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Molecules 2018, 23(6), 1416; https://doi.org/10.3390/molecules23061416

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

1
Faculty of Chemistry, Wrocław University of Science and Technology, Wybrzeże Wyspiańskiego 27, 50370 Wrocław, Poland
2
Department of Chemistry and Biochemistry, Utah State University, Logan, UT 84322-0300, USA
*
Authors to whom correspondence should be addressed.
Academic Editor: Steve Scheiner
Received: 30 May 2018 / Revised: 8 June 2018 / Accepted: 9 June 2018 / Published: 11 June 2018
(This article belongs to the Special Issue Tetrel Bonds)
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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. View Full-Text
Keywords: MP2; DFT; NBO; MEP; AIM MP2; DFT; NBO; MEP; AIM
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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Zierkiewicz, W.; Michalczyk, M.; Scheiner, S. Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions. Molecules 2018, 23, 1416.

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