Russian Chemical Bulletin

, Volume 44, Issue 4, pp 678–681 | Cite as

The effect of covalent contact between solvent molecules and the VO(DMSO) 5 2+ ion on the electronic structure of the ion

  • I. S. Ionova
  • V. L. Rubailo
  • A. A. Kiseleva
Physical Chemistry


The dissolution of the vanadyl complex VO(DMSO)5(CLO4)2 in alcohols ROH (R= Me, Et, or Prn) results in the appearance of a new absorption band at 372 nm in the electronic absorption spectra of the vanadyl ion. The calculation of the OVO52+ ion by the Xα-scattering wave method is carried out to interpret the spectra. It is shown that the new band in the spectrum of the VO(DMSO)4OHR2+ complex corresponds to the b2→a1 transition in the OVO52+ ion. However, this transition is not a pure d-d transition due to strong covalent bonding and a significant contribution from the AO 2p of oxygen to the a1 MO. The appearance of the new absorption band in the electronic spectra of the vanadyl complexes is caused by the participation of ligand orbitals in bond formation.

Key words

vanadyl complexes, electronic structure electronic spectra 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    J. Selbin,Chem. Rev., 1965,65, 157.Google Scholar
  2. 2.
    L. J. Berliner and J. Reuben,Biological Magnetic Resonance, Plenum Press, New York, 1981,3, 62.Google Scholar
  3. 3.
    Comprehensive Inorganic Chemistry, Pergamon Press,3, 515.Google Scholar
  4. 4.
    A. V. Nikitin, S. V. Kholujskaja, and V. L. Roubaijlo,J. Chem. Research, 1994, No. 9, 358.Google Scholar
  5. 5.
    A. A. Konovalova, S. V. Bainova, V. D. Kopanev, and Yu. A. Buslaev,Koord. Khim., 1985,11, 1349 [Sov. J. Coord. Chem., 1985,11 (Engl. Transl.)].Google Scholar
  6. 6.
    C. Weidemann and D. Rehder,Inorg. Chim. Acta, 1986,120, 15.Google Scholar
  7. 7.
    J. Selbin and L. H. Holmes,J. Org. Nucl. Chem., 1962,24, 1111.Google Scholar
  8. 8.
    V. L. Rubailo,D. Sc. (Chem.) Thesis, Institute of Chemical Physics, RAS, Moscow, 1993.Google Scholar
  9. 9.
    J. C. Slater,Quantum Theory of Molecules and Solids, McGraw-Hill, New York, 1965.Google Scholar

Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • I. S. Ionova
    • 1
  • V. L. Rubailo
    • 1
  • A. A. Kiseleva
    • 2
  1. 1.N. N. Semenov Institute of Chemical PhysicsRussian Academy of SciencesMoscowRussian Federation
  2. 2.Institute of Physical ChemistryRussian Academy of SciencesMoscowRussian Federation

Personalised recommendations