Author ORCID Identifier
Steve Scheiner https://orcid.org/0000-0003-0793-0369
NSF, Division of Chemistry (CHE) 1954310
NSF, Division of Chemistry (CHE)
Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.
Several cyano groups are added to an alkane, alkene, and alkyne group so as to construct a Lewis acid molecule with a positive region of electrostatic potential in the area adjoining these substituents. Although each individual cyano group produces only a weak π-hole, when two or more such groups are properly situated, they can pool their π-holes into one much more intense positive region that is located midway between them. A NH3 base is attracted to this site, where it forms a strong noncovalent bond to the Lewis acid, amounting to as much as 13.6 kcal/mol. The precise nature of the bonding varies a bit from one complex to the next but typically contains a tetrel bond to the C atoms of the cyano groups or the C atoms of the linkage connecting the C≡N substituents. The placement of the cyano groups on a cyclic system like cyclopropane or cyclobutane has a mild weakening effect upon the binding. Although F is comparable to C≡N in terms of electron-withdrawing power, the replacement of cyano by F substituents substantially weakens the binding with NH3.
Scheiner, S. Versatility of the Cyano Group in Intermolecular Interactions. Molecules 2020, 25, 4495. https://doi.org/10.3390/molecules25194495