APPLICATION OF C-13 AND N-15 SPECTROSCOPY TO THE STUDY OF ELECTRONIC DELOCALIZATION IN N-N BONDS - NITROSAMINES, HYDRAZONES, TRIAZENES AND RELATED PROTONATED SPECIES

13C and 15N spectroscopies at natural abundance have been applied to the study of nitrogen lone‐pair delocalization in NN containing compounds: nitrosamines, nitramines, hydrazines, hydrazones and triazenes. Structure‐chemical shift correlations have been derived for nitrosamines; the 13C upfield effect of a γ substituent has been used for assigning the configuration of both diastereoisomers in N,N‐unsymmetrically substituted nitrosamines. Equations have been computed which permit the prediction of the electronic delocalization, expressed in terms of free enthalpy of activation ΔG ≠298, as a function of δ15N and of the length of the NN bond. 15N spectroscopy has also been applied to the study of the protonated species of nitrosamines and of acceptor‐donor complexes of nitrosamines with Lewis acids. The behaviour of such NN containing compounds is compared to that of amides. Copyright © 1979 Heyden & Son Ltd.