Two series of conformation ally restricted polycyclic compounds (1-3 and 4-7) have been synthesized as model systems for studying the through-space interactions between face-to-face, center-to-edge (parallel-offset) oriented arenes. These compounds feature different X substituents on one of the interacting rings. By monitoring the variation of the DeltaG(not equal) for the rotation around the aryl-aryl bond in 1-7 as a function of X by 2D [H-1,H-1] EXSY NMR spectroscopy, it was found that the barriers increase on passing from electron-donating to electron-withdrawing substituted derivatives. Quantum mechanical calculations [MP2/DVZ (2d,p)//B3LYP/DVZ(2d,p)] gave barrier values and variations in agreement with the experimental data. The results are consistent with a repulsive arene-arene interaction dominated by electrostatic effects.

Through-space interactions between face-to-face, center-to-edge oriented arenes: importance of polar-pi effects / F. Cozzi, R. Annunziata, M. Benaglia, M. Cinquini, L. Raimondi, K. Baldridge, J. Siegel. - In: ORGANIC & BIOMOLECULAR CHEMISTRY. - ISSN 1477-0520. - 1:1(2003), pp. 157-162.

Through-space interactions between face-to-face, center-to-edge oriented arenes: importance of polar-pi effects

F. Cozzi
Primo
;
R. Annunziata
Secondo
;
M. Benaglia;M. Cinquini;L. Raimondi;
2003

Abstract

Two series of conformation ally restricted polycyclic compounds (1-3 and 4-7) have been synthesized as model systems for studying the through-space interactions between face-to-face, center-to-edge (parallel-offset) oriented arenes. These compounds feature different X substituents on one of the interacting rings. By monitoring the variation of the DeltaG(not equal) for the rotation around the aryl-aryl bond in 1-7 as a function of X by 2D [H-1,H-1] EXSY NMR spectroscopy, it was found that the barriers increase on passing from electron-donating to electron-withdrawing substituted derivatives. Quantum mechanical calculations [MP2/DVZ (2d,p)//B3LYP/DVZ(2d,p)] gave barrier values and variations in agreement with the experimental data. The results are consistent with a repulsive arene-arene interaction dominated by electrostatic effects.
Settore CHIM/06 - Chimica Organica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/181584
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