicate that the reduction occurs mainly on the aryl−C≡C fragment. The cyclic voltammetry experiments under CO2 atmosphere show an increase in the faradaic current of the reduction wave compared to the experiments under argon atmosphere, indicating a possible catalytic activity towards the carbon dioxide reduction reaction (CO2RR). [ABSTRACT FROM AUTHOR]