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Surfing π Clouds for Noncovalent Interactions: Arenes versus Alkenes
Author(s) -
Aliev Abil E.,
Arendorf Josephine R. T.,
Pavlakos Ilias,
Moreno Rafael B.,
Porter Michael J.,
Rzepa Henry S.,
Motherwell William B.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201409672
Subject(s) - chemistry , alkene , intramolecular force , conformational isomerism , non covalent interactions , hydrogen bond , computational chemistry , stereochemistry , crystallography , molecule , organic chemistry , catalysis
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 CH 2 CH 3 , CHCH 2 , CCH, and CN 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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