A new insight into using chlorine leaving group and nucleophile carbon kinetic isotope effects to determine substituent effects on the structure of S(N)2 transition states

Kenneth C. Westaway*, Yao-Ren Fang, Susanna MacMillar, Olle Matsson, Raymond A. Poirier, Shahidul M. Islam

*Corresponding author for this work

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Chlorine leaving group k(35)/k(37), nucleophile carbon k(11)/k(14), and secondary alpha-deuterium [(k(H)/k(D))(alpha)] kinetic isotope effects (KIEs) have been measured for the S(N)2 reactions between para-substituted benzyl chlorides and tetrabutylammonium cyanide in tetrahydrofuran at 20 degrees C to determine whether these isotope effects can be used to determine the substituent effect on the structure of the transition state. The secondary alpha-deuterium KIEs indicate that the transition states for these reactions are unsymmetric. The theoretical calculations at the B3LYP/aug-cc-pVDZ level of theory support this conclusion; i.e., they suggest that the transition states for these reactions are unsymmetric with a long NC-C-alpha and reasonably short C-alpha-Cl bonds. The chlorine isotope effects suggest that these KIEs can be used to determine the substituent effects on transition state structure with the KIE decreasing when a more electron-withdrawing para-substituent is present. This conclusion is supported by theoretical calculations. The nucleophile carbon k(11)/k(14) KIEs for these reactions, however, do not change significantly with substituent and, therefore, do not appear to be useful for determining how the NC-C-alpha transition-state bond changes with substituent. The theoretical calculations indicate that the NC-C-alpha bond also shortens as a more electron-withdrawing substituent is placed on the benzene ring of the substrate but that the changes in the NC-C-alpha transition-state bond with substituent are very small and may not be measurable. The results also show that using leaving group and nucleophile carbon KIEs to determine the substituent effect on transition-state structure is more complicated than previously thought. The implication of using both chlorine leaving group and nucleophile carbon KIEs to determine the substituent effect on transition-state structure is discussed.

Original languageEnglish
Pages (from-to)8110-8120
Number of pages11
JournalJournal of Physical Chemistry A
Volume111
Issue number33
DOIs
Publication statusPublished - 23 Aug 2007
Externally publishedYes

Keywords

  • CYANIDE ION
  • BENZYL CHLORIDES
  • INCOMING GROUP
  • BENZENESULFONATES
  • REACTIVITY
  • SOLVENT
  • MODEL

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