We have been puzzled by the involvement of weak organic and inorganic bases in the synthesis of metal‐N‐heterocyclic carbene (NHC) complexes. Such bases are insufficiently strong to permit the presumed required deprotonation of the azolium salt (the carbene precursor) prior to metal binding. Experimental and computational studies provide support for a base‐assisted concerted process that does not require free NHC formation. The synthetic protocol was found applicable to a number of Transition Metal‐ and Main Group‐centered NHC compounds and could become the synthetic route of choice to form M‐NHC bonds.
- N-Heterocyclic carbene
- Weak base