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

Sanna, Daniele and Buglyó, Péter and Bíró, Linda and Micera, Giovanni and Garribba, Eugenio (2012) Coordinating properties of pyrone and pyridinone derivatives, tropolone and catechol toward the VO2+ ion: an experimental and computational approach. European Journal of Inorganic Chemistry, Vol. 2012 (7), p. 1079-1092. eISSN 1099-0682. Article.

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DOI: 10.1002/ejic.201101249

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 pHpotentiometric 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-[VOL2(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 bischelated 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(H2O)], and (iii) the 51V hyperfine coupling constant (Az) of [VOL2], cis-[VOL2(H2O)] and cis-[VOL2(OH)] was also found and discussed.

Item Type:Article
ID Code:7561
Status:Published
Refereed:Yes
Uncontrolled Keywords:Vanadium, bioinorganic chemistry, structure elucidation, EPR spectroscopy, UV/Vis spectroscopy, density functional calculations
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 02 Centri > Centro di eccellenza interdisc. sviluppo ricerca biotecnologica e studio biodiversità della Sardegna e dell'area mediterranea
001 Università di Sassari > 01-a Nuovi Dipartimenti dal 2012 > Chimica e Farmacia
002 Altri enti e centri di ricerca del Nord Sardegna > CNR-Consiglio Nazionale delle Ricerche > Istituto di chimica biomolecolare, Sassari
Publisher:Wiley
eISSN:1099-0682
Deposited On:11 May 2012 13:19

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