Bis-NHC precursors composed of an azolium and a 2-halogenoazole group connected by different linkers have been site-selectively metallated to give heterobimetallic complexes from a single-frame bis-NHC ligand. The azolium group reacts with a base and oxidized metal centers to give NHC complexes with no participation of the halogenoazole, while the halogenoazole reacts in an oxidative addition with low-valent transition metals to give azolato complexes with no participation of the azolium group.