Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines

Михаил Анатольевич Кузнецов, Виталий Валерьевич Суслонов, Рафаэль Равилович Костиков, Александр Феодосиевич Хлебников, Александр Юльевич Иванов, Татьяна Алексеевна Корнилова, Николай Валерьевич Шестернин, Gennady Shustov

Research output

1 Citation (Scopus)

Abstract

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.
Original languageEnglish
Pages (from-to)172-177
Number of pages6
JournalChemistry of Heterocyclic Compounds
Volume55
Issue number2
Publication statusPublished - 2019

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Nuclear magnetic resonance
Thermolysis
Hexanes
Isomerization
Structural analysis
Isomers
Dimers
Methanol
Conformations
Derivatives
X rays
Temperature
diphenyl

Scopus subject areas

  • Chemistry(all)

Cite this

Кузнецов, Михаил Анатольевич ; Суслонов, Виталий Валерьевич ; Костиков, Рафаэль Равилович ; Хлебников, Александр Феодосиевич ; Иванов, Александр Юльевич ; Корнилова, Татьяна Алексеевна ; Шестернин, Николай Валерьевич ; Shustov, Gennady. / Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines. In: Chemistry of Heterocyclic Compounds. 2019 ; Vol. 55, No. 2. pp. 172-177.
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title = "Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines",
abstract = "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.",
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author = "Кузнецов, {Михаил Анатольевич} and Суслонов, {Виталий Валерьевич} and Костиков, {Рафаэль Равилович} and Хлебников, {Александр Феодосиевич} and Иванов, {Александр Юльевич} and Корнилова, {Татьяна Алексеевна} and Шестернин, {Николай Валерьевич} and Gennady Shustov",
year = "2019",
language = "English",
volume = "55",
pages = "172--177",
journal = "Chemistry of Heterocyclic Compounds",
issn = "0009-3122",
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Кузнецов, МА, Суслонов, ВВ, Костиков, РР, Хлебников, АФ, Иванов, АЮ, Корнилова, ТА, Шестернин, НВ & Shustov, G 2019, 'Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines', Chemistry of Heterocyclic Compounds, vol. 55, no. 2, pp. 172-177.

Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines. / Кузнецов, Михаил Анатольевич; Суслонов, Виталий Валерьевич; Костиков, Рафаэль Равилович; Хлебников, Александр Феодосиевич; Иванов, Александр Юльевич; Корнилова, Татьяна Алексеевна; Шестернин, Николай Валерьевич; Shustov, Gennady.

In: Chemistry of Heterocyclic Compounds, Vol. 55, No. 2, 2019, p. 172-177.

Research output

TY - JOUR

T1 - Spatial structure and non-trivial stereodynamic of tricyclic perhydro-1,2,4,5-tetrazines

AU - Кузнецов, Михаил Анатольевич

AU - Суслонов, Виталий Валерьевич

AU - Костиков, Рафаэль Равилович

AU - Хлебников, Александр Феодосиевич

AU - Иванов, Александр Юльевич

AU - Корнилова, Татьяна Алексеевна

AU - Шестернин, Николай Валерьевич

AU - Shustov, Gennady

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

M3 - Article

VL - 55

SP - 172

EP - 177

JO - Chemistry of Heterocyclic Compounds

JF - Chemistry of Heterocyclic Compounds

SN - 0009-3122

IS - 2

ER -