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Comparative investigation of ±σ–hole interactions of carbon-containing molecules with Lewis bases, acids and di-halogens

Mahmoud A. A. Ibrahim, Amna H. M. Mahmoud, and Nayra A. M. Moussa

Computational Chemistry Laboratory, Chemistry Department, Faculty of Science, Minia University, Minia, Egypt



Received: 19 September 2019  Accepted: 2 May 2020


Herein, the potentiality of carbon-containing molecules (W–C–F3, where W is a withdrawing atom or group) to interact with Lewis bases (B), Lewis acids (A) and σ–hole-containing molecules (X2) with W–C···B/A/X2 angle of 180° was reported. σ–hole and +σ–hole terminologies were implemented to describe the interactions of W–C–F3 with nucleophilic and electrophilic sites, respectively. To characterize such interactions, quantum mechanical calculations including geometrical optimization, ±σ–hole test, interaction energy calculation, quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) index calculation were performed at MP2/aug-cc-pVTZ(PP) level of theory. The results showed (1) the electrostatic potentiality of the W–C–F3 molecules to favorably interact with Lewis bases and acids, (2) the dependency of ±σ–hole interaction energies on the σ–hole size of the tetrel atom and (3) descending of interaction energies in the order W–C–F3···B > W–C–F3···X2 > W–C–F3···A. QTAIM, and NCI calculations revealed the noncovalent nature of the ±σ–hole interactions. Further, an investigation on F–C–X3 model was carried out to highlight the emerging role of X3 atoms in ±σ–hole interactions. Comprising of the findings, the most favorable interaction energies were denoted when the F–C–X3 interact with X2 molecules compared to those with B and A molecules.

Keywords: Noncovalent interactions; Tetrel bond; −σ–Hole interaction; +σ–Hole interaction; Point-of-charge approach

Full paper is available at

DOI: 10.1007/s11696-020-01187-1


Chemical Papers 74 (10) 3569–3580 (2020)

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