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Coordinating Properties of Pyrone and Pyridinone Derivatives, Tropolone and Catechol toward the VO 2+ Ion: An Experimental and Computational Approach
Author(s) -
Sanna Daniele,
Buglyó Péter,
Bíró Linda,
Micera Giovanni,
Garribba Eugenio
Publication year - 2012
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201101249
Subject(s) - chemistry , tropolone , protonation , square pyramidal molecular geometry , aqueous solution , aromaticity , potentiometric titration , acetylacetone , catechol , medicinal chemistry , computational chemistry , stereochemistry , crystallography , inorganic chemistry , molecule , ion , organic chemistry , crystal structure
The interaction of the VO 2+ 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 [VO L ] + , cis ‐[VO L 2 (H 2 O)] and cis ‐[VO L 2 (OH)] – species in aqueous solutions and a square‐pyramidal [VO L 2 ] complex in the solid state, which transforms into cis ‐[VO L 2 (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(1 H )pyridinone (Hdhp), and 1,2‐diethyl‐3‐hydroxy‐4(1 H )pyridinone (Hdepp)] derivatives and catechol (H 2 cat), 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–O ket and C–O phen bonds with (i) the p K a of the ligands, (ii) the p K of deprotonation of the equatorially coordinated water molecule in cis ‐[VO L 2 (H 2 O)], and (iii) the 51 V hyperfine coupling constant ( A z ) of [VO L 2 ], cis ‐[VO L 2 (H 2 O)] and cis ‐[VO L 2 (OH)] – was also found and discussed.