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Linewidth variation in the dinitronitrosomethyl dianion radical in the slow exchange mode
Author(s) -
Russell Glen A.,
Norris Robert K.
Publication year - 1970
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.1270020610
Subject(s) - nitromethane , chemistry , nitro , nitrogen , laser linewidth , medicinal chemistry , organic chemistry , physics , laser , alkyl , optics
The treatment of nitromethane or dinitromethane in aqueous alkaline solutions (1 to 2·5 M hydroxide) with nitrogen dioxide yields the dianion radical of dinitronitrosomethane [C(NO 2 ) 2 (NO) \documentclass{article}\pagestyle{empty}\begin{document}$ \buildrel\textstyle.\over= $\end{document} ] which at 30° has hfsc of a N NO 2= 10·75 and 0·65 and a N NO = 5·80 g. Restricted rotation about the CNO bond causes magnetic non‐equivalence of the two nitro groups which can slowly exchange giving rise to line broadening. The use of 15 N labeled nitrogen dioxide gave the dianion radical\documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm [C(}^{{\rm 15}} {\rm NO}_{\rm 2} {\rm)(}^{{\rm 14}} {\rm NO}_{\rm 2} {\rm)(}^{{\rm 15}} {\rm NO)} \buildrel\textstyle.\over= {\rm]} $$\end{document}which exists in two equally populated conformations, each of which shows the expected line broadening for a ‘slow exchange’ process in which the nitro groups are being interconverted.