A Computational Model for the Stereoelectronic Effects of Carboxylate Lone Pairs

The effects of carboxylate syn and anti lone pairs on the basicity of a water molecule were investigated using a combination of ab initio calculations and Monte Carlo simulations. This system serves as a quantitative computational model for the stereoelectronic effects of the carboxylate lone pairs. It was found that there is only a small difference in reactivity for this particular situation (1 kcal mol−1), in agreement with recent results and suggesting that earlier ideas overestimated the magnitude of the stereoelectronic effect.