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Comparative Study
. 2018 Jun 11;23(6):1416.
doi: 10.3390/molecules23061416.

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

Wiktor Zierkiewicz  1 , Mariusz Michalczyk  2 , Steve Scheiner  3
Affiliations
Comparative Study

Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions

Wiktor Zierkiewicz et al. Molecules. .

Abstract

The σ-hole tetrel bonds formed by a tetravalent molecule are compared with those involving a π-hole above the tetrel atom in a trivalent bonding situation. The former are modeled by TH₄, TH₃F, and TH₂F₂ (T = Si, Ge, Sn) and the latter by TH₂=CH₂, THF=CH₂, and TF₂=CH₂, all paired with NH₃ as Lewis base. The latter π-bonded complexes are considerably more strongly bound, despite the near equivalence of the σ and π-hole intensities. The larger binding energies of the π-dimers are attributed to greater electrostatic attraction and orbital interaction. Each progressive replacement of H by F increases the strength of the tetrel bond, whether σ or π. The magnitudes of the maxima of the molecular electrostatic potential in the two types of systems are not good indicators of either the interaction energy or even the full Coulombic energy. The geometry of the Lewis acid is significantly distorted by the formation of the dimer, more so in the case of the σ-bonded complexes, and this deformation intensifies the σ and π holes.

Keywords: AIM; DFT; MEP; MP2; NBO.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
MEPs of TH4, TH3F and TH2F2 (T = Si, Ge or Sn) computed on the 0.001 au isodensity surface at the MP2/aug-cc-pVDZ-PP level. Colour ranges, in kcal/mol, are: red greater than 15, yellow between 8 and 15, green between 0 and 8, blue below 0 kcal/mol. The letters a and b mean different types of Vs,max.
Figure 2
Figure 2
MEPs of TH2-nFn=CH2 isolated molecules, computed on the 0.001 au isodensity surface at the MP2/aug-cc-pVDZ-PP level. Colour ranges, in kcal/mol, are: red greater than 15, yellow between 8 and 15, green between 0 and 8, blue below 0 kcal/mol. The letters c, d and e mean different types of Vs, max.
Figure 3
Figure 3
Optimized structures of σ-hole bonded tetrel complexes. (a) and (b) refer to σ-hole positions in Figure 1 (N—dark blue, T—green, H—white, F—Light blue).
Figure 4
Figure 4
Optimized structures of π-hole bonded tetrel complexes (N—dark blue, T—green, H—white, F—light blue).
See this image and copyright information in PMC

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