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Cospatial σ-Hole and Lone Pair Interactions of Square-Pyramidal Pentavalent Halogen Compounds with π-Systems: A Quantum Mechanical Study.
Ibrahim, Mahmoud A A; Ahmed, Ossama A M; El-Taher, Sabry; Al-Fahemi, Jabir H; Moussa, Nayra A M; Moustafa, Hussein.
Afiliação
  • Ibrahim MAA; Chemistry Department, Faculty of Science, Minia University, Minia 61519, Egypt.
  • Ahmed OAM; Chemistry Department, Faculty of Science, Minia University, Minia 61519, Egypt.
  • El-Taher S; Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt.
  • Al-Fahemi JH; Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt.
  • Moussa NAM; Chemistry Department, Faculty of Applied Sciences, Umm Al-Qura University, Makkah 21955, Saudi Arabia.
  • Moustafa H; Chemistry Department, Faculty of Science, Minia University, Minia 61519, Egypt.
ACS Omega ; 6(4): 3319-3329, 2021 Feb 02.
Article em En | MEDLINE | ID: mdl-33553949
ABSTRACT
In the spirit of the mounting interest in noncovalent interactions, the present study was conducted to scrutinize a special type that simultaneously involved both σ-hole and lone pair (lp) interactions with aromatic π-systems. Square-pyramidal pentavalent halogen-containing molecules, including X-Cl-F4, F-Y-F4, and F-I-X4 compounds (where X = F, Cl, Br, and I and Y = Cl, Br, and I) were employed as σ-hole/lp donors. On the other hand, benzene (BZN) and hexafluorobenzene (HFB) were chosen as electron-rich and electron-deficient aromatic π-systems, respectively. The investigation relied upon a variety of quantum chemical calculations that complement each other. The results showed that (i) the binding energy of the X-Y-F4···BZN complexes increased (i.e., more negative) as the Y atom had a larger magnitude of σ-hole, contrary to the pattern of X-Y-F4···HFB complexes; (ii) the interaction energies of X-Y-F4···BZN complexes were dominated by both dispersion and electrostatic contributions, while dispersive interactions dominated X-Y-F4···HFB complexes; and (iii) the X4 atoms in F-I-X4···π-system complexes governed the interaction energy pattern the larger the X4 atoms were, the greater the interaction energies were, for the same π-system. The results had illuminating facets in regard to the rarely addressed cases of the σ-hole/lp contradictory scene.

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2021 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2021 Tipo de documento: Article