Indexed on: 13 Dec '06Published on: 13 Dec '06Published in: Journal of Porous Materials
Oxovanadium(IV) tetradentate Schiff-base complexes; [VO(X2-haacac)] (X = H, Cl, CH3 and NO2), X2-haacac = substituted bis(2-hydroxyanil)acetylacetone; and encapsulated in the nanopores of zeolite NaY; [VO(X2-haacac)]-NaY; have been synthesized and characterized. The host-guest nanocomposite materials; [VO(X2-haacac)]-NaY; was characterized by chemical analysis and spectroscopic methods (FT-IR, UV/VIS, XRD, BET and DRS). The analytical data indicated a composition corresponding to the mononuclear complex of Schiff-base ligand. The characterization data showed the absence of extraneous complexes, retention of zeolite crystalline structure and encapsulation in the nanopores. Substitution of the aromatic hydrogen atoms of the Schiff-base ligand by electron withdrawing groups like −Cl, and −NO2 has two major effects: (1) retention and concentration of the oxovanadium(IV) complex in the zeolite cavities is enhanced (due to the larger size of the substituents) and (2) the electronic and spectral properties of the encapsulated complex are modified. Liquid-phase selective hydroxylation of phenol with H2O2 to a mixture of catechol and hydroquinone in CH3CN has been reported using oxovanadium(IV) Schiff-base complexes encapsulated in zeolite-Y as catalysts. Reaction conditions have been optimized by considering the concentration of substrate and oxidant, amount of catalyst, effect of time, volume of solvent and temperature. Under the optimized reaction conditions, [VO((NO2)2-haacac)]-NaY has shown the highest conversion of 42.3% after 6 h. All these catalysts are more selective toward catechol formation. Encapsulated oxovanadium(IV) complex is catalytically very efficient as compared to other neat complexes for the hydroxylation of phenol and is stable to be recycled without much deterioration.
Indexed on: 30 May '09
Published on: 30 May '09 in Journal of Inclusion Phenomena and Macrocyclic Chemistry