Intramolecular Nonbonded Attractive Interactions: 1-Substituted Propenes

Whereas cis-substituted alkenes are normally significantly less stable than the trans-isomers, there is a group of 1-substituted propenes (X = F, OMe, Cl, Br, SMe) where the cis-isomers are the more stable. The calculated structures show that there is steric repulsion with the cis-isomers. However,...

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Published inJournal of chemical theory and computation Vol. 5; no. 4; pp. 1033 - 1037
Main Authors Wiberg, Kenneth B, Wang, Yi-gui, Petersson, George A, Bailey, William F
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 14.04.2009
Subjects
Quantum Electronic Structure
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Summary:Whereas cis-substituted alkenes are normally significantly less stable than the trans-isomers, there is a group of 1-substituted propenes (X = F, OMe, Cl, Br, SMe) where the cis-isomers are the more stable. The calculated structures show that there is steric repulsion with the cis-isomers. However, this is overcome by attractive Coulombic interactions when X = F or OMe and by attractive dispersive interactions when X = Cl or Br. It was possible to calculate the magnitude of the latter term via the summation of the appropriate MP2 pair energies. The calculated and observed energy differences could be reproduced by a summation of steric, electrostatic, and dispersive interactions.
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ISSN:1549-9618
1549-9626
DOI:10.1021/ct900059e