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Title: /sup 13/C and /sup 15/N chemical shift tensors of para-substituted benzonitriles

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100327a013· OSTI ID:6046723

The principal elements of the /sup 13/C and /sup 15/N chemical shift tensors of a series of 10 para-substituted benzonitriles, enriched in /sup 15/N, have been determined. For the /sup 15/N case the static powder patterns and spinning sideband methods have been employed and compared. For the /sup 13/C case, the two-dimensional Fourier Transform flipper and spinning sideband methods were employed and compared. Each method suffers from the effects of dipolar interactions with nearby nuclei, especially those that are quadrupolar. No evidence is found for compelling empirical correlations between the individual tensor elements, or such combinations of them as the asymmetry or anisotropy parameters, and traditional chemical reactivity parameters employed in linear free energy relationships. Pople's independent-electron molecular orbital perturbation theory is useful in understanding the gross relationships between chemical structure and chemical shift tensor elements and in explaining why certain tensor elements show the largest or smallest resonance-withdrawing or resonance-donating effects of substituents.

Research Organization:
Colorado State Univ., Fort Collins (USA)
OSTI ID:
6046723
Journal Information:
J. Phys. Chem.; (United States), Vol. 92:16
Country of Publication:
United States
Language:
English