Carbenes in ionic liquids

The chemistry of 1,3-dialkylimidazolium-based ionic liquids (ILs) can easily be linked to that of N-heterocyclic carbenes (NHCs) in the presence of sufficiently basic counteranions. B3LYP/6-31+G*, B3LYP/aug-cc-pVTZ and MP2/6-311+G** studies show that increasing the basicity of the anionic component the relative stability of the ion pair and that of the hydrogen bonded complex of the corresponding free acid and NHC itself can be shifted toward the formation of NHC. In the case of the acetate anion, the ion pair and the NHC-acetic acid complex have similar stability. Photoelectron spectroscopic studies show that the vapor of EMIM-acetate is dominated by the NHC-acetic acid complex. The mass spectrum of the same compound shows the presence of both acetic acid and 1-ethyl-3-methylimidazolium-2-ylidene, in agreement with the low pressure during the MS experiment, which facilitates dissociation. The possibility of systematic and simple variation of the NHC content of the ILs facilitates the extension of carbene chemistry in ionic liquids.