The reactivity of bidentate Au^III–Cl species, [(C^N)AuCl₂], with a bisphosphine or carbon donor ligands results in reductive elimination. Combined experimental and computational investigations lead to the first evidence of a direct intramolecular C(sp²)–N(sp²) bond formation from a monomeric [(C^N)AuCl₂] gold(III) complex. We show that bidentate ligated Au(III) systems bypass transmetallation to form C(sp²)–N(sp²) species and NHC–Au–Cl. Mechanistic investigations of the reported transformation reveal a ligand-induced reductive elimination via a key Au^III intermediate. Kinetic studies of the reaction support a second-order rate process.