Advertisement

Russian Chemical Bulletin

, Volume 56, Issue 10, pp 1964–1971 | Cite as

EPR spectra and structures of dinuclear copper(II) complexes with acyldihydrazones of benzenedicarboxylic acids

  • G. M. Larin
  • A. N. Gusev
  • Yu. V. Trush
  • K. V. Rabotyagov
  • V. F. Shul’gin
  • G. G. Aleksandrov
  • I. L. Eremenko
Article

Abstract

Spacer-armed dinuclear copper(II) complexes with condensation products of isophthalic and terephthalic acid dihydrazides with salicylaldehyde and 2-hydroxyacetophenone were synthesized and studied by EPR and X-ray diffraction. The compositions and structures of most of the complexes were determined by elemental analysis, thermogravimetric analysis, and IR spectroscopy. The structure of the copper(II) complex with acyldihydrazone of salicylaldehyde and 1,3-benzenedicarboxylic acid (H4L) with the composition [Cu2L1·2morph·MeOH] (morph is morpholine) was established by X-ray diffraction. The CuII atoms are spaced by 10.29 Å and are structurally nonequivalent. One copper cation has a square-planar coordination formed by donor atoms (2 N + O) of the doubly deprotonated acylhydrazine fragment and the N atom of the morpholine molecule. The second copper atom is additionally coordinated by a methanol molecule through the oxygen atom, so that this copper atom is in a tetragonal-pyramidal coordination with the oxygen atom in the axial position. The EPR spectra of liquid solutions of the complexes based on 1,4-benzenedicarboxylic acid acyldihydrazones and 1,3-benzenedicarboxylic acid bis(salicylidene)hydrazone at room temperature show a four-line hyperfine structure with the constant a Cu = 54.4–67.0·10−4 cm−1 (g = 2.105–2.147), which is indicative of the independent behavior of the paramagnetic centers. The EPR spectrum of a solution of the complex based on isophthalic acid and 2-hydroxyacetophenone shows the seven-line hyperfine structure corresponding to two equivalent copper nuclei (g = 2.11, a Cu = 36.5·10−4 cm−1).

