A bimetallic carbene complex architecture that incorporates a cyclopentadienyl-annulated imidazol-2-ylidene moiety is characterized. The ligand architecture enables direct electronic interaction between the π- and σ-bonded metals. A preliminary example of aqueous Suzuki coupling employing a metallocene-fused imidazol-2-ylidene-derived catalyst is described.

A new phenanthrene-fused N-heterocyclic carbene was generated and characterized in solution. The synthesis of air-stable Rh, Ir, and Ag complexes, supported by the new phenanthrene-fused imidazol-2-ylidene ligand, is described. Deprotonation of phenanthrene-fused imidazolium salt 4 in the presence of [M(COD)Cl]2 (M = Rh, Ir) afforded complexes 6 and 7 in excellent yields. The silver complex was obtained by reaction of 4 with Ag2O. The solid state