The π‐hole tetrel bond betweenX₂TOandCO₂: Substituent effects and its potential adsorptivity forCO₂

Abstract

Quantum chemical calculations are applied to study the complexes between X2TO (X = H, F, Cl, Br, CH3; T = C, Si, Ge, Sn) and CO2. The carbon atom of CO2 as a Lewis acid participates in the C···O carbon bond, whereas its oxygen atom as a base engages in the O···T tetrel bond with X2TO. Most of complexes are stabilized by a combination of both C···O and O···T interactions. The interaction energy increases in the T = C < Ge < Sn < Si sequence for most complexes. Both the electron‐withdrawing halogen group and the electron‐donating methyl group increase the interaction energy, up to 51 kJ/mol in F2SiO···CO2. One F2SiO molecule can bind with different numbers of CO2 molecules (1–4); as the number of CO2 molecules increases, the average interaction energy for each CO2 decreases and each CO2 molecule can contribute with at least 27 kJ/mol. Therefore, silicon‐containing molecules are good absorbents for CO2.

Molecular orbital versus DFT calculations in CO2-sequestration reactions with anions: Basis set extrapolation and solvent effects

“…These electronic and geometrical parameters have been reported to correlate with the anion/CO 2 bond strength. 38,39 The amount of charge transferred from the anion to CO 2 strongly depends on the nature of the atom bonding to the carbon atom. As a general trend, the amount of charge transfer occurs in the following order: P > S N > O, reflecting the reverse of the atomic electronegativity.…”

Types of noncovalent bonds within complexes of thiazole with CF4 and SiF4

“…It is not uncommon for positive potentials to occur directly above planar molecules. 44–58 For example, the F substituents on hexafluorobenzene extract density from the carbon ring which leaves the area above this ring with a positive potential. Likewise for a simpler molecule such as F 2 CO where the positive region is situated above the C. These positive areas above planar molecules are commonly designated as π-holes, and like their σ-hole cousins, can engage in strong noncovalent bonding with a nucleophile.…”

Cooperativity between H-bonds and tetrel bonds. Transformation of a noncovalent C⋯N tetrel bond to a covalent bond

“…Hou et al studied the π-hole TBs formed by X 2 TO (X = H, F, Cl, Br, CH 3 ; T = C, Si, Ge, Sn) and CO 2 and found that the interaction energy can be as high as 51 kJ mol −1 . 30 Chandra et al identified a C⋯N π-hole TB between CO 2 and NH 3 by means of infrared spectroscopy and quantum chemical methods. 31…”