ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

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

E-mail: m.ibrahim@compchem.net

Received: 19 September 2019  Accepted: 2 May 2020

Abstract:

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 www.springerlink.com.

DOI: 10.1007/s11696-020-01187-1

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