13C NMR: Substituent effects on one-bond 15N?13C coupling constants in anilines and anilinium ions

¹J(¹⁵N¹³C) values obtained from FT ¹³C NMR spectra were measured for a number of ¹⁵N-enriched aniline derivatives and are found to exhibit varying degrees of dependence on the nature of the ring substituent. Theoretical calculations of ¹J(¹⁵N¹³C) values for representative members of the systems examined were made using INDO parameters and a ‘sum-over-states’ perturbation approach. The calculated coupling constants are generally in fair agreement with experimental values when the integral products S_N²(o)S_C²(o) and (r^?3)_N(r^?3)_C have values of 34.437 au^?6 and 2.770 au^?6, respectively.