σ‐Hole Interactions of Tetrahedral Group IV–VIII Lewis Acid Centers with Lewis Bases: A Comparative Study

• Published in: ChemistrySelect (Weinheim) Vol. 6; no. 43; pp. 11856 - 11864
• Main Authors: Ibrahim, Mahmoud A. A., Mohamed, Yasmeen A. M., Abuelliel, Hassan A. A., Rady, Al‐shimaa S. M., Soliman, Mahmoud E. S., Ahmed, Muhammad Naeem, Mohamed, Lamiaa A., Moussa, Nayra A. M.
• Format: Journal Article
• Language: English
• Published: 22.11.2021
• Subjects: Basicity; external electric field; noncovalent interaction; tetrahedral Lewis acid; σ-hole interaction
• ISSN: 2365-6549; 2365-6549
• DOI: 10.1002/slct.202103092

In the current study, σ‐hole interactions of group IV–VIII element‐containing molecules in tetrahedral geometry with Lewis bases were comparatively scrutinized. The FSiF3, OPF3, NSF3, FClO3, and OArO3 molecules were devoted as Lewis acid centers to interact with NH3 and NCH Lewis bases. According to the results, the most significant σ‐hole interactions were ascribed to the FSiF3⋅⋅⋅ and FClO3⋅⋅⋅Lewis base complexes with interaction energy up to –29.74 kcal mol−1 in the case of the FSiF3⋅⋅⋅NH3 complex. Symmetry‐adapted perturbation theory‐based energy decomposition analysis (SAPT‐EDA) demonstrated that the electrostatic energy (Eelst) was the most prevalent force dominating the explored interactions, while the exchange energies exhibited unfavorable contribution. Quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) results emphasized the closed‐shell nature for all the investigated complexes except FSiF3⋅⋅⋅NH3 complex that demonstrated a covalent nature. Crucially, the utilization of the positively‐ and negatively‐directed external electric field (EEF) led to amelioration and debilitation of the strength of the studied interactions, respectively. The present findings provide knowledge essential to further expanded applications in the fields pertinent to materials science and crystal engineering. A thorough study of the σ‐hole interactions of tetrahedral group IV–VIII element‐containing molecules with Lewis bases was executed on the FSiF3⋅⋅⋅, OPF3⋅⋅⋅, NSF3⋅⋅⋅, FClO3⋅⋅⋅, and OArO3⋅⋅⋅NH3/NCH complexes. Substantial interaction energies were observed for the FSiF3⋅⋅⋅ and FClO3⋅⋅⋅Lewis base complexes. Utilization of the positively‐ and negatively‐directed external electric field (EEF) gave rise to amelioration and debilitation of the strength of the studied complexes, respectively.