日本語
 
User Manual Privacy Policy ポリシー/免責事項 連絡先
  詳細検索ブラウズ

アイテム詳細


公開

学術論文

Hydrogen splittings of bis-bicyclic hydrazine radical cations

MPS-Authors
/persons/resource/persons94523

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

URL

http://pubs.acs.org/doi/pdf/10.1021/ja00066a029
(全文テキスト(全般))

https://dx.doi.org/10.1021/ja00066a029
(全文テキスト(全般))

フルテキスト (公開)
公開されているフルテキストはありません
付随資料 (公開)
There is no public supplementary material available
引用

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


引用: http://hdl.handle.net/11858/00-001M-0000-0019-AA3C-9
要旨
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