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

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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. .

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

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{5eea99e71fe34cc5bbf5e95ae7bae23f,

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.",

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

author = "Kostikov, {Rafael R.} and Kornilova, {Tatiana A.} and Khlebnikov, {Alexander F.} and Ivanov, {Alexander Yu.} and Gennady Shustov and Suslonov, {Vitaly V.} and Shesternin, {Nikolay V.} and Kuznetsov, {Mikhail A.}",

note = "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",

year = "2019",

doi = "10.1007/s10593-019-02435-3",

language = "English",

volume = "55",

pages = "172--177",

journal = "Chemistry of Heterocyclic Compounds",

issn = "0009-3122",

publisher = "Springer Nature",

number = "2",

}

RIS

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