Comparisons of the halogen-bonded and hydrogen-bonded complexes of furan, thiophene and pyridine with Lewis acids (ClF, HCl)

• Published in: Computational and theoretical chemistry 2012-02, Vol.981, p.1-6
• Main Authors: Wang, Zhaoxu, Liu, Zhengjun, Ding, Xunlei, Yu, Xianyong, Hou, Bo, Yi, Pinggui
• Format: Article
• Language: English
• Subjects: Energy decomposition analysis; Intermolecular interaction; Laplacian properties; X3LYP
• ISSN: 2210-271X
• DOI: 10.1016/j.comptc.2011.11.013

Energy profiles of the corresponding tautomerism processes between σ- and π-type structures of the C 4H 4O/C 4H 4S/C 5H 5N⋯HCl/ClF complexes at the X3LYP/aug-cc-pVTZ level. [Display omitted] ► σ- and π-type interactions are observed between C 4H 4O/C 4H 4S/C 5H 5N and ClF/HCl. ► C 4H 4S…HCl/ClF and C 4H 4O…ClF prefer π-type geometry, violating Legon-Millen rule. ► σ- and π-type geometries are easily transformed for C 4H 4O/C 4H 4S…ClF/HCl. ► The electrostatic and orbital interactions play the key roles. The geometries, interaction energies, tautomerization processes, electron density and Laplacian properties of the weak interaction systems formed by heteroaromatic rings (C 4H 4O, C 4H 4S and C 5H 5N) and Lewis acids (ClF, HCl) have been studied at the spin-restricted DFT method (X3LYP) with the aug-cc-pVTZ basis sets. Two types of interactions are observed among these systems: the σ-type and the π-type geometry. The low energy barriers (