Reversible Carbene Formation in the Ionic Liquid 1‐Ethyl‐3‐Methylimidazolium Acetate by Vaporization and Condensation

The role of N‐heterocyclic carbenes in the chemistry of ionic liquids based on imidazolium salts has long been discussed. Here, we present experimental evidence that 1‐ethyl‐3‐methylimidazolium‐2‐ylidene (EMIm) can coexist with its protonated imidazolium cation (EMImH⁺) at low temperatures. If the vapor of the ionic liquid EMImH⁺]AcO^?] is trapped in solid argon or nitrogen at 9 K, only acetic acid (AcOH) and the carbene, but no ionic species, are found by IR spectroscopy. This indicates that during the evaporation of EMImH⁺]AcO^?] proton transfer occurs to form the neutral species. If the vapor of EMImH⁺]AcO^?] is trapped at 9 K as film in the absence of a host matrix, a solid consisting of EMImH⁺, EMIm, AcO^?, and AcOH is formed. During warming to room temperature the proton transfer in the solid to form back the IL EMImH⁺]AcO^?] can be monitored by IR spectroscopy. This clearly demonstrates that evaporation and condensation of the IL EMImH⁺]AcO^?] results in a double proton transfer, and the carbene EMIm is only metastable even at low temperatures.