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Ab initio derived group additivity model for intramolecular hydrogen abstraction reactions

Ruben Van de Vijver (UGent) , Maarten Sabbe (UGent) , Marie-Françoise Reyniers (UGent) , Kevin Van Geem (UGent) and Guy Marin (UGent)
(2018) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 20(16). p.10877-10894
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Abstract
A set of group additivity values for intramolecular hydrogen abstraction reactions of alkanes, alkenes and alkynes is reported. Calculating 448 reaction rate coefficients at the CBS-QB3 level of theory for 1-2 up to 1-7 hydrogen shift reactions allowed the estimation of DGAV1 values for 270 groups. The influence of substituents on (1) the attacking radical, (2) the attacked carbon atom, and (3) the carbon chain between the attacking and attacked reactive atom has been systematically studied. Substituents have been varied between hydrogen atoms and sp3 , sp2 and sp hybridized carbon atoms. It has been assumed that substituents further away from the reactive atoms or their connecting carbon chain have negligible influences on the kinetics. This group additivity model is applicable to a wide variety of reactions in the 300–1800 K temperature range. Correlations for tunneling coefficients have been generated which are complementary to the DGAV1’s to obtain accurate rate coefficients without the need for imaginary frequencies or electronic energies of activation. These correlations depend on the temperature and activation energy of the exothermic step. The group additivity model has been successfully applied to a test set of reactions also calculated at the CBS-QB3 level of theory. A mean absolute deviation of 1.18 to 1.71 has been achieved showing a good overall accuracy of the model.
Keywords
CENTERED RADICAL-ADDITION, REACTION-RATE PREDICTION, ATOM TRANSFER-REACTIONS, N-ALKYL RADICALS, GAS-PHASE, HYDROCARBON RADICALS, ACTIVATION-ENERGIES, HEXYL RADICALS, REACTION-RATES, H-ABSTRACTION

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Chicago
Van de Vijver, Ruben, Maarten Sabbe, Marie-Françoise Reyniers, Kevin Van Geem, and Guy Marin. 2018. “Ab Initio Derived Group Additivity Model for Intramolecular Hydrogen Abstraction Reactions.” Physical Chemistry Chemical Physics 20 (16): 10877–10894.
APA
Van de Vijver, R., Sabbe, M., Reyniers, M.-F., Van Geem, K., & Marin, G. (2018). Ab initio derived group additivity model for intramolecular hydrogen abstraction reactions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 20(16), 10877–10894.
Vancouver
1.
Van de Vijver R, Sabbe M, Reyniers M-F, Van Geem K, Marin G. Ab initio derived group additivity model for intramolecular hydrogen abstraction reactions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2018;20(16):10877–94.
MLA
Van de Vijver, Ruben, Maarten Sabbe, Marie-Françoise Reyniers, et al. “Ab Initio Derived Group Additivity Model for Intramolecular Hydrogen Abstraction Reactions.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 20.16 (2018): 10877–10894. Print.
@article{8561393,
  abstract     = {A set of group additivity values for intramolecular hydrogen abstraction reactions of alkanes, alkenes and
alkynes is reported. Calculating 448 reaction rate coefficients at the CBS-QB3 level of theory for 1-2
up to 1-7 hydrogen shift reactions allowed the estimation of DGAV1 values for 270 groups. The influence
of substituents on (1) the attacking radical, (2) the attacked carbon atom, and (3) the carbon chain
between the attacking and attacked reactive atom has been systematically studied. Substituents have been
varied between hydrogen atoms and sp3
, sp2 and sp hybridized carbon atoms. It has been assumed that
substituents further away from the reactive atoms or their connecting carbon chain have negligible
influences on the kinetics. This group additivity model is applicable to a wide variety of reactions in the
300--1800 K temperature range. Correlations for tunneling coefficients have been generated which are
complementary to the DGAV1{\textquoteright}s to obtain accurate rate coefficients without the need for imaginary
frequencies or electronic energies of activation. These correlations depend on the temperature and
activation energy of the exothermic step. The group additivity model has been successfully applied to a
test set of reactions also calculated at the CBS-QB3 level of theory. A mean absolute deviation of 1.18 to
1.71 has been achieved showing a good overall accuracy of the model.},
  author       = {Van de Vijver, Ruben and Sabbe, Maarten and Reyniers, Marie-Fran\c{c}oise and Van Geem, Kevin and Marin, Guy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  language     = {eng},
  number       = {16},
  pages        = {10877--10894},
  title        = {Ab initio derived group additivity model for intramolecular hydrogen abstraction reactions},
  url          = {http://dx.doi.org/10.1039/C7CP07771H},
  volume       = {20},
  year         = {2018},
}

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