Journal of Molecular Catalysis A-Chemical, Vol.210, No.1-2, 23-29, 2004
Catalytic hydrolysis of carboxylic acid esters by Cu(II) and Zn(II) complexes containing a tetracoordinate macrocyclic Schiff base ligand in Brij35 micellar solution
The macrocyclic Schiff base complexes of Cu(II) and Zn(II) in Brij35 micellar solution are investigated kinetically for the catalytic hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl picolinate (PNPP) at 30degreesC. The results indicate that different mechanisms are operative for the two complexes in the hydrolysis of PNPA and PNPP. The Cu(II) complex can only catalyze the hydrolysis of PNPP by the mechanism which involves the nucleophilic attack of external hydroxide ion on the carbonyl, while the Zn(II) complex can accelerate the hydrolysis of both PNPP and PNPA, by way of the intramolecular nucleophilic attack of zinc-bound hydroxide ion on carbonyl for PNPP and the less effective intermolecular nucleophilic attack of zinc-bound hydroxide ion on carbonyl for PNPA, respectively. The catalytic activity of Zn(H) complex is close to or even higher than that of Cu(II) complex. The reason is discussed in details. (C) 2003 Elsevier B.V. All rights reserved.
Keywords:macrocyclic Schiff base complex;carboxylic acid ester hydrolysis;metallomicelle;catalysis;kinetics