1. Effect of the molecular structure on the strength of the C-NO2 bond in a series of monofunctional nitrobenzene derivatives
- Author
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Daniil L. Egorov, A. G. Shamov, D.D. Sharipov, G. M. Khrapkovskii, and Denis V. Chachkov
- Subjects
inorganic chemicals ,Bond length ,Chemical bond ,Chemistry ,Bond strength ,Enthalpy ,Physical chemistry ,General Chemistry ,Bond energy ,Photochemistry ,Bond order ,Bond-dissociation energy ,Homolysis - Abstract
Geometric parameters and formation enthalpy and the enthalpy of the radicals formed during the homolytic breakage of C-NO2 bond in 37 aromatic nitro compounds were calculated using different bases of the hybrid density functional method B3LYP, as well as the composite CBS-QB3 methods. On the basis of thermochemical data, were calculated the C-NO2 bond dissociation energy and the activation energy of the radical gas-phase decomposition. Donor substituents were shown to cause an increase in the C-NO2 bond dissociation energy, while the acceptors decrease it. The values of activation energies of gas-phase decomposition of aromatic nitro compounds calculated basing on the C-NO2 bond dissociation energy are in good agreement with experiment.
- Published
- 2011
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