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Cited by 42Physical Organic Chemistry and Reaction KineticsPhotolysis and Reactive IntermediatesFree Radicals and Antioxidants

The DOI matches its Crossref record; 41 of the 41 references it cites were found in a registry or an index.

Reactivity and Secondary Kinetic Isotope Effects in the S N 2 Reaction Mechanism: Dioxygen Radical Anion and Related Nucleophiles

Davico, Gustavo E., Bierbaum, Veronica M.·2000·Journal of the American Chemical Society
DOI 10.1021/ja993093x
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Abstract

We have measured the rate constants for the reactions of O 2 • - and several related anions and radical anions with alkyl halides. The results suggest that O 2 • - reacts with alkyl halides more rapidly than anticipated, based on anion basicities as well as on results from ab initio calculations. In addition, deuterated neutrals were used and the kinetic isotope effects (KIE) determined. These values were also calculated by using ab initio calculations and transition state theory. The agreement between experiment and theory is excellent, except for O 2 • - indicating that this reaction proceeds by a different reaction mechanism. We discuss competition between electron transfer and substitution mechanisms to explain the observed remarkable nucleophilicity of O 2 • - . A detailed analysis of the different contributions to the calculated KIEs shows that the total value is primarily determined by the C−H stretching and the CH 3 out-of-plane bending modes. The former factor is very inverse ( k H / k D < 1), and it does not change significantly for different reactions. However, the bending factor changes markedly from one reaction to another and therefore becomes the factor that determines how the total KIEs change for different reactions. As a result, the KIEs are related to the crowdedness of the transition states. This effect is discussed in detail with respect to the conventional looseness interpretation.

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Crossref · 10.1021/ja993093x

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41 of 41 references verified0 citation errors · 0 not checkable

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  • O2•− is a nucleophile in reactions with alkyl halides and alkyl tosylates in DMSO, leading to alkylperoxy radicals and then peroxy anions via one-electron reduction.

    “O2•− is a nucleophile in the reaction with alkyl halides and alkyl tosylates in DMSO and leads to the formation of alkylperoxy radicals and subsequently to peroxy anions via one-electron reduction [56,129], Figure 47.”

    From Superoxide Anion Chemistry—Its Role at the Core of the Innate Immunity (2023) · cites this paper as [129]

Citations

Cites

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Research works printed but not linked: 13

  1. Gronert S., 1991, J. Am. Chem. Soc., 113, 10
  2. Viggiano A. A., 1996, J. Phys. Chem., 100, 14402
  3. Dewar M. J. S., 1990, J. Am. Chem. Soc., 112, 105
  4. Hu W.-P., 1994, J. Am. Chem. Soc., 116, 800
  5. O'Hair R. A. J., 1994, J. Am. Chem. Soc., 116, 10
  6. Boyd R. J., 1993, J. Am. Chem. Soc., 115, 52
  7. Zhao X. G., 1992, J. Chem. Phys., 97, 83
  8. Tucker S. C., 1990, J. Am. Chem. Soc., 112, 47
  9. Matsson O., 1998, Adv. Phys. Org. Chem., 31, 248
  10. Frisch M. J., 1992, Revision C
  11. Sastry G. N., 1998, J. Am. Chem. Soc., 120, 2145
  12. Williams I. H., 1984, J. Am. Chem. Soc., 106, 12
  13. Truhlar D. G., 1992, ACS Symp. Ser.

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Metadata

Authors
Davico, G. E., & Bierbaum, V. M.
Affiliations
University of Colorado Boulder (US)
Corresponding author
Bierbaum, Veronica M.
ORCID
Bierbaum, Veronica M.
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2000-02-12
Volume
122
Issue
8
Pages
1740-1748
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/ja993093x
OpenAlex
W2069638328
Cited by
42
References
41
Citations by year
2026: 1 · 2024: 1 · 2023: 1 · 2022: 1 · 2018: 2 · 2017: 1 · 2016: 1 · 2014: 1 · 2013: 4
FWCI
3.19
Type
journal article
Language
en
Open access
closed
Locations
Journal of the American Chemical Society (publishedVersion)
Funders
Division of Chemistry
Topics
  • Physical Sciences › Chemistry › Organic Chemistry › Physical Organic Chemistry and Reaction Kinetics
  • Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photolysis and Reactive Intermediates
  • Physical Sciences › Chemistry › Organic Chemistry › Free Radicals and Antioxidants
Keywords
SN2 reaction mechanism, kinetic isotope effects, alkyl halides, nucleophilicity, transition state theory, C-H stretching, rate constants

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