Influence of alkali metal cations upon the Kolbe-Schmitt reaction mechanism.

The mechanisms of the carboxylations of lithium, potassium, rubidium, and cesium phenoxides are investigated by means of the DFT method with the LANL2DZ basis set. It is shown that the reactions of all alkali metal phenoxides with carbon dioxide occur via very similar reaction mechanisms. The reactions can proceed in the ortho and para positions. The exception is lithium phenoxide which yields only salicylic acid in the Kolbe-Schmitt reaction. It is found that the yield of the para substituted product increases with increasing the ionic radius of the alkali metal used. An explanation for this experimental and theoretical observation is proposed.