The Bond Dissociation Energy of the N-O Bond.

Bond dissociation energy (BDE) has been calculated for a series of compounds that contain N-O bonds. These structures encompass model N,N,O-trisubstituted hydroxylamines that include O-methoxy, O-acyl, and O-phenyl hydroxylamines. The calculations used three accurate composite methods, CBS-QB3, CBS-APNO, and G4 methods and the computationally more affordable M06-2X/6-311+G(3df,2p) density functional theory (DFT) functional. The calculated N-O single-bond BDEs are 5-15 kcal/mol higher than a generic N-O BDE of 48 kcal/mol quoted in the literature and in textbooks. The M06-2X DFT functional provides BDEs that are in excellent agreement with the higher-level composite methods. We also provided a comparison of the N-O BDE for pyridine-N-oxide to simple trialkylamine oxides. Based on an experimental BDE of 63.3 ± 0.5 kcal/mol for pyridine-N-oxide, our best estimate gives 56.7 ± 0.9 kcal/mol N-O BDE for trimethylamine-N-oxide and 59.0 ± 0.8 kcal/mol for triethylamine-N-oxide.