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An Ab Initio Study of SN2 Reactivity at C6 in Hexopyranose Derivatives. I. Influence of Dipole-dipole Interactions in the Transition Structure
Journal of Physical Chemistry A
  • Richard Dawes, Missouri University of Science and Technology
  • Kathleen M. Gough
  • Philip Gregory Hultin
Abstract
It is widely accepted that dipole-dipole interactions in the SN2 transition structure can play a dominant role in determining reaction rates. a model of this type was proposed some years ago to explain the remarkably low reactivity of galactopyranose-6-O-sulfonates toward SN2 displacement, and similar arguments have recently been restated in the context of gas-phase reactions. in this paper, we present ab initio calculations (B3LYP/6-31+G(d,p)) on model structures and an analysis of charge densities using the theory of atoms in molecules. We find that the maximum possible impact of local dipole-dipole interactions is insufficient to account for the observed reactivity differences.
Department(s)
Chemistry
Keywords and Phrases
  • Dipole-dipole interactions,
  • Galacto-configured sulfonates,
  • Hexopyranose derivatives,
  • Transition structure, Chemical bonds,
  • Chemical reactions,
  • Chloride minerals,
  • Electric charge,
  • Fluorine,
  • Hydroxylation,
  • Integration,
  • Mathematical models, Derivatives, carbohydrate,
  • carbon, article,
  • chemical structure,
  • chemistry,
  • computer simulation, Carbohydrates,
  • Carbon,
  • Computer Simulation,
  • Models, Molecular,
  • Molecular Structure
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2005, American Chemical Society (ACS), All rights reserved.
Publication Date
1-1-2005
Disciplines
Citation Information
Richard Dawes, Kathleen M. Gough and Philip Gregory Hultin. "An Ab Initio Study of SN2 Reactivity at C6 in Hexopyranose Derivatives. I. Influence of Dipole-dipole Interactions in the Transition Structure" Journal of Physical Chemistry A Vol. 109 Iss. 1 (2005) p. 213 - 217 ISSN: 1089-5639
Available at: http://works.bepress.com/richard_dawes/38/