Observations of tetrel bonding between sp3-carbon and THF

• Published in: Chemical science (Cambridge) Vol. 11; no. 20; pp. 5289 - 5293
• Main Authors: Heywood, Victoria L, Alford, Thomas P J, Roeleveld, Julius J, Siebe J Lekanne Deprez, Verhoofstad, Abraham, Jarl Ivar van der Vlugt, Domingos, Sérgio R, Schnell, Melanie, Davis, Anthony P, Mooibroek, Tiddo J
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 07.05.2020; The Royal Society of Chemistry
• Subjects: Chemistry; Crystal structure; Crystallinity; Crystallography; Quantum chemistry; Tetrahydrofuran; Vapor phases
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d0sc01559h

We report the direct observation of tetrel bonding interactions between sp3-carbons of the supramolecular synthon 3,3-dimethyl-tetracyanocyclopropane (1) and tetrahydrofuran in the gas and crystalline phase. The intermolecular contact is established via σ-holes and is driven mainly by electrostatic forces. The complex manifests distinct binding geometries when captured in the crystalline phase and in the gas phase. We elucidate these binding trends using complementary gas phase quantum chemical calculations and find a total binding energy of −11.2 kcal mol−1 for the adduct. Our observations pave the way for novel strategies to engineer sp3-C centred non-covalent bonding schemes for supramolecular chemistry.