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Spatial Structure and Nontrivial Stereodynamics of Tricyclic Perhydro-1,2,4,5-Tetrazines

  • Rafael R. Kostikov
  • Tatiana A. Kornilova
  • Alexander F. Khlebnikov
  • Gennady V. Shustov
  • Alexander Yu. Ivanov
  • Vitaly V. Suslonov
  • Nikolay V. Shesternin
  • Mikhail A. KuznetsovEmail author
Article
  • 10 Downloads

Thermolysis of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes in methanol leads to the respective dimers, 5,11-diaryltetrahydro-1H,7Hdipyrazolo[1,2-a:1',2'-d]tetrazines. X-ray structural analysis of these compounds reveals the perhydrotetrazine ring adopting a chair conformation with the equatorially fused five-membered rings and with the equatorial orientation of the aryl substituents. A hindered rotation of the aryl substituents around the C–Ar bonds was observed by low-temperature NMR. Another NMR-observed process that takes place at low temperature is a reversible isomerization of the major eeee conformer into a slightly less stable aeee isomer. Density functional theory calculations (B3LYP/6-31+G(d)) on the conformational transformations of the parent tricyclic perhydrotetrazine and its 5,11-diphenyl derivative are in good agreement with the experimental findings and reveal that a conformation with the orthogonal orientation of the planes of the aryl substituents in respect to the average plane of the six-membered ring has the lowest energy.

Keywords

perhydro-1,2,4,5-tetrazines conformations of tricyclic perhydrotetrazines DFT quantum-chemical calculations variable temperature NMR spectra X-ray structures 

Notes

Acknowledgements

This work was supported by the Russian Foundation for Basic Research (grant № 15-03-05319).

NMR, HRMS, and XRD analyses were performed at the Saint Petersburg State University Center for Magnetic Resonance, Center for Chemical Analysis and Materials Research, and X-ray Diffraction Center, respectively.

Supplementary material

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Rafael R. Kostikov
    • 1
  • Tatiana A. Kornilova
    • 1
  • Alexander F. Khlebnikov
    • 1
  • Gennady V. Shustov
    • 2
  • Alexander Yu. Ivanov
    • 1
  • Vitaly V. Suslonov
    • 1
  • Nikolay V. Shesternin
    • 1
  • Mikhail A. Kuznetsov
    • 1
    Email author
  1. 1.Institute of Chemistry, Saint Petersburg State UniversitySaint PetersburgRussia
  2. 2.Department of Chemistry, University of the Fraser ValleyAbbotsfordCanada

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