I. A. Romanskii
Russian Chemical Bulletin, International Edition, Vol. 57, No. 9, pp. 1842—1849, September, 2008
A mechanism is proposed of intramolecular reorganization leading to equalization of the
energies of reactants and products in a nonequilibrium proton transfer reaction. The model
proposed allows one to extend a conventional quantum chemical treatment to gas phase proton
transfer. Taking the reaction of toluene deprotonation with the CH2CN– anion (a conjugate
base of acetonitrile) as an example, it was shown that the activation energy and its components
can be determined from direct ab initio calculations. The effect of disbalance of structural
changes relative to the "equilibrium" proton transfer is considered.
Intramolecular reorganization
2.* The Brønsted correlation for a series of gas phase reactions
of deprotonation of para substituted toluene derivatives with the СH2CN– anion
Russian Chemical Bulletin, International Edition, Vol. 57, No. 9, pp. 1850—1857, September, 2008
A proton transfer model proposed earlier that includes equalization of energies of the reac
tant and product by an intramolecular mechanism was used to study gas phase reactions of
deprotonation of para substituted toluene derivatives (substituents were NH2, OH, CH3, H, Cl,
NC, CN, and NO2) with the СH2CN– anion. The energy parameters of the reactions were
determined from ab initio calculations. The Brønsted correlation based on the results obtained
was analyzed in the framework of conventional quantum chemical formalism (the Marcus
equation). The problem of disbalance of the changes in the geometry of the activated complex
relative to its position on the reaction coordinate was considered taking some geometric param
eters of the system as examples.