Affordable Access

Publisher Website

A theoretical study of steric effects in SN2 reactions

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Publication Date
Volume
196
Identifiers
DOI: 10.1016/0009-2614(92)85984-i

Abstract

Abstract The gas phase reaction of chloride ion with alkyl chlorides (methyl, ethyl, propyl, i-propyl, i-butyl, t-butyl and neo-pentyl) has been studied by ab initio methods. Geometries of stationary points along the reaction coordinate have been optimized at the MP2/6-31G* level of theory and improved energies have been calculated with the 6-311 + G(2d) basis. Although all reactions are “narcissistic”, i.e. reactant and product are identical, it is found that some of the transition structures have unequal CCl bond lengths. The breaking/forming CCl bond for the t-butyl system is significantly longer than for the other alkyl groups, for which the change with increasing steric bulk is as expected. The calculated relative activation energies are compared with available gas-phase data and relevant solution values.

There are no comments yet on this publication. Be the first to share your thoughts.

Statistics

Seen <100 times
0 Comments

More articles like this

Steric effects and solvent effects on SN2 reaction...

on The Journal of Physical Chemis... Aug 13, 2009

A theoretical study of substituent effects on ally...

on The Journal of Organic Chemist... Oct 14, 2005

A theoretical study of SN2O2isomers

on Chemical Physics Letters Jan 01, 2000

Comment on "The interplay between steric and elect...

on Chemistry - A European Journal May 17, 2010
More articles like this..