Steric effects and solvent effects in ionic reactions.

Published

Journal Article

Rates of SN2 reactions of chloride ion with methyl- and tert-butyl-substituted chloroacetonitrile were measured by using Fourier transform-ion cyclotron resonance spectrometry to follow the isotopic exchange reaction. Barrier heights for these reactions indicate that steric effects in the gas phase are diminished relative to apparent steric effects in solution. We attribute the increased barrier in solution to a solvation effect. Monte Carlo simulations done using statistical perturbation theory confirm that steric hindrance to solvation contributes to SN2 barriers in solution.

Full Text

Duke Authors

Cited Authors

  • Regan, CK; Craig, SL; Brauman, JI

Published Date

  • March 2002

Published In

Volume / Issue

  • 295 / 5563

Start / End Page

  • 2245 - 2247

PubMed ID

  • 11910104

Pubmed Central ID

  • 11910104

Electronic International Standard Serial Number (EISSN)

  • 1095-9203

International Standard Serial Number (ISSN)

  • 0036-8075

Digital Object Identifier (DOI)

  • 10.1126/science.1068849

Language

  • eng