We have obtained preliminary ab initio results for the interaction of carbenes with water, alcohols, and dimethylether. Two types of complexes were observed: ylide-like complexes in which the oxygen on water, alcohol, or dimethylether is directed toward the carbene carbon, and hydrogen-bonded complexes in which a hydrogen bond to either the carbene or the oxygen-containing species is formed.
Further ab initio work on the oxonium complexes using larger basis sets and at higher levels of theory should shed light on questions of structure, binding energy, and electron transfer. Because of the weakly-bound nature of the hydrogen-bonded complexes, it is not clear that these structures will remain local minima on the potential energy surface at higher levels of theory. Work is in progress to investigate these systems at higher levels of theory with larger basis sets. Also, studies of the addition of the complexes to double bonds should provide information about reversibility and mechanisms.
We thank the National Center for Supercomputing Applications and Illinois State University for support of this research.