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Transition state geometry in radical hydrogen atom abstraction

Evgenii Timofeevich Denisov 1
Evgenii Timofeevich Denisov
, 
Alexander Fedorovich Shestakov 1
Alexander Fedorovich Shestakov
, 
Taisa Grigor'evna Denisova 1
Taisa Grigor'evna Denisova
1 Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry, Russian Academy of Sciences, Chernogolovka, Moscow region
Published 30 November 2011
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Denisov E. T., Shestakov A. F., Denisova T. G. Transition state geometry in radical hydrogen atom abstraction // Russian Chemical Reviews. 2012. Vol. 81. No. 12. pp. 1117-1132.
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Denisov E. T., Shestakov A. F., Denisova T. G. Transition state geometry in radical hydrogen atom abstraction // Russian Chemical Reviews. 2012. Vol. 81. No. 12. pp. 1117-1132.
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TY - JOUR
DO - 10.1070/RC2012v081n12ABEH004275
UR - https://rcr.colab.ws/publications/10.1070/RC2012v081n12ABEH004275
TI - Transition state geometry in radical hydrogen atom abstraction
T2 - Russian Chemical Reviews
AU - Denisov, Evgenii Timofeevich
AU - Shestakov, Alexander Fedorovich
AU - Denisova, Taisa Grigor'evna
PY - 2012
DA - 2011/11/30
PB - ANO Editorial Board of the journal Uspekhi Khimii
SP - 1117-1132
IS - 12
VL - 81
ER -
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@article{2012_Denisov,
author = {Evgenii Timofeevich Denisov and Alexander Fedorovich Shestakov and Taisa Grigor'evna Denisova},
title = {Transition state geometry in radical hydrogen atom abstraction},
journal = {Russian Chemical Reviews},
year = {2012},
volume = {81},
publisher = {ANO Editorial Board of the journal Uspekhi Khimii},
month = {Nov},
url = {https://rcr.colab.ws/publications/10.1070/RC2012v081n12ABEH004275},
number = {12},
pages = {1117--1132},
doi = {10.1070/RC2012v081n12ABEH004275}
}
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Denisov, Evgenii Timofeevich, et al. “Transition state geometry in radical hydrogen atom abstraction.” Russian Chemical Reviews, vol. 81, no. 12, Nov. 2012, pp. 1117-1132. https://rcr.colab.ws/publications/10.1070/RC2012v081n12ABEH004275.
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Abstract

The data on quantum chemical calculations of interatomic distances in the transition state of the radical reactions of hydrogen atom abstraction, X•+HY → XH+Y•, are generalized and described systematically. Depending on the reaction centre structure, these reactions are subdivided into classes with the X...Y interatomic distance being the same within each class. Data on the transition state geometry obtained by the methods of intersecting parabolas and intersecting Morse curves are presented. The reaction centre X...H...Y is shown to be almost linear, the hydrogen atom position in it being determined by the reaction enthalpy. The effects of triplet repulsion, electronegativities and radii of the atoms X and Y, the presence of π-bonds adjoining the reaction centre and steric effects on the X...Y interatomic distance is analyzed and characterized. Bibliography — 62 references.