Hole interactions of aerogen oxides with Lewis bases: an insight into σ-hole and lone-pair-hole interactions

Mahmoud A A Ibrahim; Mohammed N I Shehata; Hassan A A Abuelliel; Nayra A M Moussa; Shaban R M Sayed; Muhammad Naeem Ahmed; Mohamed K Abd El-Rahman; Eslam Dabbish; Tamer Shoeib

doi:10.1098/rsos.231362

Hole interactions of aerogen oxides with Lewis bases: an insight into σ-hole and lone-pair-hole interactions

R Soc Open Sci. 2023 Dec 13;10(12):231362. doi: 10.1098/rsos.231362. eCollection 2023 Dec.

Authors

Mahmoud A A Ibrahim^{1

2}, Mohammed N I Shehata¹, Hassan A A Abuelliel¹, Nayra A M Moussa¹, Shaban R M Sayed³, Muhammad Naeem Ahmed⁴, Mohamed K Abd El-Rahman⁵, Eslam Dabbish⁶, Tamer Shoeib⁶

Affiliations

¹ Computational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia 61519, Egypt.
² School of Health Sciences, University of KwaZulu-Natal, Westville Campus, Durban 4000, South Africa.
³ Department of Botany and Microbiology, College of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia.
⁴ Department of Chemistry, The University of Azad Jammu and Kashmir, Muzaffarabad 13100, Pakistan.
⁵ Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.
⁶ Department of Chemistry, The American University in Cairo, New Cairo 11835, Egypt.

Abstract

σ-Hole and lone-pair (lp)-hole interactions of aerogen oxides with Lewis bases (LB) were comparatively inspected in terms of quantum mechanics calculations. The ZO_n ⋯ LB complexes (where Z = Kr and Xe, n = 1, 2, 3 and 4, and LB = NH₃ and NCH) showed favourable negative interaction energies. The complexation features were explained in light of σ-hole and lp-hole interactions within optimum distances lower than the sum of the respective van der Waals radii. The emerging findings outlined that σ-hole interaction energies generally enhanced according to the following order: KrO₄ ⋯ < KrO⋯ < KrO₃⋯ < KrO₂⋯LB and XeO₄⋯ < XeO⋯ < XeO₂⋯ < XeO₃⋯LB complexes with values ranging from -2.23 to -12.84 kcal mol^-1. Lp-hole interactions with values up to -5.91 kcal mol^-1 were shown. Symmetry-adapted perturbation theory findings revealed the significant contributions of electrostatic forces accounting for 50-65% of the total attractive forces within most of the ZO_n⋯LB complexes. The obtained observations would be useful for the understanding of hole interactions, particularly for the aerogen oxides, with application in supramolecular chemistry and crystal engineering.

Keywords: aerogen oxides; lone-pair-hole interactions; point-of-charge analysis; symmetry-adapted perturbation theory analysis; σ-hole interactions.

Associated data

figshare/10.6084/m9.figshare.c.6960782