Expanding the Chemistry of Cationic <i>N</i>‐Heterocyclic Carbenes: Alternative Synthesis, Reactivity, and Coordination Chemistry

AbstractA new synthetic route to complexes of the cationic N‐heterocyclic carbene ligand 2 has been developed by the attachment of a cationic pentamethylcyclopentadienylruthenium ([RuCp*]+) fragment to a metal‐coordinated benzimidazol‐2‐ylidene ligand. The coordination chemistry and the steric and electronic properties of the cationic carbene were investigated in detail by experimental and theoretical methods. X‐ray structures of three carbene–metal complexes were determined. The cationic ligand 2 is a poorer overall electron donor relative to the related neutral carbene, which is evident from cyclic voltammetry (CV) and IR measurements.