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Influence of the number of water molecules on the mechanism of N-sulfinylaniline hydrolysis

Title:

Influence of the number of water molecules on the mechanism of N-sulfinylaniline hydrolysis

Ivanova, Elena V. and Muchall, Heidi M. (2005) Influence of the number of water molecules on the mechanism of N-sulfinylaniline hydrolysis. Canadian Journal of Chemistry, 83 (9). pp. 1588-1596. ISSN 0008-4042

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Official URL: http://dx.doi.org/10.1139/v05-171

Abstract

The mechanism of the uncatalyzed hydrolysis of N-sulfinylaniline (Ph-N=S=O) has been studied with B3LYP/6-31+G(2d,2p) in the gas phase, with explicit treatment of water molecules. Hydrolysis involves water attack on sulfur, with a close to perpendicular alignment of a water molecule and the NSO plane in both prereaction complexes and transition states for the rate-determining step. Consequently, the distance of the weak S···O interaction, together with the efficiency of protonation of either nitrogen (attack across the N=S bond) or oxygen (attack across the S=O bond) atoms of the NSO group, determines the height of the activation barrier for hydrolysis. While the reaction with one water molecule is characterized by an unreasonably high enthalpy of activation, a cooperative effect from the weak interactions appears with the inclusion of a second water molecule, where both participate in the reaction, and the activation enthalpy drops significantly. The preference for attack across the S=O bond that is found in the reaction with one water molecule switches to a dominance of attack across the N=S bond in the reaction with three water molecules.

Divisions:Concordia University > Faculty of Arts and Science > Chemistry and Biochemistry
Item Type:Article
Refereed:Yes
Authors:Ivanova, Elena V. and Muchall, Heidi M.
Journal or Publication:Canadian Journal of Chemistry
Date:September 2005
Funders:
  • Natural Sciences and Engineering Research Council of Canada
Keywords:N-sulfinylaniline, hydrolysis, mechanism, density functional theory (DFT)
ID Code:6764
Deposited By:DANIELLE DENNIE
Deposited On:12 Jul 2010 16:44
Last Modified:08 Dec 2010 18:09
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