Key words

copper(IIdinuclear complexes acylhydrazones molecular and crystal structure EPR hyperfine structure organic radicals 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    G. M. Larin, B. B. Umarov, V. V. Minin, Yu. V. Rakitin, V. G. Yusupov, N. A. Parpiev, and Yu. A. Buslaev, Dokl. Akad. Nauk SSSR, 1988, 303, 139 [Dokl. Chem., 1988 (Engl. Transl.)]Google Scholar
  2. 2.
    K. A. Foster, D. R. Brown, M. D. Timken, D. G. Van Derveer, R. L. Belford, and E. K. Barefield, J. Coord. Chem., 1988, 19, 123.Google Scholar
  3. 3.
    G. M. Larin, V. V. Minin, and Yu. V. Rakitin, Neorg. Mater., 1994, 30, 1424 [Inorg. Mater., 1994, 30 (Engl. Transl.].Google Scholar
  4. 4.
    G. M. Larin, V. F. Shul’gin, E. D. Mel’nikova, V. Ya. Zub, and Yu. V. Rakitin, Izv. Akad. Nauk, Ser. Khim., 2001, 585 [Russ. Chem. Bull., Int. Ed., 2001, 50, 812].Google Scholar
  5. 5.
    G. M. Larin, Koord. Khim., 1992, 18, 699 [Russ. J. Coord. Chem., 1992, 18 (Engl. Transl.)].Google Scholar
  6. 6.
    G. M. Larin, V. F. Shul’gin, A. N. Gusev, and A. N. Chernega, Izv. Akad. Nauk, Ser. Khim., 2004, 740 [Russ. Chem. Bull., Int. Ed., 2004, 53, 775].Google Scholar
  7. 7.
    V. F. Shul’gin, A. N. Gusev, V. Ya. Zub, and G. M. Larin, Izv. Akad. Nauk, Ser. Khim., 2005, 1752 [Russ. Chem. Bull., Int. Ed., 2005, 54, 1804].Google Scholar
  8. 8.
    G. M. Sheldrick, SHELX97, Program for the Solution of Crystal Structures, Göttingen University, Göttingen, Germany, 1997.Google Scholar
  9. 9.
    V. A. Klimova, Osnovnye mikrometody analiza organicheskikh soedinenii [Basic Micromethods for the Analysis of Organic Compounds], Khimiya, Moscow, 1975, 75 (in Russian).Google Scholar
  10. 10.
    G. Schwarzenbach and H. Flashka, Complexometric Titrations, 2nd. Engl. ed., Methuen, London, 1969.Google Scholar
  11. 11.
    Yu. V. Rakitin, G. M. Larin, and V. V. Minin, Interpretatsiya spektrov EPR koordinatsionnykh soedinenii [Interpretation of EPR Spectra of Coordination Compounds], Nauka, Moscow, 1993, 399 pp. (in Russian).Google Scholar
  12. 12.
    G. M. Larin, V. F. Shul’gin, E. A. Sarnit, and Yu. V. Rakitin, Koord. Khim., 1999, 25, 356 [Russ. J. Coord. Chem., 2002, 51, 2268].Google Scholar
  13. 13.
    G. M. Larin, V. F. Shul’gin, E. D. Mel’nikova, V. Ya. Zub, and Yu. V. Rakitin, Izv. Akad. Nauk, Ser. Khim., 2002, 585 [Russ. Chem. Bull., Int. Ed., 2002, 51, 632].Google Scholar
  14. 14.
    G. M. Larin, V. F. Shul’gin, and E. A. Sarnit, Mendeleev Commun., 1999, 129.Google Scholar
  15. 15.
    G. M. Larin, V. F. Shul’gin, and E. A. Sarnit, Zh. Neorg. Khim., 2000, 45, 1007 [Russ. J. Inorg. Chem., 2000, 45, 909 (Engl. Transl.)].Google Scholar
  16. 16.
    G. M. Larin, V. F. Shul’gin, E. A. Sarnit, and Yu. V. Rakitin, Izv. Akad. Nauk, Ser. Khim., 2001, 777 [Russ. Chem. Bull., Int. Ed., 2001, 50, 812].Google Scholar
  17. 17.
    V. F. Shul’gin, A. N. Gusev, V. Ya. Zub, and G. M. Larin, Izv. Akad. Nauk, Ser. Khim., 2002, 2107 [Russ. Chem. Bull., Int. Ed., 2002, 51, 2268].Google Scholar
  18. 18.
    V. F. Shul’gin, A. N. Gusev, V. Ya. Zub, and G. M. Larin, Izv. Akad. Nauk, Ser. Khim., 2003, 1230 [Russ. Chem. Bull., Int. Ed., 2003, 52, 1301].Google Scholar
  19. 19.
    G. M. Larin, V. F. Shul’gin, A. N. Gusev, and A. N. Chernega, Dokl. Akad. Nauk, 2003, 390, 627 [Dokl. Chem., 2003 (Engl. Transl.)]Google Scholar
  20. 20.
    G. M. Larin, V. F. Shul’gin, A. N. Gusev, and A. N. Chernega, Izv. Akad. Nauk, Ser. Khim., 2007, 229 [Russ. Chem. Bull, 2007, 56, 236].Google Scholar
  21. 21.
    T. D. Smith and Y. R. Pilbrow, Coord. Chem. Rev., 1974, 13, 173.CrossRefGoogle Scholar
  22. 22.
    Yu. V. Yablokov, V. K. Voronkova, and L. V. Mosina, Paramagnitnyi rezonans obmennykh klasterov [Paramagnetic Resonance of Exchange Clusters], Nauka, Moscow, 1988, 181 pp. (in Russian).Google Scholar
  23. 23.
    E. F. Hastly, T. J. Colburn, and D. N. Hedrickson, Inorg. Chem., 1973, 12, 2414.CrossRefGoogle Scholar
  24. 24.
    E. F. Hastly, L. J. Wilson, and D. N. Hedrickson, Inorg. Chem., 1978, 17, 1834.CrossRefGoogle Scholar
  25. 25.
    R. M. Silverstein, G. C. Bassler, and T. C. Morrill, Spectrometric Identification of Organic Compounds, 3d ed. John Wiley and Sons, Inc., New York-London-Sydney-Toronto, 1974.Google Scholar
  26. 26.
    V. A. Kogan, V. V. Zelentsov, G. M. Larin, and V. V. Lukov, Kompleksy perekhodnykh metallov s gidrazonami [Transition Metal Complexes with Hydrazones], Nauka, Moscow, 1990, 112 pp. (in Russian).Google Scholar
  27. 27.
    J. D. Ranford, J. J. Vittal, and Yu. M. Wang, Inorg. Chem., 1988, 37, 1226.CrossRefGoogle Scholar
  28. 28.
    B. Singh, K. K. Narang, and R. Srivastaval, Synth. React. Inorg. Metal.-Org. Chem., 2002, 32, 1561.CrossRefGoogle Scholar
  29. 29.
    G. Orpen, L. Brammer, F. H. Allen, O. Kennard, D. G. Watson, and R. Taylor, J. Chem. Soc., Dalton Trans, 1989, S1.Google Scholar
  30. 30.
    A. I. Rivkind and Yu. V. Yablokov, Dokl. Akad. Nauk SSSR, 1964, 158, 1401 [Dokl. Chem., 1964, 980 (Engl. Transl.)].Google Scholar
  31. 31.
    A. I. Rivkind and Yu. V. Yablokov, Zh. Strukt. Khim., 1966, 7, 30 [J. Struct. Chem., 1966, 7, 25 (Engl. Transl.)].Google Scholar
  32. 32.
    G. M. Larin, A. V. Rotov, and V. I. Dzyuba, Dokl. Akad. Nauk, 1995, 334, 779 [Dokl. Chem., 1995 (Engl. Transl.)].Google Scholar
  33. 33.
    G. M. Larin, A. V. Rotov, and V. I. Dzyuba, Izv. Akad. Nauk, Ser. Khim., 1999, 726 [Russ. Chem. Bull., 1999, 48, 722 (Engl. Transl.)].Google Scholar
  34. 34.
    V. I. Dzyuba, A. V. Rotov, Yu. V. Rakitin, and G. M. Larin, Tez. dokl. V Vsesoyuzn. soveshch. “Spektroskopiya koordinatsionnykh soedinenii” [Abstrs. of Papers, V All-Union Conf. “Spectroscopy of Coordination Compounds”], Krasnodar, 1988, 175 (in Russian).Google Scholar
  35. 35.
    D. Snaathorst, H. M. Doesburg, J. A. A. Perenboom, and C. P. Keijzers, Inorg. Chem., 1981, 20, 2526.CrossRefGoogle Scholar
  36. 36.
    S. Das, G. P. Muthukumaragopal, and S. Pal, New. J. Chem., 2003, 7, 1102.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • G. M. Larin
    • 1
  • A. N. Gusev
    • 2
  • Yu. V. Trush
    • 2
  • K. V. Rabotyagov
    • 2
  • V. F. Shul’gin
    • 2
  • G. G. Aleksandrov
    • 1
  • I. L. Eremenko
    • 1
  1. 1.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.V. I. Vernadskii Taurida National UniversitySimferopolUkraine

Personalised recommendations