Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH<sub>3</sub>, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH<sub>3</sub> so as to form a chalcogen bond. In the case of T = C, these b...

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Autores principales:	Rafał Wysokiński, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	molecular electrostatic potential solvent effects AIM LMOEDA Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/2383cf7e9f3444df9bb5f3060cb1cf34
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spelling	oai:doaj.org-article:2383cf7e9f3444df9bb5f3060cb1cf342021-11-11T18:25:06ZAbility of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments10.3390/molecules262163941420-3049https://doaj.org/article/2383cf7e9f3444df9bb5f3060cb1cf342021-10-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6394https://doaj.org/toc/1420-3049Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH<sub>3</sub>, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH<sub>3</sub> so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.Rafał WysokińskiWiktor ZierkiewiczMariusz MichalczykSteve ScheinerMDPI AGarticlemolecular electrostatic potentialsolvent effectsAIMLMOEDAOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6394, p 6394 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	molecular electrostatic potential solvent effects AIM LMOEDA Organic chemistry QD241-441
spellingShingle	molecular electrostatic potential solvent effects AIM LMOEDA Organic chemistry QD241-441 Rafał Wysokiński Wiktor Zierkiewicz Mariusz Michalczyk Steve Scheiner Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
description	Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH<sub>3</sub>, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH<sub>3</sub> so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.
format	article
author	Rafał Wysokiński Wiktor Zierkiewicz Mariusz Michalczyk Steve Scheiner
author_facet	Rafał Wysokiński Wiktor Zierkiewicz Mariusz Michalczyk Steve Scheiner
author_sort	Rafał Wysokiński
title	Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
title_short	Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
title_full	Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
title_fullStr	Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
title_full_unstemmed	Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments
title_sort	ability of lewis acids with shallow σ-holes to engage in chalcogen bonds in different environments
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/2383cf7e9f3444df9bb5f3060cb1cf34
work_keys_str_mv	AT rafałwysokinski abilityoflewisacidswithshallowsholestoengageinchalcogenbondsindifferentenvironments AT wiktorzierkiewicz abilityoflewisacidswithshallowsholestoengageinchalcogenbondsindifferentenvironments AT mariuszmichalczyk abilityoflewisacidswithshallowsholestoengageinchalcogenbondsindifferentenvironments AT stevescheiner abilityoflewisacidswithshallowsholestoengageinchalcogenbondsindifferentenvironments
_version_	1718431811385688064

Ability of Lewis Acids with Shallow σ-Holes to Engage in Chalcogen Bonds in Different Environments

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