Quantification of CH⋅⋅⋅π Interactions: Implications on How Substituent Effects Influence Aromatic Interactions

Attractive interactions between a substituted benzene ring and an α‐substituted acetate group were determined experimentally by using the triptycene model system. The attractive interaction correlates well with the Hammett constants σm (R2=0.90), but correlates much better with the acidity of the α‐...

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Bibliographic Details
Published in:Chemistry : a European journal 2010-11, Vol.16 (41), p.12357-12362
Main Authors: Gung, Benjamin W., Emenike, Bright U., Lewis, Michael, Kirschbaum, Kristin
Format: Article
Language:English
Subjects:
Acetates
aromatic interactions
Benzene
CHP
computational chemistry
Constants
Correlation
Displays
Hammett plots
Rings (mathematics)
Straight lines
substituent effects
triptycenes
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Summary:Attractive interactions between a substituted benzene ring and an α‐substituted acetate group were determined experimentally by using the triptycene model system. The attractive interaction correlates well with the Hammett constants σm (R2=0.90), but correlates much better with the acidity of the α‐protons (R2=0.98). A predominant CH⋅⋅⋅π interaction was found to control the conformational preference of model compounds 1 a–g. Despite the predominance of the CH⋅⋅⋅π interaction in compounds 1 a–g, a Hammett plot displays a fairly straight line for the substituent effect. These results show that when using Hammett plots in a simplified model system, a system designed to study the effect of X⋅⋅⋅π interactions could capture the XH⋅⋅⋅π interaction instead.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201001362