Mechanism of Alkaline Hydrolysis of Cyclic and Acyclic Sulfates: An ab Initio Study with Solvation Correction

Abstract

The large difference in the activation barriers for the alkaline hydrolysis of cyclic and acyclic sulfate esters (the activation barrier of the cyclic sulfate is 10.3 kcal/mol lower than that for the acyclic sulfate, leading to 106−107-fold rate acceleration) is investigated. Ab initio studies of the reaction paths for the basic hydrolysis of ethylene sulfate (ES) and dimethyl sulfate (DMS) have been performed in vacuum and in solution. The calculations focus on the attack of the hydroxyl ion on sulfur, the rate-determining step for these reactions. In analogy with the calculated results for the isoelectronic phosphate esters (EP and DMP), differential solvation is the dominant factor that leads to the faster rate of hydrolysis of the cyclic ester. In both systems, the preferential solvation of the cyclic ester transition states is due primarily to the greater exposure and resulting stabilization of the attacking hydroxide ion. Although the differential solvation effects are the same, the overall effect o...