Synthesis And Characterization Of Novel Pyrazole Derivatives And Its Complexes

Since 1960s, poly(pyrazol-1-yl)methane ligands have been developed greatly in transition metal chemistry, bioinorganic chemistry and organ metallic chemistry, which means numerous of complexes of these ligands with metals have been prepared and studied for their catalysis on olefin polymerization. In recent years, people have been attracted to design and synthesize N, N, O ligands derived from bis(pyrazol-l-yl)methane, and more attentions have also been paid on the synthesis and application of their metal complexes due to the"scorpionate"ligands characters, such as simulation for active centers of metalloenzymes and for the catalytic oxo-polymerization of phenols by peroxidase. This dissertation is dedicated to synthesize and explore metal coordination polymers with novel structure and specific function as polymerization catalysts and biologic template.Three novel pyrazole N,N,O"scorpionate"ligands, two new N-pyrazolylpropanamide compounds, and their complexes were designed, synthesized and characterized respectively.The main points of this dissertation are described as follows:Three novel pyrazole ligands and two new N-pyrazole amide compounds were synthesized and characterized. 1,3-bis(3,5-dimethyl pyrazol-1-yl)propan-2-ol(L1), 1,3-bis(5-methyl-3-phenylpyrazol-1-yl)propan-2-ol (L2), and 1,3-Bis[3-(2-pyridyl)-1H-pyrazol-1-yl]-propan-2-ol (L3) are the novel pyrazole ligands with N,N,O"scorpionate"structure. 3-(3,5-dimethyl-1H-pyrazol-1-yl)propanamide(L4) and 3-(3-(pyridin-2-yl)-1H-pyrazol-1-yl)propanamide(L5) are attributed to new N-pyrazole amide compounds. The characterization of the above five compounds was conducted by Elemental Alalysis, Infrared spectrum, Mass spectrum and 1HNMR spectrum, and the crystal structure of L5 was determined by X-ray diffraction analysis. The synthesis routes and conditions of these ligands were aiso investigated.Eleven new complexes were synthesized by Cu(II),Zn(II),Ni(II),Co(II) ions with L1,L2 ligands, and their structures were characterized by Elemental Alalysis and Infrared spectrum. Nine Single crystals of those complexes were obtained, and five complexes were characterized by X-ray diffraction analysis. The unit-cell parameters were listed below: compound 1 [Cu2(μ-dmpzpo-O,N,N')2]Cl2·2CH3OH was orthorhombic with space group C c c m and unit-cell parameters of a=19.459(4)?, b=20.338(4)?, c=8.1711(16)?; compound 4 [Zn2(μ-dmpzpo-O,N,N')2 (NO3)2]·CH3OH·H2O was monoclinic with space group P 2(1)/c and unit-cell parameters of a=11.804(2)?, b=10.285(2)?, c=13.698(3)?; compound 5 [Cu(C19H17N6O)Br]·4H2O was monoclinic with space group C 2/c and unit-cell parameters of a=24.305(5)?, b=13.818(3)?, c=14.477(3)?; compound 7 [Zn4(C19H18N6O)4 (CO3)2](ClO4)4·9CH3OH was monoclinic with space group P -1and unit-cell parameters of a=16.228(3)?, b=16.242(3)?, c=22.109(4)?; compound 8 [Zn2(C19H18N6O)2](NO3)4·H2O was trigonal with space group R3 and unit-cell parameters of a=37.004(5)?, b=37.004(5)?, c=10.387(2)?. The crystal X-ray analyses show that all metal complexes of L1 ligand are dinuclear commonly and two metal atoms are similar at coordination environment, in which two metal atoms were bridged by two oxygen atoms of hydroxyl anions and forming a square-planar environment. While metal complexes derived from ligand L3 contain mononuclear and dinuclear compounds, with no ligation of the oxygen atom of the hydroxyl group of the ligand. The three-dimensional networks are stablized by hydrogen bonds and Van de Wall interactions.