Comparison of ^±σ-hole and ^±R˙-hole interactions formed by tetrel-containing complexes: a computational study

Abstract

The characteristics and nature of ±R˙-hole interactions were uncovered for the first time and compared to their ±σ-hole analogs in ˙TF3⋯ and W–T–F3⋯B/R˙/A complexes.

Type I–IV Halogen⋯Halogen Interactions: A Comparative Theoretical Study in Halobenzene⋯Halobenzene Homodimers

“…The Point-of-charge (PoC) approach was documented as an informative tool for elucidating the electrostatic inclination of the group III-VIII element-containing molecules to participate in noncovalent interactions [ 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 ]. With the help of the PoC approach, negatively and positively charged points were utilized to parody the nucleophilic and electrophilic effects on the inspected molecular systems, respectively.…”

“…Overall, all the inspected halogen-containing molecules showed a propensity to participate in type I–IV halogen⋯halogen interactions. Clearly, the energetic features outlined that the highest binding energy was discerned to type II interactions, which is inconsistent with the chalcogen⋯chalcogen analogs that announced the preference of type IV interactions [ 53 ]. On the other hand, the lowest E binding was relevant to type III interactions synchronically to chalcogen⋯chalcogen counterparts.…”

Unusual chalcogen⋯chalcogen interactions in like⋯like and unlike YCY⋯YCY complexes (Y = O, S, and Se)

“…was implemented for the MEP calculations in accord with previous recommendations that confirmed its valuable description for the surface of chemical systems. 62 With the support of the point-of-charge (PoC) approach, a purely electrostatic model for chalcogen-based interactions was established using negatively-and positively-charged points with a value of AE0.50 a.u., which were dedicated to Lewis base and acid mimics, [63][64][65][66] respectively. In addition, the YÁ Á ÁPoC distance effect was systematically elucidated in the range from 2.5 to 6.0 Å along the x-axis (i.e., the outer equatorial surface of the chalcogen atom) and z-axis (i.e., the axial portion of the chalcogen atom) with +C = YÁ Á ÁPoC angles of 1801 and 901, respectively (see Fig.…”

“…A point-of-charge (PoC) approach was recently documented as an informative tool to thoroughly study the s-, p-, lone-pair (lp)-, and radical (R )-hole interactions from an electrostatic perspective, with the utilization of negative and positive PoCs mimicking the roles of Lewis base and acid, respectively. 66,[84][85][86][87][88][89] With the implementation of PoC calculations, molecular stabilization energies (E stabilization ) of YQ Q QCQ Q QYÁ Á ÁPoC systems were calculated using AE0.50 a.u. PoCs at YÁ Á ÁPoC distances in the range of 2.5-6.0 Å along the x-axis and z-axis with +CQ Q QYÁ Á ÁPoC angles of 1801 and 901, respectively (see the Computational methods section for details).…”

σ-Hole and LP-Hole Interactions of Pnicogen···Pnicogen Homodimers under the External Electric Field Effect: A Quantum Mechanical Study

“…In a series of studies, the covalently bonded atoms of group IV–VII were reported with recognizable ability to form regions of depletion in electron density, 9 − 12 dubbed as σ-, 13 π-, 14 lone-pair (lp)-, 15 and radical (R • )-holes. 16 The holes of group IV–VII element-containing molecules can interact with Lewis bases, forming tetrel, 17 − 19 pnicogen, 20 − 25 chalcogen, 26 − 31 and halogen 13 , 31 − 36 bonds, respectively. Among hole-bonding complexes, the interactions of pnicogen-containing molecules with Lewis bases have found sustained attention of a variety of theoretical 37 − 42 and experimental studies 43 − 45 by dint of their significant importance in chemical reactions 46 − 48 and biological systems.…”