Interactions of hypervalent IF5 and XeF4O molecules via σ-hole site with Lewis bases and anions: a comparative ab initio study

Author's Department

Chemistry Department

Fifth Author's Department

Chemistry Department

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https://doi.org/10.1039/d5ra04648c

All Authors

Mahmoud A.A. Ibrahim Asmaa M.M. Mahmoud Rehab R.A. Saeed Mohammed N.I. Shehata Tamer Shoeib Jabir H. Al-Fahemi

Document Type

Research Article

Publication Title

Rsc Advances

Publication Date

8-18-2025

doi

10.1039/d5ra04648c

Abstract

Interactions of hypervalent IF5 and XeF4O molecules within the square pyramidal geometry via σ-hole site with Lewis bases (LB = NH3 and NCH) and anions (X− = F−, Cl−, Br−, and I−) were comparatively investigated using ab initio methods. The energetic features outlined remarkable interaction (Eint) and binding (Ebind) energies for all complexes aligned from −5.65 to −91.02 kcal mol−1 and from −5.53 to −65.89 kcal mol−1, respectively. More negative Eint and Ebind values were demonstrated for XeF4O⋯LB complexes, compared to IF5⋯LB complexes, along with nominal deformation energies for all complexes. Turning to IF5⋯ and XeF4O⋯X− complexes, Ebind demonstrated the proficiency of the latter complexes, which was in synchronic with the Vs,max claims. On the contrary, IF5⋯X− complexes demonstrated higher negative Eint values in comparison to XeF4O⋯X− complexes, which may be attributed to the considerable favorable deformation energies relevant to the former complexes rather than the latter candidates. Moreover, the Eint and Ebind were disclosed to ameliorate in coincidence with the Lewis basicity strength as follows: IF5/XeF4O⋯NCH < ⋯NH3 < ⋯I− < ⋯Br− < ⋯Cl− < ⋯F−. Quantum theory of atoms in molecules/noncovalent interactions index observations affirmed that the interactions of IF5/XeF4O molecules via σ-hole site with NH3 and NCH were characterized with open- and closed-shell nature, respectively, while the IF5/XeF4O⋯X− complexes were characterized with the coordinative covalent nature. Symmetry-adapted perturbation theory results pinpointed the predominance of the inspected interactions with the electrostatic forces. The acquired results will be advantageous for the ubiquitous investigation of understanding the impact of geometrical deformation on the interactions of hypervalent molecules and their applications in diverse fields such as materials science and crystal engineering.

First Page

29811

Last Page

29821

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