The straightforward synthetic protocol leading to carbene-metal-amido (CMA) complexes (metal = Au, Cu) using a mild base and an environmentally desirable solvent (EtOH) is explored, with a focus on complexes bearing backbone-substituted N-heterocyclic carbene (NHC) ligands, including BIAN-NHCs (BIAN = bis(imino)acenaphthene). The novel CMAs are structurally characterized and the gold-based CMAs bearing diverse NHCs are screened as simple, Brønsted-basic pre-catalysts. The readily accessible complexes display high catalytic activity in the intermolecular and intramolecular hydrocarboxylation of internal alkynes and alkynoic acids respectively, while the screening reveals the ancillary ligand effect of NHCs in these catalytic systems.