Structural Chemistry Of Copper, Cobalt And Nickel Complexes With β-ketoxime And β-hydrazono-oxime Ligands

Considerable interest has been shown in transition metal complexes with β-ketoxime and β-hydrazono-oxime ligands owning to their variable structure types, their special catalytical, electric, magnetic properties and biological activities. Therefore, the author has carried out the study on the structural chemistry of copper, cobalt and nickel complexes containing β-ketoxime and β-hydrazono-oxime ligands. The main results of this dissertation are summarized below.Study on syntheses and crystal structures of the complexes with β-ketoxime and β-hydrazono-oxime ligands and study on cyclic Cu3 complexes have been summarized out systemically.The 33 complexes with β-ketoxime, β-hydrazono-oxime and related ligands have been synthesized. These thirty-three title compounds are hexanuclear copper complex 1, four trinuclear copper complexes 2-5, complexes with 2-ketone-1,3-cyclohexan–dioxime ligand 6-7, two β-ketoximes 8-9, compounds with 2-ketone-1,3-cyclopentan–dioxime ligand and its potassium complex 10-12, complexes with Violuric acid(H3vi) 13-16, 3-(salicyloylhydrazono) butan-2-one oxime ligand and its seven complexes 17-24, N-acetyl-salicylhydrazidate complex 27, some other complexes with β-hydrazono -oxime 25-26 and related complexes 28-33.The crystal structures of the 33 title complexes have been studied. In contrast to the common structure core Cu3(μ3-O/X) in most of the known cyclic Cu3 complexes, the unusual Cu3(μ2-Cl)(μ2-O)3 core and Cu3(μ2-O)3 core are found in the hexanuclear copper complex 1 and the cyclic trinuclear copper complexes 2-5. Two Cu3(μ2-O)3 cores in complex [Cu3(H2L22-)2(HL1-)(Cl-)(CH3OH)]2 1 are connected through two oxime groups. Complex 1 represents the first structural characterization of a hexanuclear complex with two Cu3(μ2-O)3 cores. In the complexes ([Cu3(μ2-Cl-)(H2L22-)2(HL1-)]·CH3OH (2) and [Cu3(μ2-Cl-)(H2L32-)2(HL1-)] (3), the two neighboring structure units with Cu3(μ2-Cl)(μ2-O)3 core are bridged by one oxime nitrogen atom and one oxime oxygen atom to generate one dimensional chain based on cyclic Cu3 structure units. There is a novel Cu3(μ2-ClO4)(μ2-O)3 core in complex[Cu3(H2L32-)2(HL1-)(ClO4-)(H2O)2] (4), the three Cu(II) ions in the core have two different coordination environments square pyramid and octahedron. There are many intermolecular hydrogen bonds between the Cu3(μ2-ClO4)(μ2-O)3 cores and between the Cu3(μ2-O)3 cores neighboring in cyclic trinuclear copper complexes 4 and 5, respectively. Therefore, the complexes 4 and 5 have an extended hydrogen bond chain structure. Complexes 1~4 and 12 are also a kind of complexes with a unusual α, β, γ-vic-trione-α, γ-dioxime ligands. In the Cu and Co complexes with violuric acid 13~16, Violuric acid ligand coordinates through one carbonyl oxygen and one oxime nitrogen to a metal ion, forming the five-membered chelating rings. A series of complexes with 3-(salicyloylhydrazono) butan-2-one oxime, complexes 18-24, have been synthesized and characterized. The Two cobalt atoms are combined through the oxime group N-O bond of 3-(salicyloylhydrazono) butan-2-one oxime ligands, forming a binuclear structure unit in complex [Co2(C11H11N3O3)2(C5H5N)4]·ClO4·OH 20. Complex [Fe6(C9H7N2O3)6(C5H5N)6]·0.5C5H5N 27 is a hexanuclear ferric Metallacrown containing [-Fe-N-N-]6 core ring. The binding mode of the ligand enforces the stereo-chemistry of the metal ions only into a propeller configuration. There are two bridging OAc- ligands and two terminal OAc- ligands in the binuclear copper Complex molecule [Cu2(CH3COO)4(C3H4N2)4(H2O)] 28, while there are four bridging OAc- ligands in most known binuclear Cu complexes with Cu2(RCOO-)4A2 type.The main IR frequencies of the ligands and complexes have been assigned empirically. Some title complexes are also characterized by UV spectra and DTA-TGA data.