A DFT study on nucleophilicity and site selectivity of nitrogen nucleophiles

► Nucleophilicty of 32 nitrogen nucleophiles have been calculated. ► DFT/B3LYP/6-31G (d, p) level of theory and nucleophilicity index N introduced by Domingo et al. have been used. ► Nucleophilicities of the pyridine series correlate well with Mayr's nucleophilicity and inverse of electrophilicity index values. ► Use of nucleophilicity index Nk and philicity index ωk- for local nucleophilicity trend and site selectivity. ► Both the local indices Nk and ωk- reproduced the experimentally observed trend.