Quantitative study of interactions between oxygen lone pair and aromatic rings: Substituent effect and the importance of closeness of contact

Benjamin W. Gung, Yan Zou, Zhigang Xu, Jay C. Amicangelo, Daniel G. Irwin, Shengqian Ma, Hong Cai Zhou

Research output: Contribution to journalArticle

83 Scopus citations

Abstract

(Figure Presented) Current models describe aromatic rings as polar groups based on the fact that benzene and hexafluorobenzene are known to have large and permanent quadrupole moments. This report describes a quantitative study of the interactions between oxygen lone pair and aromatic rings. We found that even electron-rich aromatic rings and oxygen lone pairs exhibit attractive interactions. Free energies of interactions are determined using the triptycene scaffold and the equilibrium constants were determined by low-temperature 1H NMR spectroscopy. An X-ray structure analysis for one of the model compounds confirms the close proximity between the oxygen and the center of the aromatic ring. Theoretical calculations at the MP2/aug-cc-pVTZ level corroborate the experimental results. The origin of attractive interactions was explored by using aromatic rings with a wide range of substituents. The interactions between an oxygen lone pair and an aromatic ring are attractive at van der Waals' distance even with electron-donating substituents. Electron-withdrawing groups increase the strength of the attractive interactions. The results from this study can be only partly rationalized by using the current models of aromatic system. Electrostatic-based models are consistent with the fact that stronger electron-withdrawing groups lead to stronger attractions, but fail to predict or rationalize the fact that weak attractions even exist between electron-rich arenes and oxygen lone pairs. The conclusion from this study is that aromatic rings cannot be treated as a simple quadrupolar functional group at van der Waals' distance. Dispersion forces and local dipole should also be considered.

Original languageEnglish (US)
Pages (from-to)689-693
Number of pages5
JournalJournal of Organic Chemistry
Volume73
Issue number2
DOIs
StatePublished - Jan 18 2008

All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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