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Russian Journal of Coordination Chemistry

, Volume 45, Issue 7, pp 489–495 | Cite as

Heterospin Copper(II) Catecholate Complex with the TEMPO–Iminopyridine Ligand

  • A. V. Cherkasova
  • K. A. Kozhanov
  • A. A. Zolotukhin
  • A. S. Bogomyakov
  • A. V. Cherkasov
  • V. K. CherkasovEmail author
Article
  • 14 Downloads

Abstract

The heterospin copper(II) complex, ((pyridin-2-ylmethylene)-4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl)-3,6-di-tert-butylcatecholatocopper(II) (I), is synthesized and characterized by IR spectroscopy, magnetochemistry, EPR, and X-ray diffraction analysis. The one-electron oxidation of complex I by AgBF4 affords the biradical copper(I) complex: bis[((pyridin-2-ylmethylene)-4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl)]copper(I) (II). An analysis of the parameters of isotropic EPR spectra of complexes I and II indicates that they are biradicals with the fast (I) and intermediate (II) exchange interaction between the radical centers.

Keywords:

biradical heterospin complexes copper(II) molecular spectroscopy 

Notes

ACKNOWLEDGMENTS

The X-ray diffraction studies were carried out in the framework of the state task (theme no. 44.2, registration no. AAAA-A16-116122110053-1) using the scientific equipment of the Center for Collective Use “Analytical Center of the Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences.”

FUNDING

This work was supported by the Russian Science Foundation, grant no. 14-13-01296.

REFERENCES

  1. 1.
    Ovcharenko, V., Metal-Nitroxide Complexes: Synthesis and Magnetostructural Correlations, Ch. 13, Stable Radicals: Fundamentals and Applied Aspects of Odd-Electron Compounds, Wiley, 2010, p. 461.Google Scholar
  2. 2.
    Fedin, M.V., Veber, S.L., Bagryanskaya, E.G., et al., Coord. Chem. Rev., 2015, vols. 289−290, p. 341.CrossRefGoogle Scholar
  3. 3.
    Eaton, S.S., Coord. Chem. Rev., 1978, vol. 26, p. 20.CrossRefGoogle Scholar
  4. 4.
    Eaton, S.S. and Eaton, G.R., Coord. Chem. Rev., 1988, vol. 83, p. 29.CrossRefGoogle Scholar
  5. 5.
    Pierpont, C.G. and Buchanan, R.M., Coord. Chem. Rev., 1981, vol. 38, p. 45.Google Scholar
  6. 6.
    Pierpont, C.G., Coord. Chem. Rev., 2001, vols. 219−221, p. 415.CrossRefGoogle Scholar
  7. 7.
    Pierpont, C.G., Coord. Chem. Rev., 2001, vols. 216–217, p. 99.CrossRefGoogle Scholar
  8. 8.
    Hendrickson, D.N. and Pierpont, C.G., Valence Tautomeric Transition Metal Complexes. Spin Crossover in Transition Metal Compounds II, Berlin: Springer, 2004, vol. 234, p. 63.Google Scholar
  9. 9.
    Pierpont, C.G. and Lange, C.W., The Chemistry of Transition Metal Complexes Containing Catechol and Semiquinone Ligands. Progress in Inorganic Chemistry, New York: Wiley, 2007, р. 331.Google Scholar
  10. 10.
    Pierpont, C.G. and Kelly, J.K., Coordination Chemistry of o-Semiquinones. PATAI’S Chemistry of Functional Groups, New York: Wiley, 2009.Google Scholar
  11. 11.
    Poddel’sky, A.I., Cherkasov, V.K., and Abakumov, G.A., Coord. Chem. Rev., 2009, vol. 253, p. 291.CrossRefGoogle Scholar
  12. 12.
    Boymel, P.M., Eaton, G.R., and Eaton, S.S., Inorg. Chem., 1980, vol. 19, no. 3, p. 727.CrossRefGoogle Scholar
  13. 13.
    Boymel, P.M., Braden, G.A., Eaton, G.R., et al., Inorg. Chem., 1980, vol. 19, no. 3, p. 735.CrossRefGoogle Scholar
  14. 14.
    Hard, S. and Eaton, G.R., J. Magn. Res., 1983, vol. 51, p. 470.Google Scholar
  15. 15.
    More, J.K., More, K.M., Eaton, G.R., et al., J. Am. Chem. Soc., 1984, vol. 106, p. 5395.CrossRefGoogle Scholar
  16. 16.
    Zolotukhin, A.A., Bubnov, M.P., Arapova, A.V., et al., Inorg. Chem., 2017, vol. 56, p. 14751.CrossRefGoogle Scholar
  17. 17.
    Armarego, W.L.F. and Chai, C., Purification of Laboratory Chemicals, Butterworth-Heinemann, 2013.Google Scholar
  18. 18.
    Kim, S., Kim, E., Lee, H.J., et al., Polyhedron, 2014, vol. 69, p. 149.CrossRefGoogle Scholar
  19. 19.
    Abakumov, G.A., Lobanov, A.V., Cherkasov, V.K., et al., Inorg. Chim. Acta, 1981, vol. 49, p. 135.CrossRefGoogle Scholar
  20. 20.
    Stoll, S. and Schweiger, A., J. Magn. Res., 2006, vol. 178, p. 42.CrossRefGoogle Scholar
  21. 21.
    Kozhanov, K.A., Bubnov, M.P., Teplova, I.A., et al., J. Mol. Struct., 2017, vol. 1147, p. 541.CrossRefGoogle Scholar
  22. 22.
    APEX3. Version 2016-9, Madison: Bruker AXS Inc., 2016.Google Scholar
  23. 23.
    Krause, L., Herbst-Irmer, R., Sheldrick, G.M., et al., J. Appl. Crystallogr., 2015, vol. 48, p. 3.CrossRefGoogle Scholar
  24. 24.
    Sheldrick, G.M., Acta Crystallogr., Sect. C: Struct. Chem., 2015, vol. 71, p. 3.CrossRefGoogle Scholar
  25. 25.
    Davidson, R.A., Hao, J., Rheingold, A.L., et al., Polyhedron, 2017, vol. 133, p. 348.CrossRefGoogle Scholar
  26. 26.
    Buchachenko, A.L. and Vasserman, A.M. Stabil’nye radikaly. Elektronnoe stroenie, reaktsionnaya sposobnost’ i primenenie (Stable Radicals. Electronic Structure, Reactivity, and Applications), Moscow: Khimiya, 1973.Google Scholar
  27. 27.
    Abakumov, G.A., Cherkasov, V.K., Nevodchikov, V.I., et al., Izv. Akad. Nauk., Ser. Khim., 1996, no. 2, p. 464.Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • A. V. Cherkasova
    • 1
  • K. A. Kozhanov
    • 1
  • A. A. Zolotukhin
    • 1
  • A. S. Bogomyakov
    • 2
  • A. V. Cherkasov
    • 1
  • V. K. Cherkasov
    • 1
    Email author
  1. 1.Razuvaev Institute of Organometallic Chemistry, Russian Academy of SciencesNizhny NovgorodRussia
  2. 2.International Tomography Center, Siberian Branch, Russian Academy of SciencesNovosibirskRussia

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