17 research outputs found
Oxidation of benzoin catalyzed by oxovanadium (IV) schiff base complexes
BACKGROUND: The oxidative transformation of benzoin to benzil has been accomplished by the use of a wide
variety of reagents or catalysts and different reaction procedures. The conventional oxidizing agents yielded mainly
benzaldehyde or/and benzoic acid and only a trace amount of benzil. The limits of practical utilization of these
reagents involves the use of stoichiometric amounts of corrosive acids or toxic metallic reagents, which in turn
produce undesirable waste materials and required high reaction temperatures.
In recent years, vanadium complexes have attracted much attention for their potential utility as catalysts for various
types of reactions.
RESULTS: Active and selective catalytic systems of new unsymmetrical oxovanadium(IV) Schiff base complexes for
the oxidation of benzoin is reported. The Schiff base ligands are derived between 2-aminoethanol and 2-hydroxy-1-
naphthaldehyde (H2L1) or 3-ethoxy salicylaldehyde (H2L3); and 2-aminophenol and 3-ethoxysalicylaldehyde (H2L2) or
2-hydroxy-1-naphthaldehyde (H2L4). The unsymmetrical Schiff bases behave as tridentate dibasic ONO donor
ligands. Reaction of these Schiff base ligands with oxovanadyl sulphate afforded the mononuclear oxovanadium(IV)
complexes (VIVOLx.H2O), which are characterized by various physico-chemical techniques.
The catalytic oxidation activities of these complexes for benzoin were evaluated using H2O2 as an oxidant. The best
reaction conditions are obtained by considering the effect of solvent, reaction time and temperature. Under the
optimized reaction conditions, VOL4 catalyst showed high conversion (>99%) with excellent selectivity to benzil
(~100%) in a shorter reaction time compared to the other catalysts considered.
CONCLUSION: Four tridentate ONO type Schiff base ligands were synthesized. Complexation of these ligands with
vanadyl(IV) sulphate leads to the formation of new oxovanadium(IV) complexes of type VIVOL.H2O.
Elemental analyses and spectral data of the free ligands and their oxovanadium(IV) complexes were found to be in
good agreement with their structures, indicating high purity of all the compounds.
Oxovanadium complexes were screened for the oxidation of benzoin to benzil using H2O2 as oxidant. The effect of
time, solvent and temperature were optimized to obtain maximum yield. The catalytic activity results demonstrate
that these catalytic systems are both highly active and selective for the oxidation of benzoin under mild reaction
conditions.Web of Scienc
High-throughput synthesis and electrochemical screening of a library of modified electrodes for NADH oxidation
We report the combinatorial preparation and high-throughput screening of a library of modified electrodes designed to catalyze the oxidation of NADH. Sixty glassy carbon electrodes were covalently modified with ruthenium(II) or zinc(II) complexes bearing the redox active 1,10-phenanthroline-5,6-dione (phendione) ligand by electrochemical functionalization using one of four different linkers, followed by attachment of one of five different phendione metal complexes using combinatorial solid-phase synthesis methodology. This gave a library with three replicates of each of 20 different electrode modifications. This library was electrochemically screened in high-throughput (HTP) mode using cyclic voltammetry. The members of the library were evaluated with regard to the surface coverage, midpeak potential, and voltammetric peak separation for the phendione ligand, and their catalytic activity toward NADH oxidation. The surface coverage was found to depend on the length and flexibility of the linker and the geometry of the metal complex. The choices of linker and metal complex were also found to have significant impact on the kinetics of the reaction between the 1,10-phenanthroline-5,6-dione ligand and NADH. The rate constants for the reaction were obtained by analyzing the catalytic currents as a function of NADH concentration and scan rate, and the influence of the surface molecular architecture on the kinetics was evaluated.<br/