Reactions of concerted decomposition of cyclic molecules, as studied by the quantum chemistry methods and parabolic model

Abstract

Reactions of concerted decomposition of cyclic molecules (Diels—Alder retro-reactions) were studied using quantum chemical modeling and the method of intersecting parabolas (M3IP model). According to results of quantum chemical calculations and topological analysis of transition states (TSs) of five concerted decomposition reactions of cyclic molecules, all TSs represent six-membered rings in which the bonds being cleaved are weak covalent ones. The presence of ring heteroatoms (N, O, or S) has a strong impact on the TS geometry and on the energy characteristics of the reactions. The M3IP model was used to process the experimental results to develop an algorithm for calculating the activation energies (E) of the reactions in question and the classical potential barriers to thermally neutral reaction (E_e⁰). Factors influencing the energies E were determined and assessed. These include the enthalpy of reaction, substituents, ring heteroatoms, the force constants of bonds, and the bond dissociation energies. A comparison of the activation energies E and the enthalpies of reaction ΔH obtained from the M3IP and density functional B3LYP/6-311++G** calculations revealed good agreement between them.