title: Intramolecular Nonbonded Attractive Interactions: 1-Substituted Propenes.
abstract: 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.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, and Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060.
authors.forename: Kenneth B
authors.initials: KB
authors.lastname: Wiberg
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, and Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060.
authors.forename: Yi-Gui
authors.initials: YG
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, and Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060.
authors.forename: George A
authors.initials: GA
authors.lastname: Petersson
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, Wesleyan University, Middletown, Connecticut 06459-0180, and Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060.
authors.forename: William F
authors.initials: WF
authors.lastname: Bailey