Theoretical study of alkyl-pi and aryl-pi interactions. Reconciling theory and experiment.

TitleTheoretical study of alkyl-pi and aryl-pi interactions. Reconciling theory and experiment.
Publication TypeJournal Article
Year of Publication2002
AuthorsRibas, Jordi, Cubero Elena, F Luque Javier, and Orozco Modesto
JournalJ Org Chem
Volume67
Pagination7057-65
Date Published2002 Oct 4
ISSN0022-3263
Abstract

Quantum mechanical and quantum mechanical/molecular mechanical calculations in conjunction with continuum solvation models have been used to analyze CH-pi interactions in model systems of aryl- and alkyl-aromatic interactions, as well as in a model folding system designed to study those interactions. High level calculations reproduced accurately the interaction of CH-pi interactions in both alkyl- and aryl-based model systems. Dispersion effects dominate the interaction, but the electrostatics term is also relevant for aryl CH-pi interactions. Theoretical calculations were also used to examine the influence of CH-pi interactions in determining the conformational flexibility of folding models. Finally, a critical comparison of the results obtained from high level calculations on model systems and the experimental data derived for folding models in apolar solvents was carried out, which allowed us to reconcile the apparent discrepancy found between both data.