PCM study of bond dissociation energies in N-nitroso compounds

A PCM continuum model, at the B3LYP, B3P86, and B3PW91 three-parameter hybrid DFT methods with 6-31G∗∗ and 6-311G∗∗ basis sets, is used to study the bond dissociation energies (BDEs) of N-nitroso compounds. Compared the computed results with the experimental values, it is noted that B3P86 method is a better method to compute the bond dissociation energies of N-nitroso compounds among the DFT methods selected. The substituent effects on the BDEs of the N-NO bond are analyzed and it is shown that the BDE of the N-NO bond increases with the increment of the Hammett constants of substituent groups for the second series of N-nitroso compounds. Subsequently, some NO-donors such as N-nitroso compounds, O-nitrosyl carboxylate compounds and S-Nitrosothiols are compared.