Spectral Properties of Oxovanadium(IV) Complexes. IV. Correlation of ESR Spectra with Ligand Type

  • L. J. Boucher
  • Edmund C. Tynan
  • Teh Fu Yen


ESR spectral parameters, A 0, A , A and go, g, g as well as electronic absorption maxima are listed for a number of oxovanadium(IV) complexes with a series of representative ligands. The four donor atoms of the ligands are: oxygen (β-diketones, oxalate, water), oxygen—nitrogen (β-ketimines, salicylaldimines), nitrogen (porphyrins, thiocyanate), sulfur (dithiocarbonate), chloride, and cyanide. The electronic structures of the square-based pyramidal oxovanadium(IV) complexes are discussed with the aid of spectral data. A plot of g values versus A values for each of the complexes maps out regions for donor types. Within each group, solvent and substituent effects on the spectra are also noted. The origin of the ESR correlation is related to the empirical dependence of the isotropic contact term on the molecular orbital coefficients and energy of the vanadium orbitals. Extension of this approach to systems in which the donor atom is unknown is suggested.


Electron Spin Resonance Spectrum Donor Atom Vanadium Atom Ligand Type Orbital Coefficient 
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Copyright information

© Plenum Press, New York 1969

Authors and Affiliations

  • L. J. Boucher
    • 1
  • Edmund C. Tynan
    • 1
  • Teh Fu Yen
    • 1
  1. 1.Department of ChemistryMellon Institute, Carnegie-Mellon UniversityPittsburghUSA

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