Theoretical and infrared spectroscopy study of the structure of copper(II) poly-5-vinyltetrazolate and the products of its thermolysis

Authors

Keywords:

density functional theory, IR spectroscopy, poly-5-vinyltetrazole, thermolysis, copper(II) poly-5-vinyltetrazolate

Abstract

The structure of copper(II) poly-5-vinyltetrazolate and the products of its thermolysis has been studied by means of density functional theory and infrared spectroscopy. Copper(II) poly-5-vinyltetrazolate has been obtained and subsequently subjected to thermolysis. Infrared spectra of copper(II) poly-5-vinyltetrazolate and the products of its thermolysis have been recorded. The possible ways of coordination of copper(II) ions with tetrazole-containing ligands were established by analyzing the calculated molecular electrostatic potential distribution and comparing the calculated IR-spectra of the model structures to the experimental ones. It has been shown that the best agreement between the calculated and experimental data is observed for the model with three-coordinated copper(II) ions, which includes both the tetrazole-containing ligands coordinating two copper(II) ions through N(1)- and N(3)-atoms of the tetrazole ring, and the tetrazolecontaining ligands coordinating one copper(II) ion through either the N(2)- or the N(3)-atom. Recently we have shown that the product of thermolysis of copper(II) poly-5-vinyltetrazolate exhibits high catalytic activity in homocoupling of phenylacetylene and Huisgen [3 + 2]-cycloaddition. To establish the structure of the products of thermolysis of copper(II) poly-5-vinyltetrazolate, seven possible products have been proposed based on the analysis of the structure of copper(II) poly-5-vinyltetrazolate and the experimental IR-spectrum. IR-spectra of all proposed products have been calculated and the results of the calculations have been compared with the experimental IR-spectrum of copper(II) poly-5-vinyltetrazolate thermolysis product. It has been shown that the main product of thermolysis is cis-polycyanoacetylene.

Author Biographies

  • Vitaly E. Matulis, Belarusian State University, 4 Niezaliežnasci Avenue, Minsk 220030, Belarus

    PhD (chemistry), docent; associate professor at the department of inorganic chemistry

  • Ekaterina G. Ragoyja, Belarusian State University, 4 Niezaliežnasci Avenue, Minsk 220030, Belarus

    student of the faculty of chemistry

  • Alexander V. Zuraev, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

    PhD (chemistry); researcher at the laboratory of chemistry of condensed systems

  • Yuri V. Grigoriev, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

    PhD (chemistry); head of the laboratory of chemistry of condensed systems

  • Oleg A. Ivashkevich, Belarusian State University, 4 Niezaliežnasci Avenue, Minsk 220030, Belarus

    academician of the National Academy of Sciences of Belarus, doctor of science (chemistry); first vicerector

