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Journal Article

Hydrogen splittings of bis-bicyclic hydrazine radical cations


Neugebauer,  Franz A.
Department of Organic Chemistry, Max Planck Institute for Medical Research, Max Planck Society;

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Nelsen, S. F., Petillo, P. A., De Felippis, J., Wang, Y., Chen, L. J., Yunta, M. J. R., et al. (1993). Hydrogen splittings of bis-bicyclic hydrazine radical cations. Journal of the American Chemical Society, 115(13), 5608-5615. doi:10.1021/ja00066a029.

Cite as: http://hdl.handle.net/11858/00-001M-0000-0019-AA3C-9
1H-NMR spectra of bis-bicyclic hydrazine radical cations allowed determination of the magnitude and sign of the proton splitting constants under -2 G, and assignments to position using deuterium labeling were made for several cases. ENDOR spectra measured the hydrogen splittings over 2 G. Bridgehead hydrogen splitting constants for sesquibicyclic compounds (bis−N,N'−bicyclics) were observed in the range -0.10 to +O. 14 for six examples containing 2,3-diazabicyclo[2.2.2]octylr ings, -0.14 to -0.04 for two 2,3-diazabicyclo[2.2.2]octenylc ompounds, +0.02 to +0.21 for four compounds containing 5,6-diazabicyclo[3.2.2]nonyl and -nonenyl rings, and +0.35 to +0.84 for compounds containing 2,3-diazabicyclo[2.2.1] heptyl rings. There is not a simple correlation of these bridgehead splitting constants with the lone pair N, C-Hb dihedral angle. For the nine sesquibicyclic hydrazine radical cations studied, the exo splittings in dimethylene bridges were positive, and the endo splittings were negative in sign. Examination of the W and non-W exo y hydrogen splittings in systems containing bicyclo[2.2.2]octyl rings allowed estimation of the energy difference between double nitrogen inversion conformations