Theoretical Models for Solvation and Catalysis in Carbonyl Addition

Ian H. Williams, Dale Spangler, Douglas A. Femec, Gerald M. Maggiora, Richard L. Schowen

Research output: Contribution to journalArticle

Abstract

Alternative modes of catalysis of formaldehyde hydration by a single ancillary water molecule are investigated by ab initio calculations at the STO-3G level. A cyclic transition state (FW2†) involving formaldehyde with two molecules of water is characterized and is only 0.8 kcal mol-1 higher in energy than the isolated reactants. The results indicate that gas-phase formaldehyde hydration probably proceeds via FW2† in a concerted mechanism with a Gibbs free energy of activation of 27 kcal mol-1. Addition of a water dimer to formaldehyde via FW2* is predicted to occur in water with a Gibbs free energy of activation of 16 kcal mol-1, in agreement with experiment. Empirical extrapolation to the liquid phase of entropies of activation calculated for reaction of one or two waters in the gas phase suggests that a mechanism involving three water molecules would be consistent with experiments for dioxan solution. Specific solvation by four water molecules is predicted to stablize the zwitterionic adduct H2O+CH2O- (an unbound state in the gas phase) by 111 kcal mol-1 relative to H2O+CH2O- and 4H2O or by 37 kcal mol-1 relative to (H2O)3 and CH22H2O. Thus a stepwise mechanism for formaldehyde hydration also may be feasible, although the energy barrier to formation of a solvated zwitterionic intermediate has not yet been calculated.

Original languageEnglish
Pages (from-to)31-40
Number of pages10
JournalJournal of the American Chemical Society
Volume105
Issue number1
DOIs
Publication statusPublished - 1 Jan 1983

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this