Synthesis, Characterization And Structure Of Transition Metal Complexes Of 4-acyl Pyrazolone Hydrazone And Hydrazide

Coordination chemistry is one of the most active research field. The design, synthesis and relative properties of functional coordination compounds are focus in the field of coordination chemistry. Research on 4-acyl pyrazolone derivatives has also received considerable attention because 4-acyl pyrazolone derivatives have potential to form different types of coordination compound due to tautomeric effect of enol form and keto form. The compound of pyrazolone derivatives and their transiton metal complexes have broad-specturm anti-viral, antitumor and antisepsis biological activity. Therefore, 4-acyl pyrazolone derivatives are widely used in biological, clinical, analytical applications and extraction metallurgy. Meanwhile compounds of hydrazone and acylhydrazone exhibit different coordination modes and also possess biological activity. So we expect the formation of polyfunctional ligands and polynuclear metal complexes using the combination of 4-acyl pyrazolones and salicycylidene hydrazone, nicotinic hydrazide and salicylidene hydrazide. In order to further enrich and extend the studies on the functional complexes, such as predetermination of molecular architectures and the properties of the binuclear or multinuclear complexes, seven novel 4-acyl pyrazolone derivatives and their transition metal complexes have been synthesized and characterized on the basis of elemental analyses, IR spectra, thermal analyses and single crystal X-ray diffractions. The general formula of the complexes and the crystal structures were ensured. Meanwhile, antitumor tests of some ligands and complexes were carried out. The paper consists of seven parts: In the first part, a novel 4-acyl pyrazolone derivative N-(1-phenyl-3-methyl-4-benzylacetyl-pyrazolone-5)-salicylidene hydrazone (PMPaP-SAH) and its transition metal complexes have been synthesized and characterized by elemental analyses, IR spectra, molar conductance, TG-DTA and single crystal X-ray diffractions, X-ray diffraction analysis showed that the zinc complex is tetranuclear with a rectangular Zn4 core and metal ions are held together by four μ-phenoxo bridges that lead to the formation of a macromolecular cyclic system, The coordination geometry around the Zn ion is best described as trigonal bipyramid. However, Cu, Ni, Co complexes are binuclear complexes, in which the ligand is in the deprotonated form by losing two hydrogen atoms and functions as bivalent tetradentate moiety coordinating to metal ions. By the comparison of crystal structures of ligand and zinc complex, the structure inversion and bonding mode of ligand were presumed. In the second part, N-(1-phenyl-3-methyl-4-propyl-pyrazolone-5)-salicylidene hydrazone (PMPP-SAH) and its metal complexes have been synthesized and characterized by elemental analyses, IR spectra, TG-DTA and single crystal X-ray diffraction. The X-ray diffraction analysis of zinc complex shows that it's a mononuclear complex. The coordination geometry around the ion is best described as tetrahedron, and PMPP-SAH is in the deprotonated form by losing one hydrogen atoms and functions as monovalent bidentate ligand coordinating to zinc ion. Speculated that Cu, Co, Ni complexes are binuclear, and the ligand is in the deprotonated form by losing two hydrogen atoms and functions as bivalent tetradentate moiety coordinating to metal ions. Comparing the crystal structure of ligand and zinc complex, the structure inversion and bonding mode of ligand were presumed. Meanwhile, anticancer tests of ligand and copper complex were carried out. The result shows that ligand and copper complex both have strong anticancer biological activity and the anticancer activity of copper complex is stronger than ligand. In the third part, N-(1,3-diphenyl-4-propyl-pyrazolone-5)-salicylidene hydrazone (DPPP-SAH) and its metal complexes have been synthesized and characterized by elemental analyses, TG-DTA, IR spectra and single crystal X-ray diffraction. The result shows that Zn complex is a mononuclear complex, while Cu, Co, Ni complexes are binuclear. Combine the results of the above parts, we discussed the influence of the different substituents in the 3 and 4 position of the pyrazolone upon the coordination mode. In the fourth part, two novel ligand N(1-phenyl-3-methyl-4-benzal/acetyl-pyrazolone-5)-...