Vanadium(iv and v) complexes of pyrazolone based ligands: Synthesis, structural characterization and catalytic applications.

The ONO donor ligands obtained from the condensation of 4-benzoyl-3-methyl-1-phenyl-2-pyrazoline-5-one (Hbp) with benzoylhydrazide (H2 bp-bhz I), furoylhydrazide (H2 bp-fah II), nicotinoylhydrazide (H2 bp-nah III) and isonicotinoylhydrazide (H2 bp-inh IV), upon treatment with [VIV O(acac)2 ], lead to the formation of [VIV O(bp-bhz)(H2 O)] 1, [VIV O(bp-fah)(H2 O)] 2, [VIV O(bp-nah)(H2 O)] 3 and [VIV O(bp-inh)(H2 O)] 4, respectively. At neutral pH the in situ generated aqueous K[H2 VV O4 ] reacts with ligands I and II, forming potassium salts, K(H2 O)2 [VV O2 (bp-bhz)] 5 and K(H2 O)2 [VV O2 (bp-fah)] 6, while ligands III and IV give neutral complexes, [VV O2 (Hbp-nah)] 9 and [VV O2 (Hbp-inh)] 10, respectively. Acidification of aqueous solutions of 5 and 6 with HCl also gives neutral complexes [VV O2 (Hbp-bhz)] 7 and [VV O2 (Hbp-fah)] 8, respectively. Complexes 1-4, upon slow aerial oxidation in methanol, convert into monooxidovanadium(v) complexes, [VV O(bp-bhz)(OMe)] 11, [VV O(bp-fah)(OMe)] 12, [VV O(bp-nah)(OMe)] 13 and [VV O(bp-inh)(OMe)] 14, respectively. All complexes were characterized by various spectroscopic techniques like FT-IR, UV-visible, EPR (for complexes 1-4) and NMR (1 H,13 C and51 V), elemental analysis, thermogravimetry and single crystal X-ray diffraction (for complexes 5-10 and 12). In the solid state, all complexes characterized by X-ray diffraction show the metal ion 5-coordinated in a distorted square pyramidal geometry. Complexes 11-14 were tested as catalysts for the one-pot three-component (ethylacetoacetate, benzaldehyde and ammonium acetate) dynamic covalent assembly, via Hantzsch reaction, using hydrogen peroxide as oxidant in solution and under solvent-free conditions. The complexes are also active catalysts for the oxidation of tetralin to tetralone with H2 O2 as oxidant. The influence of the amounts of catalyst and oxidant, and solvent, temperature and time on the catalyzed reactions was investigated.