title: A theoretical study of substituent effects on allylic ion and ion pair SN2 reactions.
abstract: An ab initio study of ionic and ion pair displacement reactions involving allylic systems has been carried out at the RHF/6-31+G* level. The geometries and natural charges show the absence of conjugative stabilization in the ionic transition states, thus differing from traditional explanations. The high reactivity of allyl halides is explained by electrostatic polarization of the double bond. Substituent effects were also studied; in general, electron-withdrawing groups lower the barriers of the ionic S(N)2 reactions but increase the barriers of the ion pair reactions. The allylic reactions are compared with related benzylic systems. Hammett correlations give rho of opposite sign for the ionic and ion pair displacement reactions, in agreement with some experimental results.
authors.affiliation: Department of Chemistry, University of California-Berkeley, Berkeley, California 94720-1460, USA. astreit@berkeley.edu
authors.forename: A
authors.initials: A
authors.lastname: Streitwieser
authors.forename: E G
authors.initials: EG
authors.lastname: Jayasree
authors.forename: S S-H
authors.initials: SS
authors.lastname: Leung
authors.forename: G S-C
authors.initials: GS
authors.lastname: Choy