Synthesis and characterization of novel unsymmetrical macrobicyclic tricompartmental mono and binuclear nickel(II) complexes: Electrochemical and kinetic studies of phosphate hydrolysis

摘要

A series of macrobicyclic mono and binuclear nickel(II) complexes of type [NiL](ClO4) and [Ni2L](ClO4)(2), where L is macroyclic ligand derived from the precursor compound 3,4:10,11-dibenzo-1,13[N,N'-bis{(3-formyl-2-hydroxy-5-methyl)benzyl}diaza]-5,9-dioxocyclopentadecane, have been synthesized in order to examine electrochemical and catalytic studies on the basis of macrocyclic ring size. The macrocycle consists of three dissimilar compartments arising from ether oxygen, tertiary nitrogen and imine nitrogen atoms. Electrochemical studies have shown that the mononuclear nickel(H) complexes undergo quasireversible single step one electron reduction and oxidation and binuclear nickel(II) complexes undergo two quasireversible one electron reduction and oxidation. The EPR silent nature is ascribed to Ni(II) state and all the nickel(II) complexes have square planar geometry and are diamagnetic in nature. The complexes were subjected to hydrolysis of 4-nitrophenyl phosphate and the catalytic activities of the complexes are found to increase with macrocyclic ring size of the complexes. As the macrocyclic ring size of the complexes increases, the spectral, electrochemical and catalytic studies of the complexes show remarkable variation due to distortion in the geometry around the nickel(H) centre. (c) 2006 Elsevier B.V. All rights reserved.