Abstract
The classical (Johnson-Bovey) and quantum mechanical (Haigh-Mallion) approach accounting for the shielding contribution to protons in the proximity of aromatic nuclei are compared with respect to their applicability in conformational analysis. This is accomplished by means of the1H-NMR spectra of various cyclophanes their geometries being fairly well known from X-ray data or other independent methods. The chemical shifts of the monitor protons (all of them being situated above or below the plane of the benzene ring considered) are consistent with shielding effects predicted by the classical theory notwithstanding the fact that the benzene hexagons are not strictly planar in any of these systems. In contrast, the quantum mechanical treatment considerably underestimates the shielding of protons in those regions.
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Keller, H., Langer, E. & Lehner, H. Zur Anwendbarkeit von Ringstrommodellen in der Konformationsanalyse. Monatshefte für Chemie 108, 1371–1378 (1977). https://doi.org/10.1007/BF01046451
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DOI: https://doi.org/10.1007/BF01046451