References

  1. Ostrovskii VA, Koldobskii GI, Trifonov RE. Tetrazoles. In: Katritzky AR, Ramsden CA, Scriven EVF, Taylor RJK, editors. Comprehensive Heterocyclic Chemistry III. Volume 6. Oxford: Elsevier; 2008. p. 257– 423.
  2. Voitekhovich SV, Lesniak V, Gaponik N, Eychmüller A.Tetrazoles: unique capping ligands and precursors for nanostructured materials. Small. 2015;11(43):5728–5739. DOI: 10.1002/smll.201501630.
  3. Finnegan WG, Henry RA, Skolnik S, inventors. Polymers of substituted tetrazoles. Patent US 3004959A. 1961 October 17.
  4. Lesnikovich AI, Levchik SV, Balabanovich AI, Ivashkevich OA, Gaponik PN. The thermal decomposition of tetrazoles. Thermochimica Acta. 1992;200:427– 441. DOI: 10.1016/0040-6031(92)85135-I.
  5. Zimmerman DM, Olofson RA. The rapid synthesis of 1-substituted tetrazoles. Tetrahedron Letters. 1969;10(58):5081–5084. DOI: 10.1016/S0040-4039(01)88889-4.
  6. Levchik SV, Ivashkevich OA, Balabanovich AI, Lesnikovich AI, Gaponik PN, Costa L. Thermal decomposition of tetrazole-containing polymers. I. Poly-5-vinyltetrazole thermolysis. Thermochimica Acta. 1990;168:211–221. DOI: 10.1016/0040-6031(90)80640-K.
  7. Klapötke TM, Sproll SM. Nitrogen-rich polymers based on 5-bromo-1-vinyl-1H-tetrazole. European Journal of Organic Chemistry. 2010;2010(6):1169–1175. DOI: 10.1002/ejoc.200901226.
  8. Levchik SV, Balabanovich AI, Ivashkevich OA, Gaponik PN, Costa L. Thermal decomposition of tetrazole-containing polymers. V. Poly-1-vinyl-5-aminotetrazole. Polymer Degradation and Stability. 1995;47(3):333–338. DOI: 10.1016/0141-3910(94)00130-8.
  9. Gaponik PN, Ivashkevich OA, Karavai VP, Lesnikovich AI, Chernavina NI, Sukhanov GT, Gareev GA. Polymers and copolymers based on vinyltetrazoles. 1. Synthesis of poly(5-vinyltetrazole) by polymer-analogous conversion of polyacrylonitrile. Macromolecular Materials and Engineering. 1994;219(1):77–88. DOI: 10.1002/apmc.1994.052190107.
  10. Gaponik PN, Ivashkevich OA, Lesnikovich AI, Chernavina NI, Sukhanov GT, Gareev GA. Polymers and copolymers based on vinyltetrazoles. 2. Alkylation of poly(5-vinyltetrazole). Die Angewandte Makromolekulare Chemie. 1994;219(1):89–99. DOI: 10.1002/apmc.1994.052190108.
  11. Lesnikovich AI, Levchik SV, Ivashkevich OA, Bolvanovich EE, Gaponik PN, Korsunskii BL. Thermal decomposition of tetrazole-containing polymers. Part 3. Thermolysis of poly-1-vinyltetrazole. Thermochimica Acta. 1993;215:303–313. DOI: 10.1016/0040-6031(93)80106-K.
  12. Zuraev AV, Grigoriev YV, Ivashkevich LS, Lyakhov AS, Ivashkevich OA. Copper-polymer nanocomposite catalyst for synthesis of 1,4-diphenylbutadiyne-1,3. Zeitschrift für anorganische und allgemeine chemie. 2017;643(19):1215–1219. DOI: 10.1002/zaac.201700213.
  13. Zuraev AV, Grigoriev YV, Budevich VA, Ivashkevich OA. Copper-polymer nanocomposite: an efficient catalyst for green Huisgen click synthesis. Tetrahedron Letters. 2018;59(16):1583–1586. DOI: 10.1016/j.tetlet.2018.03.028.
  14. Becke AD. Density-functional thermochemistry. III. The role of exact exchange. Journal of Chemical Physics.1993;98(7):5648–5652. DOI: 10.1063/1.464913.
  15. McLean AD, Chandler GS. Contracted Gaussian basis sets for molecular calculations. 1. Second row atoms, Z = 11–18. Journal of Chemical Physics. 1980;72(10):5639–5648. DOI: 10.1063/1.438980.
  16. Rappoport D, Furche F. Property-optimized Gaussian basis sets for molecular response calculations. Journal of Chemical Physics. 2010;133(13):134105–134111. DOI: 10.1063/1.3484283.
  17. Francl MM, Pietro WJ, Hehre WJ. Self-consistent molecular orbital methods. XXIII. A polarization-type basis set for secondrow elements. Journal of Chemical Physics. 1982;77(7):3654 –3665. DOI: 10.1063/1.444267.
  18. Dolg M, Wedig U, Stoll H. Energy-adjusted ab initio pseudopotentials for the first row transition elements. Journal of Chemical Physics. 1987;86(2):866–872. DOI: 10.1063/1.452110.
  19. Igel-Mann G, Stoll H, Preuss H. Pseudopotentials for main group elements (IIIA through VIIA). Molecular Physics. 1988;65(6):1321–1328. DOI: 10.1080/00268978800101811.
  20. Scalmani G, Frisch MJ. A continuous surface charge formalism for the polarizable continuum model of salvation. Journal of Chemical Physics. 2010;132(11):114110–114115. DOI: 10.1063/1.3359469.
  21. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, et al. Gaussian 09, revision D01, 2012. Wallingford CT: Gaussian, Inc.; 2009.
  22. Nichick MN, Voitekhovich SV, Lesnyak V, Matulis VE, Zheldakova RA, Lesnikovich AI, Ivashkevich OA. 1-Substituted tetrazole-5-thiol-capped noble metal nanoparticles. Journal of Chemical Physics C. 2011;115(34):16928–16933. DOI: 10.1021/jp205649y.

Downloads

Additional Files

Published

2020-03-05

Issue

No. 1 (2020): Journal of the Belarusian State University. Chemistry

Section

Original Articles

License

The authors who are published in this journal agree to the following:

  1. The authors retain copyright on the work and provide the journal with the right of first publication of the work on condition of license Creative Commons Attribution-NonCommercial. 4.0 International (CC BY-NC 4.0).
  2. The authors retain the right to enter into certain contractual agreements relating to the non-exclusive distribution of the published version of the work (e.g. post it on the institutional repository, publication in the book), with the reference to its original publication in this journal.
  3. The authors have the right to post their work on the Internet (e.g. on the institutional store or personal website) prior to and during the review process, conducted by the journal, as this may lead to a productive discussion and a large number of references to this work. (See The Effect of Open Access.)

How to Cite

[1]
Matulis, V.E. et al. 2020. Theoretical and infrared spectroscopy study of the structure of copper(II) poly-5-vinyltetrazolate and the products of its thermolysis. Journal of the Belarusian State University. Chemistry. 1 (Mar. 2020), 19–31. DOI:https://doi.org/10.33581/2520-257X-2020-1-19-31.