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A computational study on the sources of deuterium secondary kinetic isotope effects in carbocation-forming reactions

Title:

A computational study on the sources of deuterium secondary kinetic isotope effects in carbocation-forming reactions

Muchall, Heidi M. and Werstiuk, Nick H (1998) A computational study on the sources of deuterium secondary kinetic isotope effects in carbocation-forming reactions. Canadian Journal of Chemistry, 76 (12). pp. 1926-1930. ISSN 0008-4042

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Official URL: http://dx.doi.org/10.1139/cjc-76-12-1926

Abstract

Calculations at the HF-DFT hybrid Becke3LYP level of theory have been undertaken on protonated 2-exo- and 2-endo-norbornanols as model substrates for 2-exo- and 2-endo-norbornyl brosylates to explore the source of the experimentally determined deuterium secondary kinetic isotope effects (KIEs). Calculations on protonated alcohols as models reproduce the "normal" behaviour of 2-endo substrate 5. The observed endo g-KIE in the 7-unsubstituted 2-exo system 4 is shown to arise from internal return, while those in the 7-chloro substituted 2-exo substrates 1 and 2 can be explained with competing 1,3 (6,2)-elimination

Divisions:Concordia University > Faculty of Arts and Science > Chemistry and Biochemistry
Item Type:Article
Refereed:Yes
Authors:Muchall, Heidi M. and Werstiuk, Nick H
Journal or Publication:Canadian Journal of Chemistry
Date:December 1998
Funders:
  • Natural Sciences and Engineering Research Council of Canada
Keywords:deuterium secondary kinetic isotope effects, 2-norbornyl cation, Becke3LYP
ID Code:6767
Deposited By:DANIELLE DENNIE
Deposited On:12 Jul 2010 16:56
Last Modified:08 Dec 2010 18:08
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