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Russian Chemical Bulletin

, Volume 64, Issue 3, pp 642–649 | Cite as

Effect of an additional functional group on the structure and properties of copper(II) and nickel(II) o-iminoquinone complexes

  • A. V. Piskunov
  • I. V. Ershova
  • M. V. Gulenova
  • K. I. Pashanova
  • A. S. Bogomyakov
  • I. V. Smolyaninov
  • G. K. Fukin
  • V. K. Cherkasov
Full Articles

Abstract

Nickel(II) and copper(II) bis-o-iminosemiquinone complexes were synthesized based on 4,6-di-tert-butyl-N-(2-methoxyphenyl)-o-aminophenol (Ni(imSQOMe)2 (1) and Cu(imSQOMe)2 (2)), and methyl 2-(3,5-di-tert-butyl-2-hydroxyphenylamino)benzoate (Ni(imSQC(O)OMe)2 (3) and Cu(imSQC(O)OMe)2 (4)). The molecular structures of these complexes were established by X-ray diffraction. The metal atoms in complexes 1, 3, and 4 are in square-planar coordination, whereas the square-planar coordination of the copper atom in complex 2 is substantially distorted, as evidenced by the angle between the planes of the o-iminosemiquinone ligands (22.7°). Complexes 1 and 3 are diamagnetic. The absence of line broadening in the 1H NMR spectra of these compounds at 293 K attests to the singlet spin state. The temperature dependences of the effective magnetic moment for complexes 2 and 4 are indicative of their doublet ground spin state (S = 1/2) and the thermally populated quartet state (S = 3/2). The presence of an unpaired electron on the metal center in the ground spin state for compounds 2 and 4 was confirmed by EPR spectroscopy.

Key words

redox-active ligand o-iminobenzosemiquinolate nickel(II) copper(II) magnetic properties X-ray diffraction study electron paramagnetic resonance 

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Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • A. V. Piskunov
    • 1
    • 2
  • I. V. Ershova
    • 1
  • M. V. Gulenova
    • 2
  • K. I. Pashanova
    • 1
  • A. S. Bogomyakov
    • 3
  • I. V. Smolyaninov
    • 4
  • G. K. Fukin
    • 1
    • 2
  • V. K. Cherkasov
    • 1
    • 2
  1. 1.G. A. Razuvaev Institute of Organometallic ChemistryRussian Academy of SciencesNizhny NovgorodRussian Federation
  2. 2.N. I. Lobachevsky Nizhny Novgorod State UniversityNizhny NovgorodRussian Federation
  3. 3.International Tomography CenterSiberian Branch of the Russian Academy of SciencesNovosibirskRussian Federation
  4. 4.Southern Scientific CenterRussian Academy of SciencesAstrakhanRussian Federation

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