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.
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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.
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The Supplementary information file containing 1H and 13C{1H} NMR spectra is available at the journal website at http://link.springer.com/journal/10593.
Published in Khimiya Geterotsiklicheskikh Soedinenii, 2019, 55(2), 172–177
Rafael R. Kostikov is deceased
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Kostikov, R.R., Kornilova, T.A., Khlebnikov, A.F. et al. Spatial Structure and Nontrivial Stereodynamics of Tricyclic Perhydro-1,2,4,5-Tetrazines. Chem Heterocycl Comp 55, 172–177 (2019). https://doi.org/10.1007/s10593-019-02435-3
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DOI: https://doi.org/10.1007/s10593-019-02435-3