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