Synthesis of New Dipyrido-Annulated N‑Heterocyclic Carbenes with Ortho Substituents

A method for the introduction of various substituents at the 4 and 8 positions of 2,10-di-<i>tert</i>-butyldipyrido­[1,2-<i>c</i>;2′,1′-<i>e</i>]­imidazolium salts, is described. The new imidazolium salts bearing substituents (R′ = Cl, SPh) at the 4 and 8 positions are synthesized in three-step procedures, and carbenes generated from the imidazolium salts can be used to give the corresponding rhodium complexes. The role of the 4,8-substituents can be either bystanders or coordinating ligands according to the nature of the metal moiety.