Structural Chemistry Of Cu(Ⅱ) And Ni(Ⅱ) Complexes With Salicylhydrazone Ligands Involving Hydrazine N-N Bond

Interest in the salicylhydrazone ligands with the hydrazine N-N bond stems not only from their variable structure types and the aesthetic molecular frameworks, but also from the special catalytical, magnetic and biochemical properties associated with them. In this dissertation, the author has carried out the study on the copper(II) and nickel(II) complexes of salicylhydrazone ligands with the hydrazine N-N bond.Fourteen compounds have been synthesized by the method of the solution synthesis. These title compounds are complexes with N-salicylaldehyde-N'-(p-chlorophenoxyacyl) hydrazone (H2La) (1 and 2), complexes with N-salicylaldehyde-N'-(o-chlorophenoxyacyl) hydrazone (H2Lb) (3, 4 and 5), complexes with N-(p-chlorophenoxyacyl) salicylhydrazidate (H3Ld) (6 and 7), complexes with N-(p-nitrobenzoyl) salicylhydrazidate (H3Lc) (8, 9 and 10), compounds with N-salicylaldehyde-N'-(p-nitrobenzoyl) hydrazone (H2Le) (11, 12 and 13) and bis(salicylidene)hydrazine complex (14).The crystal structures of the title fourteen compounds have been studied by X-ray diffraction. The complexes 1 and 2 are both trinuclear copper compounds. The central copper atom is bridged to the two terminal ones through the hydrazide nitrogen atoms, forming a Cu-N-N-Cu-N-N-Cu linkage in 1 and 2. The neighboring molecules in complex 2 are bridged by N-N groups of the ligand H2La, resulting in a 1D polymer. The neighboring molecules in complex 3 are linked through the weak Cu-O(morphH) bonds and hydrogen bonds to get an extended two-dimensional network structure. The two copper atoms are combined through the hydrazine N-N bond of the ligand H2Lb, forming a binuclear structure unit in complex 4. The two binuclear units are held together by Cu2( -O)2 core to obtain a stair-like tetranuclear structure in 4. The complexes 6, 7, 8, 9 and 10 are trinuclear nickel(II) compounds with Ni3( -N2)2 core. The arrangement around the three nickel atoms in complexes 6, 7 and 8 is a normal linear. However, the arrangement in complexes 9 and 10 is an unusual U-type. The complex 9 possesses a dimeric hexanuclear nickel(II) structure which is resulted from two intermolecular hydrogen bonds. Then the neighboring dimers are linked through the other intermolecular hydrogen bonds, forming a novel double-chain structure.Some title complexes were characterized by IR spectra, electronic spectra, thermal analyses and magnetic data.