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

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 TH(4), TH(3)F, and TH(2)F(2) (T = Si, Ge, Sn) and the latter by TH(2)=CH(2), THF=CH(2), and TF(2)=CH(2), all paired wi...

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Autores principales: Zierkiewicz, Wiktor, Michalczyk, Mariusz, Scheiner, Steve
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6100375/
https://www.ncbi.nlm.nih.gov/pubmed/29891824
http://dx.doi.org/10.3390/molecules23061416
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author Zierkiewicz, Wiktor
Michalczyk, Mariusz
Scheiner, Steve
author_facet Zierkiewicz, Wiktor
Michalczyk, Mariusz
Scheiner, Steve
author_sort Zierkiewicz, Wiktor
collection PubMed
description 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 TH(4), TH(3)F, and TH(2)F(2) (T = Si, Ge, Sn) and the latter by TH(2)=CH(2), THF=CH(2), and TF(2)=CH(2), all paired with NH(3) 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.
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spelling pubmed-61003752018-11-13 Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions Zierkiewicz, Wiktor Michalczyk, Mariusz Scheiner, Steve Molecules Article 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 TH(4), TH(3)F, and TH(2)F(2) (T = Si, Ge, Sn) and the latter by TH(2)=CH(2), THF=CH(2), and TF(2)=CH(2), all paired with NH(3) 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. MDPI 2018-06-11 /pmc/articles/PMC6100375/ /pubmed/29891824 http://dx.doi.org/10.3390/molecules23061416 Text en © 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Zierkiewicz, Wiktor
Michalczyk, Mariusz
Scheiner, Steve
Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title_full Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title_fullStr Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title_full_unstemmed Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title_short Comparison between Tetrel Bonded Complexes Stabilized by σ and π Hole Interactions
title_sort comparison between tetrel bonded complexes stabilized by σ and π hole interactions
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6100375/
https://www.ncbi.nlm.nih.gov/pubmed/29891824
http://dx.doi.org/10.3390/molecules23061416
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