Oxidative Coupling of Anionic Abnormal N-Heterocyclic Carbenes: Efficient Access to Janus-Type 4,4′-Bis(2H-imidazol-2-ylidene)s

The oxidative coupling of anionic imidazol-4-ylidenes protected at the C2 position with [MnCp(CO)2] or BH3 led to the corresponding 4,4′-bis(2H-imidazol-2-ylidene) complexes or adducts, in which the two carbene moieties are connected through a single C−C bond. Subsequent acidic treatment of the later species led to the corresponding 4,4′-bis(imidazolium) salts in good yields. The overall procedure offers practical access to a novel class of Janus-type bis(NHC)s. Strikingly, the coplanarity of the two NHC rings within the mesityl derivative 4,4′-bis(IMes), favored by steric hindrance along with stabilizing intramolecular C−H⋅⋅⋅π aryl interactions, allows the alignment of the π-systems and, as a direct consequence, significant electron communication through the bis(carbene) scaffold. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim