Coordinating properties of pyrone and pyridinone derivatives, tropolone and catechol toward the VO2+ ion: An experimental and computational approach

Daniele Sanna, P. Buglyó, Linda Bírõ, Giovanni Micera, Eugenio Garribba

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Abstract

The interaction of the VO2+ ion with pyrone derivatives and tropolone, which form very effective antidiabetic compounds, is critically re-examined. The binary systems with ethylmaltol (Hema) and tropolone (Htrop) were studied in aqueous solution and in the solid state through the combined application of spectroscopic (EPR, UV/Vis and IR) and pH-potentiometric techniques. The results were compared with those of the systems with maltol (Hma) and kojic acid (Hkoj) and rationalized on the basis of DFT simulations. All the ligands L- form [VOL]+, cis-[VOL 2(H2O)] and cis-[VOL2(OH)]- species in aqueous solutions and a square-pyramidal [VOL2] complex in the solid state, which transforms into cis-[VOL2(solvent)] when it is dissolved in water or in a coordinating solvent. The coordinating properties of the ligands studied were compared with those of pyridinone [3-hydroxy-1,2- dimethyl-4(1H)pyridinone (Hdhp), and 1,2-diethyl-3-hydroxy-4(1H)pyridinone (Hdepp)] derivatives and catechol (H2cat), and were explained by postulating that from pyrones to pyridinones and to catechol the donor set changes progressively from (CO, O-) to (O-, O -). DFT calculations allowed us to determine the relative stability of the four possible structures (square pyramidal, trans- and two cis-octahedral) of the bis-chelated species and the aromaticity of the protonated, neutral and deprotonated form of the ligands through the calculation of the HOMA (harmonic oscillator model of aromaticity) index. The relationship between the electric charge on the oxygen donors, the mean distances and the difference between the lengths of C-Oket and C-Ophen bonds with (i) the pKa of the ligands, (ii) the pK of deprotonation of the equatorially coordinated water molecule in cis-[VOL2(H 2O)], and (iii) the 51V hyperfine coupling constant (Az) of [VOL2], cis-[VOL2(H2O)] and cis-[VOL2(OH)]- was also found and discussed. The chelating and spectroscopic properties of pyrone and pyridinone derivatives, tropolone and catechol (which form very effective antidiabetic compounds) towards the VO2+ ion are explained in terms of aromaticity of the fully deprotonated form of the ligands, and of total electric charge on the oxygen donors.

Original languageEnglish
Pages (from-to)1079-1092
Number of pages14
JournalEuropean Journal of Inorganic Chemistry
Issue number7
DOIs
Publication statusPublished - 2012

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Keywords

  • Bioinorganic chemistry
  • Density functional calculations
  • EPR spectroscopy
  • Structure elucidation
  • UV/Vis spectroscopy
  • Vanadium

ASJC Scopus subject areas

  • Inorganic Chemistry

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