STUDIES ON THE FORMATION AND DECOMPOSITION OF COPPER(III) AND NICKEL(III) COMPLEXES WITH MACROCYCLIC LIGANDS CONTAINING AMIDE GROUPS

The spectral characteristics of 13- and 14-membered C-functionalized m acrocyclic dioxotetraamine and the corresponding saturated polyamine c opper(II), copper(III) and nickel(III) complexes have been studied. It was shown that C-functionalized substituents, although not coordinati ng to the metal ion, have significant effects on the spectral properti es of their M(III) complexes. As for copper(II) complexes, substituent s increase the in-plane ligand field and decrease the wavelength of th e d-d absorption of their complexes. Substituents increase the pi-CT w avelength and decrease the absorption coefficients. Rate constants and activation parameters for the oxidation of Cu-II complexes by peroxod isulfate and decomposition reactions of copper(III) complexes in aqueo us solution were also measured. Activation parameters were shown to be dependent on ligand structure. Copyright (C) 1996 Elsevier Science Lt d