Aarhus University Seal / Aarhus Universitets segl

Frank Jensen

Steric effects in SN2 reactions. The influence of microsolvation

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

  • Adel Ahmed Mohamed, Helwan University, Helwan
  • ,
  • F. Jensen
Ab initio molecular orbital calculations at the B3LYP/6-31+G* and MP2/6-31+G* levels have been performed to study the effect of microsolvation on the SN2 reaction profile for Cl + RC1 (R = methyl, ethyl, i-propyl, and tert-butyl). Microsolvation corresponding to 0-4 water molecules, and 0-2 molecules of methanol, acetonitrile, acetone, dimethyl ether and propane has been investigated. The polarizable continuum solvent model has been used to investigate the effect of bulk solvation. The calculated barrier heights increase with the number of solvent molecules and the size of the R group. Microsolvation causes only small changes in the TS geometries for the methyl, ethyl, and i-propyl systems, whereas the tert-butyl TS becomes significantly looser. Microsolvation decreases the steric effect, with the modulation depending on the dielectric constant of the solvent. For water, the decrease in steric effect is shown to be due to an increased solvation of the TS, mediated by the electron donating effect of the methyl group. The polarizable continuum solvent model in general underestimates changes in steric effects due to solvation.
Original languageEnglish
JournalJournal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Volume105
Issue13
Pages (from-to)3259-3268
Number of pages10
ISSN1089-5639
DOIs
Publication statusPublished - 2001
Externally publishedYes

See relations at Aarhus University Citationformats

ID: 55281948