Stereochemical dependence of substituent γ-effects in the 19 F NMR shielding constants.

Abstract

The substituent α-, β-, and γ-effects of the elements of the second and third periods on 19 F NMR chemical shifts are evaluated including the establishment of stereochemical dependence of γ-effect, the latter particularly important in stereochemical studies of fluorine-containing compounds. Benchmark calculations performed for a series of 32 simple inorganic fluorine-containing molecules demonstrated a markedly good correlation between calculated and experimental fluorine chemical shifts characterized by a mean absolute error of 22.5ppm in the range of about 900 ppm, which corresponds to a 2.5% error in the percentage terms.