A DFT quantum mechanical study of 3-hydroxy-4-pyrone and 3-hydroxy-4-pyridinone based oxidovanadium(IV) complexes

Abstract

Oxidovanadium(IV) complexes have revealed interesting pharmacological properties which make them promising agents in the treatment of diabetes mellitus. A computational study of 17 complexes of oxidovanadium(IV) with 3-hydroxy-4-pyrone-and 3-hydroxy-4-pyridinone-based ligands was carried out at the density functional theory level. The geometry, electronic structure, and vibration modes at the metallic center were predicted, and their dependence on the nature of the ligand was evaluated. Slight distinctions between both classes of compounds were observed, namely the higher value of dipole moments and the smaller HOMO-LUMO energy gap for the 3-hydroxy-4-pyridinone-based complexes. The modes of vibration at the metallic coordination region do not vary significantly throughout the whole series, and a particular corrective scaling factor is proposed for the V=O stretching mode of this type of oxidovanadium(IV) complexes. The results presented here are of particular relevance since it was not yet possible to obtain X-ray diffraction data for the oxidovanadium(IV) complexes of 3-hydroxy-4-pyridinones, and also as the influence of the solvent, in particular the local interaction at the sixth coordination position, was considered.

Structure, Physicochemical and Biological Properties of an Aqua (2,2′,2′′‐Nitrilotriacetato)‐oxidovanadium(IV) Salt with 4‐Methylpyridinium Cation

“…Oxidovanadium(IV) complexes are the subject of interest to many research groups since it has been found that they reveal an interesting biological activity. Much attention has been focused on studies of their insulin‐mimetic (‐enhancing) properties, the anticancer properties as well as the cytoprotective activity against an oxidative damage .…”

Theoretical studies on oxovanadium(IV) complexes with sterically crowded Schiff base ligands

“…Due to the similarity of geometric structures, frontier orbitals of complex (1) are similar to complex (2) and frontier orbitals of complex (3) are similar to complex (4) and (5). Therefore, frontier orbital surfaces and energies for complex (1) and (3) As can be seen from Fig. 4, the energy gap is between 3.0-4.0 eV approximately.…”

“…Several metal ions and their complexes exhibit antidiabetic effects. Elemental vanadium plays an important role in many environmental and biological processes [1]. Coordination chemistry of vanadium has become of great interest due to the presence of vanadium in enzymatic systems [2,3].…”

Interplay of thermochemistry and Structural Chemistry, the Journal (volume 22, 2011, issues 1–3) and the discipline

“…Using DFT approach, Biernacki et al [187] investigated a series of oxovanadium(IV) complexes with 3-hydroxy-4-pyrones and 3-hydroxy-4-pyridinones, the structure of which has not yet been determined. A higher value of dipole moments and the smaller HOMO-LUMO energy gap of the 3-hydroxy-4-pyrone-based complexes have been established in comparison to 3-hydroxy-4-pyridinones-based complexes.…”