Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines. / Kostikov, Rafael R. ; Kornilova, Tatiana A. ; Khlebnikov, Alexander F. ; Ivanov, Alexander Yu. ; Shustov, Gennady; Suslonov, Vitaly V. ; Shesternin, Nikolay V. ; Kuznetsov, Mikhail A. .
в: Chemistry of Heterocyclic Compounds, Том 55, № 2, 2019, стр. 172-177.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines
AU - Kostikov, Rafael R.
AU - Kornilova, Tatiana A.
AU - Khlebnikov, Alexander F.
AU - Ivanov, Alexander Yu.
AU - Shustov, Gennady
AU - Suslonov, Vitaly V.
AU - Shesternin, Nikolay V.
AU - Kuznetsov, Mikhail A.
N1 - 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
PY - 2019
Y1 - 2019
N2 - 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 chairconformation with the equatorially fused five-membered rings and with the equatorial orientation of the aryl substituents. A hinderedrotation of the aryl substituents around the C–Ar bonds was observed by low-temperature NMR. Another NMR-observed process thattakes place at low temperature is a reversible isomerization of the major eeee conformer into a slightly less stable aeee isomer. Densityfunctional theory calculations (B3LYP/6-31+G(d)) on the conformational transformations of the parent tricyclic perhydrotetrazine and its5,11-diphenyl derivative are in good agreement with the experimental findings and reveal that a conformation with the orthogonalorientation of the planes of the aryl substituents in respect to the average plane of the six-membered ring has the lowest energy.
AB - 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 chairconformation with the equatorially fused five-membered rings and with the equatorial orientation of the aryl substituents. A hinderedrotation of the aryl substituents around the C–Ar bonds was observed by low-temperature NMR. Another NMR-observed process thattakes place at low temperature is a reversible isomerization of the major eeee conformer into a slightly less stable aeee isomer. Densityfunctional theory calculations (B3LYP/6-31+G(d)) on the conformational transformations of the parent tricyclic perhydrotetrazine and its5,11-diphenyl derivative are in good agreement with the experimental findings and reveal that a conformation with the orthogonalorientation of the planes of the aryl substituents in respect to the average plane of the six-membered ring has the lowest energy.
KW - perhydro-1,2,4,5-tetrazines, conformations of tricyclic perhydrotetrazines, DFT quantum-chemical calculations, variable temperature NMR spectra, X-ray structures
KW - DFT quantum-chemical calculations
KW - conformations of tricyclic perhydrotetrazines
KW - perhydro-1,2,4,5-tetrazines
KW - variable temperature NMR spectra
KW - X-ray structures
UR - http://www.scopus.com/inward/record.url?scp=85063033565&partnerID=8YFLogxK
U2 - 10.1007/s10593-019-02435-3
DO - 10.1007/s10593-019-02435-3
M3 - Article
VL - 55
SP - 172
EP - 177
JO - Chemistry of Heterocyclic Compounds
JF - Chemistry of Heterocyclic Compounds
SN - 0009-3122
IS - 2
ER -
ID: 39936070