Quantitative study of interactions between oxygen lone pair and aromatic rings: substituent effect and the importance of closeness of contact.
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.
Gung
Benjamin W
BW
Department of Chemistry & Biochemistry, Miami University, Oxford, Ohio 45056, USA. gungbw@muohio.edu
Zou
Yan
Y
Xu
Zhigang
Z
Amicangelo
Jay C
JC
Irwin
Daniel G
DG
Ma
Shengqian
S
Zhou
Hong-Cai
HC
D001555:Benzene Derivatives / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004583:Electrons; D057927:Hydrophobic and Hydrophilic Interactions; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D008968:Molecular Conformation; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
D001555:Benzene Derivatives; D010100:Oxygen