SYNTHESIS AND REACTIVITY OF COPPER(II) COMPLEXES WITH NEW BINUCLEATING LIGANDS DERIVED FROM 16-MEMBERED OR 20-MEMBERED N4-MACROCYCLES

New binucleating ligands. (L1) N.N′.N″.N″′-tetrakis(2-benzimidazolylmethyl)-1.4, 9, 12-tetra-azacyclohexadecane, and (L2) N, N′, N″, N″′-tetrakis(2-benzimidazolylmethyl)-l, 4.11, 14-tetra-azacvcloeicosane were prepared. From the reaction mixture of copper(II) salt and the ligand, new binuclear copper(II) complexes. Cu2(L1)(NO3)4 (1), Cu2(L2)(NO3)4 (2), Cu2(L2)Br4 (3), and trinuclear complexes. Cu3(L1)Cl6 (4), and Cu3(L2)Cl6 (5) were obtained. Cyclic voltammograms revealed that the trinuclear complexes 4 and 5 are composed with the binuclear complex (1 or 2) and [CuCl4]2. The interaction between two metal ions in the binuclear complexes are confirmed on the basis of the ESR spectra. These binuclear complexes exhibit higher catalytic activity for the oxidation of TMPD by O2 molecule than those of structurally rigid binuclear copper(II) complexes and of flexible binuclear complexes in which two copper(II) coordination sites are linked by a single polyatomic chain. © 1990, Walter de Gruyter. All rights reserved.