Electron delocalization in the radical cation of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane, a 4-nitrogen-7-electron system

J. M. Zwier, A. M. Brouwer, T. Keszthelyi, G. Balakrishnan, J. F. Offersgaard, R. Wilbrandt, F. Barbosa, U. Buser, J. Amaudrut, G. Gescheidt, S. F. Nelsen, C. D. Little

Research output: Contribution to journalArticle

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Abstract

The radical cation of 1,3,6,8-tetraazatricyclo [4.4.1.13,8]dodecane (TTD) has been studied using magnetic resonance and optical spectroscopic methods and computational techniques. With the help of deuterated isotopomers, assignments of EPR and resonance Raman spectra could be unequivocally established. The results demonstrate that the radical cation has D2d symmetry, and instantaneous electron delocalization over the four equivalent nitrogen atoms occurs. This extensive delocalization in a completely saturated system is a unique feature of the TTD radical cation. The spectroscopy of TTD, in contrast to that of simpler diamines such as 1,4-diaza[2.2.2]bicyclooctane, simultaneously reveals the consequences of orbital interactions through space and through bonds. The relationship between nitrogen pyramidalization and hyperfine coupling constants in nitrogen-centered radical cations with a number of different bonding arrangements is reviewed.

Original languageEnglish
Pages (from-to)159-167
Number of pages9
JournalJournal of the American Chemical Society
Volume124
Issue number1
DOIs
Publication statusPublished - Jan 9 2002

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Cations
Nitrogen
Positive ions
Electrons
Diamines
Magnetic resonance
Paramagnetic resonance
Raman scattering
Spectrum Analysis
Magnetic Resonance Spectroscopy
Spectroscopy
Atoms
n-dodecane

ASJC Scopus subject areas

  • Chemistry(all)

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Electron delocalization in the radical cation of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane, a 4-nitrogen-7-electron system. / Zwier, J. M.; Brouwer, A. M.; Keszthelyi, T.; Balakrishnan, G.; Offersgaard, J. F.; Wilbrandt, R.; Barbosa, F.; Buser, U.; Amaudrut, J.; Gescheidt, G.; Nelsen, S. F.; Little, C. D.

In: Journal of the American Chemical Society, Vol. 124, No. 1, 09.01.2002, p. 159-167.

Research output: Contribution to journalArticle

Zwier, JM, Brouwer, AM, Keszthelyi, T, Balakrishnan, G, Offersgaard, JF, Wilbrandt, R, Barbosa, F, Buser, U, Amaudrut, J, Gescheidt, G, Nelsen, SF & Little, CD 2002, 'Electron delocalization in the radical cation of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane, a 4-nitrogen-7-electron system', Journal of the American Chemical Society, vol. 124, no. 1, pp. 159-167. https://doi.org/10.1021/ja016999n
Zwier, J. M. ; Brouwer, A. M. ; Keszthelyi, T. ; Balakrishnan, G. ; Offersgaard, J. F. ; Wilbrandt, R. ; Barbosa, F. ; Buser, U. ; Amaudrut, J. ; Gescheidt, G. ; Nelsen, S. F. ; Little, C. D. / Electron delocalization in the radical cation of 1,3,6,8-tetraazatricyclo[4.4.1.13,8]dodecane, a 4-nitrogen-7-electron system. In: Journal of the American Chemical Society. 2002 ; Vol. 124, No. 1. pp. 159-167.
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AU - Amaudrut, J.

AU - Gescheidt, G.

AU - Nelsen, S. F.

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