Oxidative Coupling of Anionic Abnormal N‐Heterocyclic Carbenes: Efficient Access to Janus‐Type 4,4′‐Bis(2H‐imidazol‐2‐ylidene)s |
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| Authors: | Alina A Grineva Dr Dmitry A Valyaev Dr Vincent César Dr Oleg A Filippov Prof?Dr Victor N Khrustalev Prof?Dr Sergei E Nefedov Dr Noël Lugan |
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| Institution: | 1. LCC-CNRS, Université de Toulouse, CNRS, France;2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia;3. A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Russian Academy of Sciences, Moscow, Russia;4. Peoples Friendship University of Russia (RUDN University), Moscow, Russia;5. National Research Center “Kurchatov Institute”, Moscow, Russia |
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| Abstract: | 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. |
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| Keywords: | carbene ligands electronic communication manganese N-heterocyclic carbenes oxidative coupling |
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