Three VO2+ complexes of the pyridoxal-derived Schiff bases: Synthesis, experimental and theoretical characterizations, and catalytic activity in a cyclocondensation reaction

Three oxovanadium(IV) complexes of the pyridoxal Schiff bases have been newly synthesized and characterized. The used Schiff bases were N,N'-dipyridoxyl(ethylenediamine), N,N'-dipyridoxyl(1,3-propanediamine) and N,N'-dipyridoxyl(1,2-benzenediamine). Also, the optimized geometry, assignment of the IR bands and the Natural Bond Orbital (NBO) analysis of the complexes have been computed using the density functional theory (DFT) methods. Dianionic form of the Schiff bases (L2-) acts as a tetradentate N2O2 ligand. The coordinating atoms of the Schiff base are the phenolate oxygens and imine nitrogens, which occupy four base positions of the square-pyramidal geometry of the complexes. The oxo ligand occupies the apical position of the [VO(L)] complexes. In the optimized geometry of the complexes, the coordinated Schiff bases have more planar structure than their free form. Due to the highenergy gaps, all of the complexes are predicted to be stable. Good agreement between the experimental values and the DFT-computed results supports suitability of the optimized geometries for the complexes. The investigated complexes show high catalytic activities in synthesis of the tetrahydrobenzo [b]pyrans through a three-component cyclocondensation reaction of dimedone, malononitrile and some aromatic aldehydes. The complexes catalyzed the reaction in solvent free conditions and the catalysts were found to be reusable. (C) 2017 Elsevier B.V. All rights reserved.