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Updated: Apr 20, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Surfing π clouds for noncovalent interactions: arenes versus alkenes
Abil E Aliev1, Josephine R T Arendorf, Ilias Pavlakos
1Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (UK). a.e.aliev@ucl.ac.uk.
Abstract:
A comparative study of molecular balances by NMR spectroscopy indicates that noncovalent functional-group interactions with an arene dominate over those with an alkene, and that a π-facial intramolecular hydrogen bond from a hydroxy group to an arene is favored by approximately 1.2 kJ mol(-1). The strongest interaction observed in this study was with the cyano group. Analysis of the series of groups CH2CH3, CH=CH2, C≡CH, and C≡N shows a correlation between conformational free-energy differences and the calculated charge on the C(α) atom of these substituents, which is indicative of the electrostatic nature of their π interactions. Changes in the free-energy differences of conformers show a linear dependence on the solvent hydrogen bond acceptor parameter β.
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