Theoretical study on the role of cooperative solvent molecules in the neutral hydrolysis of ketene

Abstract

The results of a theoretical study of the reaction mechanism for the neutral hydration of ketene, H2C=C=O + (n + 1) H2O → CH3COOH + nH2O (n = 0–4), in solution are presented. All structures were optimized and characterized at the MP2(fc)/6-31 + G* level of theory, and then re-optimized by MP2(fc)/6-311 ++G**, and the effect of the bulk solvent is taken into account according to the conductor-like polarized continuum model (CPCM) using the gas MP2(fc)/6-311 ++G** geometries. Energies were refined for five-water hydration at higher level of theory, QCISD(T)(fc)/6-311 ++G**//MP2(fc)/6-311 ++G**. In the combined supermolecular/continuum model, one water molecule directly attacks the central C-atom, and the other four explicit water molecules are divided into two groups, one acting as catalyst(s) by participating in the proton transfer to reduce the tension of proton transfer ring, and the other being placed near the non-reactive oxygen or carbon atom in order to catalyze the hydration by engaging in hydrogen-bonding to the substrate (the so-called cooperative effect). Between the two possible nucleophilic addition reactions of water molecule, across the C=O bond or the C=C bond, the former one is preferred. Our calculations suggest that the favorable hydrolysis mechanism of ketene involves a sort of eight-membered ring transition structure formed by a three-water proton transfer loop, and a cooperative dimeric water near the non-reactive carbon-atom. The best-estimated in the present paper for the rate-determining barrier in solution, \( \Updelta G_{\text{sol}}^{ \ne } \) (298 K), is about 58 kJ/mol, reasonably close to the available experimental result.