Hydrolysis of imidazole-2-ylidenes.

The direct reaction of an imidazole-2-ylidene in a predominantly aqueous environment [about 0.1 M solution in a H(2)O (>60%)/THF solvent system] was investigated for the first time. The reaction yielded a stable solution of the corresponding imidazolium-hydroxide of pH 13, which is in agreement with results from an ab initio molecular dynamics simulation. In contrast, hydrolysis of the carbene in a mainly aprotic environment (>80% THF) gives a hydrogen-bridged carbene-water complex which could be detected by NMR and IR spectroscopies for the first time. This complex converts slowly to two isomeric ring opened products and is at higher water concentration in dynamic equilibrium with the imidazolium hydroxide. A computational mechanistic study of the carbene hydrolysis with a gradually increasing number of water molecules revealed that the imidazolium-hydroxide structure can only be optimized with three or more water molecules as reactants, and with the increasing number of water molecules its stability is increasing with respect to the carbene-water complex. In agreement with the experimental results, these findings point out that solvent stabilization and basicity of the hydroxide ion plays a crucial role in the reaction. With increasing number of water molecules the barriers connecting the reaction intermediates are getting smaller, and the ring opened hydrolysis products can be derived from imidazolium-hydroxide type intermediates. Computational studies on the hydrolysis of a nonaromatic imidazolidine-2-ylidene analogue clearly indicated the analogous ring-opened product to be by 10-12 kcal/mol more stable than the appropriate ion pair and the carbene-water complex, in agreement with the known aromatic stabilization of imidazol-2-ylidenes. Accordingly, these molecules hydrolyze with exclusive formation of the ring-opened product.