Document Type
Article
Author ORCID Identifier
Mariusz Michalczyk https://orcid.org/0000-0002-6495-6963
Wiktor Zierkiewicz https://orcid.org/0000-0002-4038-5959
Steve Scheiner https://orcid.org/0000-0003-0793-0369
Journal/Book Title
Chemical Science
Publication Date
5-5-2025
Publisher
Royal Society of Chemistry
Journal Article Version
Version of Record
Volume
16
Issue
23
First Page
10572
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial 4.0 License
Last Page
10584
Abstract
There is a great deal of strain within the propellane and pyramidane hydrocarbon molecules. Quantum chemical calculations evaluate how this strain affects the ability of the bridgehead C atom to act as an electron donor in hydrogen, halogen, chalcogen, pnicogen, and tetrel bonds, despite the absence of a formal C lone pair or CC multiple bond. The strain induces the formation of a substantial region of negative electrostatic potential on this C atom which can attract the σ-hole of an electrophile. Each such molecule also contains an occupied molecular orbital that can be described as either a C lone pair or C–C bond, which is spatially disposed to align with, and transfer charge to, a σ* antibonding orbital of an approaching Lewis acid. The degree of strain within the hydrocarbon is closely correlated with the magnitude of the negative electrostatic potential, which is in turn connected with the strength of the ensuing bond. Tetrel bonds are strongest, followed by halogen, both of which contain a significant degree of covalency.
Recommended Citation
Michalczyk, M., Zierkiewicz, W., Scheiner, S. Ability of strained C atoms to act as an electron donor. Chem. Sci., 2025, 16, 10572-10584 https://doi.org/10.1039/D5SC01632K