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

Herein, the potentiality of carbon-containing molecules (W–C–F 3 , where W is a withdrawing atom or group) to interact with Lewis bases (B), Lewis acids (A) and σ–hole-containing molecules (X 2 ) with W–C···B/A/X 2 angle of 180° was reported. − σ–hole and + σ–hole terminologies were implemented to describe the interactions of W–C–F 3 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–F 3 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–F 3 ···B > W–C–F 3 ···X 2 > W–C–F 3 ···A. QTAIM, and NCI calculations revealed the noncovalent nature of the ± σ–hole interactions. Further, an investigation on F–C–X 3 model was carried out to highlight the emerging role of X 3 atoms in ± σ–hole interactions. Comprising of the findings, the most favorable interaction energies were denoted when the F–C–X 3 interact with X 2 molecules compared to those with B and A molecules.