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Application of 13 C and 15 N spectroscopy to the study of electronic delocalization in NN bonds: Nitrosamines, hydrazones, triazenes and related protonated species
Author(s) -
Gouesnard J. P.,
Martin G. J.
Publication year - 1979
Publication title -
organic magnetic resonance
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0030-4921
DOI - 10.1002/mrc.1270120502
Subject(s) - chemistry , delocalized electron , protonation , lone pair , substituent , enthalpy , spectroscopy , natural bond orbital , medicinal chemistry , stereochemistry , crystallography , computational chemistry , organic chemistry , density functional theory , molecule , ion , physics , quantum mechanics
13 C and 15 N spectroscopies at natural abundance have been applied to the study of nitrogen lone‐pair delocalization in NN containing compounds: nitrosamines, nitramines, hydrazines, hydrazones and triazenes. Structure‐chemical shift correlations have been derived for nitrosamines; the 13 C 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 δ 15 N and of the length of the NN bond. 15 N 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 NN containing compounds is compared to that of amides.