4,5-Bis(dialkylamino)-substituted imidazolium systems: facile access to N-heterocyclic carbenes with self-umpolung option.

The first synthesis of 4,5-bis-(dimethylamino)-substituted imidazolium compounds was developed, which is based on the reaction of a 1,2-diamino-1,2-bis(phosphonio)ethene with lithiated formamidines. This represents the first application of this class of ethene derivatives for the preparation of heterocycles. These N-heterocyclic carbene (NHC) precursors show a remarkably reduced basicity and nucleophilicity of their NMe2 groups, which is due to the strong anomeric interactions of the latter with the imidazolium core. According to DFT calculations, these NHCs are capable of self-umpolung if sufficiently strong acceptor substituents are introduced at the carbene center. To test the self-umpolung capabilities of the NHCs, various substituents were attached to the carbene center and the obtained compounds were characterized by single-crystal X-ray analysis as well as quantum chemical computations. Strong acceptor substituents are required to induce self-umpolung, such as in the phosphonio-substituted derivative, for which partial self-umpolung was found. The N,N′-bis(4-dimethylaminophenyl)-substituted imidazolium compound represents a special case, as it incorporates as much as three two-step redox systems within the NHC framework. This will probably result in a high electronic flexibility of the corresponding nucleophilic carbenes, especially when they serve as ligands in transition metal complexes.