1,1′-Bis(N-benzimidazolylidene)ferrocene: synthesis and study of a novel ditopic ligand and its transition metal complexes

Diiridum complexes containing 1,1′-bis(N-benzimidazolylidene)ferrocene, a novel ditopic ligand comprised of two N-heterocyclic carbenes (NHCs) linked directly via their N-substituents to each cyclopentadienyl ring of a ferrocene moiety, were synthesized. Crystallographic analyses of these C₂-symmetric bimetallic complexes revealed the benzimidazolylidene moieties were intramolecularly stacked in nearly opposing orientations, effectively forming Janus-type bis(NHC) structures in the solid state. Using a variety of electrochemical techniques, the oxidation potentials of the ferrocenyl groups in these complexes were found to depend on the auxillary ligands coordinated to the Ir centers (i.e., 1,5-cyclooctadiene vs. carbonyl). Similarly, the ν_CO of carbonyls ligated to the Ir centers varied in accord with the oxidation state of the ferrocene contained with the bis(NHC) ligand. These results suggest that the Ir and Fe centers in these complexes are electronically coupled and that the electron donating ability of the bis(NHC) ligand reported herein can be tuned electrochemically.