Polyoxoniobates as a superior Lewis base efficiently catalyzed Knoevenagel condensation

The outstanding basicity of negative charged Lindqvist type Polyoxoniobate K7HNb6O19 center dot 13H(2)O (Nb-6) have been proved experimentally as well as by theoretical NBO calculations, the results insights high electron density on terminal and bridging oxygen atoms of niobate anion. The most negative Natural Bond Orbital charge (NBO) of oxygen in Nb-6 is -1.001, which is a much more negative value than those reported in other polyoxometalates, that corroborates its high basicity thus likely to be employed as a strong base catalyst. Experimental study suggests that Nb-6 can efficiently catalyze Knoevenagel condensation of various carbonyl compounds with active methylene compounds neglecting the steric and electronic effect of aromatic aldehydes under mild conditions. Kinetic test shows that Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate exhibits second order kinetics in the presence of Nb-6 and the calculated activation energy is 43.3 kJ mol(-1). Meanwhile, a proper mechanism according to the NBO study speculates that the most negative charged terminal oxygens in Nb-6 would be pivotal in this transformation.