NPE Effects in Bimolecular Nucleophilic Substitution

Christine D. Chalk, James McKenna, Ian H. Williams

Research output: Contribution to journalArticle

Abstract

By use of the force fields established in the two preceding papers, relative NPE effects are calculated for bromide ion exchanges (the Finkelstein reactions) for a series of simple alkyl bromides. The effects on rate constants cover a range of about 30:1, neglecting contributions (if any) from variation in rotational symmetry numbers. These calculated results are analyzed in detail and compared with related literature results, both experimental and calculated. Extension of the force fields permits computation of relative NPE effects for reaction of methyl bromide with hydroxide ion and with a series of alkoxides. Effects for alkoxides differ only slightly within the group, but the NPE contribution to the rate constant for reaction with hydroxide is nearly twice that for reaction with methoxide. Interpretations for these findings are suggested.

Original languageEnglish
Pages (from-to)272-281
Number of pages10
JournalJournal of the American Chemical Society
Volume103
Issue number2
DOIs
Publication statusPublished - 1 Jan 1981

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

NPE Effects in Bimolecular Nucleophilic Substitution. / Chalk, Christine D.; McKenna, James; Williams, Ian H.

In: Journal of the American Chemical Society, Vol. 103, No. 2, 01.01.1981, p. 272-281.

Research output: Contribution to journalArticle

Chalk, Christine D. ; McKenna, James ; Williams, Ian H. / NPE Effects in Bimolecular Nucleophilic Substitution. In: Journal of the American Chemical Society. 1981 ; Vol. 103, No. 2. pp. 272-281.
@article{3c7cb94d66934738bbf86747b717860b,
title = "NPE Effects in Bimolecular Nucleophilic Substitution",
abstract = "By use of the force fields established in the two preceding papers, relative NPE effects are calculated for bromide ion exchanges (the Finkelstein reactions) for a series of simple alkyl bromides. The effects on rate constants cover a range of about 30:1, neglecting contributions (if any) from variation in rotational symmetry numbers. These calculated results are analyzed in detail and compared with related literature results, both experimental and calculated. Extension of the force fields permits computation of relative NPE effects for reaction of methyl bromide with hydroxide ion and with a series of alkoxides. Effects for alkoxides differ only slightly within the group, but the NPE contribution to the rate constant for reaction with hydroxide is nearly twice that for reaction with methoxide. Interpretations for these findings are suggested.",
author = "Chalk, {Christine D.} and James McKenna and Williams, {Ian H.}",
year = "1981",
month = "1",
day = "1",
doi = "10.1021/ja00392a004",
language = "English",
volume = "103",
pages = "272--281",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - NPE Effects in Bimolecular Nucleophilic Substitution

AU - Chalk, Christine D.

AU - McKenna, James

AU - Williams, Ian H.

PY - 1981/1/1

Y1 - 1981/1/1

N2 - By use of the force fields established in the two preceding papers, relative NPE effects are calculated for bromide ion exchanges (the Finkelstein reactions) for a series of simple alkyl bromides. The effects on rate constants cover a range of about 30:1, neglecting contributions (if any) from variation in rotational symmetry numbers. These calculated results are analyzed in detail and compared with related literature results, both experimental and calculated. Extension of the force fields permits computation of relative NPE effects for reaction of methyl bromide with hydroxide ion and with a series of alkoxides. Effects for alkoxides differ only slightly within the group, but the NPE contribution to the rate constant for reaction with hydroxide is nearly twice that for reaction with methoxide. Interpretations for these findings are suggested.

AB - By use of the force fields established in the two preceding papers, relative NPE effects are calculated for bromide ion exchanges (the Finkelstein reactions) for a series of simple alkyl bromides. The effects on rate constants cover a range of about 30:1, neglecting contributions (if any) from variation in rotational symmetry numbers. These calculated results are analyzed in detail and compared with related literature results, both experimental and calculated. Extension of the force fields permits computation of relative NPE effects for reaction of methyl bromide with hydroxide ion and with a series of alkoxides. Effects for alkoxides differ only slightly within the group, but the NPE contribution to the rate constant for reaction with hydroxide is nearly twice that for reaction with methoxide. Interpretations for these findings are suggested.

UR - http://www.scopus.com/inward/record.url?scp=33845557163&partnerID=8YFLogxK

U2 - 10.1021/ja00392a004

DO - 10.1021/ja00392a004

M3 - Article

VL - 103

SP - 272

EP - 281

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -