13C NMR chemical shifts in substituted benzenes: analysis using natural perturbation orbitals and substitution effects

Abstract

The natural perturbation orbital (NPO) method, combined with the gauge-including atomic orbital (GIAO), was applied to nuclear magnetic resonance (NMR) chemical shifts. The substituent effects of electron-donating (NH2) and electron-withdrawing (NO2) groups on the 13C NMR chemical shifts of monosubstituted benzenes were analysed using NPOs. 13C chemical shifts at the ortho-, meta- and para-positions were efficiently decomposed into contributions from two NPO pairs (, ). These contributions were further divided into two factors, namely electron density in the vicinity of resonance nuclei and orbital energy gaps. Trends in the electron density matched with the ortho-, meta- and para-directions of the substituent effects. Specifically, NH2 shielded the ortho- and para-carbons, while NO2 deshielded the same carbons. The orbital energy gaps of ortho-carbons in NH2- and NO2-benzenes were significantly decreased, showing that these substituents shielded the ortho-carbons.