Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical
Abstract
In this study, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X• + HCR3 → XH + •CR3; X = Cl•, HO•, and Br); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3•. In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3•) = 0.0251(ΔrH) + 0.96(ΣF) 0.56(ΣR) – 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3, may depend on the nature of the substituents.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1263858
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 26; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Poutsma, Marvin L. Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical. United States: N. p., 2016.
Web. doi:10.1021/acs.jpca.6b04357.
Poutsma, Marvin L. Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical. United States. https://doi.org/10.1021/acs.jpca.6b04357
Poutsma, Marvin L. Tue .
"Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical". United States. https://doi.org/10.1021/acs.jpca.6b04357. https://www.osti.gov/servlets/purl/1263858.
@article{osti_1263858,
title = {Extension of structure-reactivity correlations for the hydrogen abstraction reaction to methyl radical and comparison to chlorine atom, bromine atom, and hydroxyl radical},
author = {Poutsma, Marvin L.},
abstractNote = {In this study, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp3-hybridized carbon by three electrophilic radicals (X• + HCR3 → XH + •CR3; X = Cl•, HO•, and Br); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3•. In spite of a limited and scattered data base, the resulting least-squares fit [log k437(CH3•) = 0.0251(ΔrH) + 0.96(ΣF) 0.56(ΣR) – 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the philicity of CH3, may depend on the nature of the substituents.},
doi = {10.1021/acs.jpca.6b04357},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 26,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}
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