Substituent Effects on the Quantum Interference of Two-Center One-Electron Bonds: [B2X6]− (X = H, F, Cl, CN, OH, CH3, and OCH3)

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2021-06, Vol.125 (21), p.4558-4564
• Main Authors: de Sousa, David Wilian Oliveira, Nascimento, Marco Antonio Chaer
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c02771

The interference energy analysis (IEA) provided by the generalized product function energy partitioning (GPF-EP) method was applied to investigate the influence of the neighboring atoms on the nature of the two-center one-electron (2c1e) bonds in the anion dimers of BX3 species (X = H, F, Cl, CN, OH, CH3, and OCH3). The species were studied at the GVB-PP­(6/12).SC­(1,2)/6-31**G++ level of calculation. The IEA has revealed that there is a balance between two main factors determining the chemical stability of the species. Quantum interference acts as the sole stabilizing effect in the formation of the chemical bonds, particularly as the result of the drop in kinetic energy, and the electronegativity of the substituent has a direct influence on the magnitude of this effect. The quasi-classical energy is responsible for the destabilizing factors, mainly the group bulkiness, and the “electron-withdrawing” effect in the case of the cyano group.