Synthesis And Characterization Of Water-soluble Mono-and Bi-nuclear Complexes And Their Mimic Catalytic Activity Research

Enzyme catalysts are well known for their ability to carry out chemical reactions with high selectivity and high efficiency under ambient conditions. The mimics of the enzymes have been developing for a long time, however, there has been great significance but still limited amount of interest in the use of complexes as catalysts because of their poor water-soluble.So far, these complexes synthesized from traditional intermediate can not mimic successfully catalytic ability of natural enzymes. In order to mimic some specific properties of enzymatic reactions more effective, and meet the development of green chemistry, we introduced hydrophilic group (-SO3-, -COOH) to both ligands and complexes that were obtained via the parent as salicylaldehyde and phenol. We expect to gain ligands and complexes possessing water-soluble group attributing to these hydrophilic characteristics, and there was few reports of relative research both in domestic and abroad. These complexes may have some industrial application (Methane Momooxygenase (MMO), Superoxide Dismutase (SOD), for example), either for medical field or for depollution processes.Based on the above reasons, more than twenty kinds of mono- and bi- nuclear metal complexes were designed and synthesized to mimic these natural enzymes in this article. This thesis is divided into five parts as following:Before my research work, the synthesis methods, application, and research process of metal complexes were summarized in the first chapter.Water-soluble mononuclear metal complexes (complex 1~8) of N, N'-substituted bis(salicylaldimine-5-sulphonic acids), and water-soluble binuclear transition-metal complexes (complex 1~16) were synthesized in the sequence of a condensation of salicylaldimine-5-sulphonic acid with appropriate primary amine and transition metals by molecular self-assembly, which were described in the second chapter and in the third chapter, respectively. Those mononuclear and binuclear metal complexes were synthesized and characterized by element analysis, IR, UV-Vis, 1H NMR, molecular conductivity. The results showed that some of the complexes have well activity of mimicking Superoxide Dismutase (SOD). The activated order of these complexes is:Mn(II)>Cu(II)>Co(II)>Ni(II )>Zn(II), IC5(p\ X 1(T*~1 X 10-smol ? I/1.The forth chapter concerned that two asymmetrical Cu( II) complexes were gained. Salicylaldimine-5-sulphonic acids was treated with the preformed morpholin under ambient conditions, which is a functionalised Mannich base that it was successfully converted to the corresponding Schiff base by condensation with 2-aminoethanol and L-a-Amino-f3-phenylpropionic acid. This gave to rise the unsymmetrical unsaturated ligands. The compounds were fully characterized by element analysis, IR, UV-Vis, *H NMR, molecular conductivity, Cyclic voltammetry means. Their results show that complexes possess anticipating the structure basically. The crystal structure of mononuclear Cu( II) complex was charactered by X-ray single-crystal diffraction analysis. Its crystal crystallized in triclinic with P-1, in which bond lengths[A] of Cu(II) are 1.877(3) Cu(l)-O(4), 1.981(3) Cu(l)-0(7), 2.007(3) Cu(l)-O(5), and angles [deg] are O(4)-Cu(l)-N(l) (94.22°), O(4)-Cu(l)-O(7) (91.18°), N(l)-Cu(l)-O(7) (169.24°), O(4)-Cu(l)-O(5) (174.09°), N(l)-Cu(l)-O(5) (84.26°), 0(7)- Cu(l)-O(5) (91.27°).In the fifth chapter we would like to describe that a mononuclear Cu( II) complex was reacted as intermediate in the synthesis of macrocyclic binuclear metal complexes, via hydroxymethylation, oxidation and condensing 2 equiv. 5-formyl-4-hydroxyl-3-hydroxymethylsulfonate with 1 equiv. of ethylenediamine and copper acetate in a one-pot reaction, in which formyl and phenolic hydroxy groups were protected by template formation in the subsequent oxidation step in order to producing binuclear metal complex in the following research work. It was a good water-soluble mononuclear metal complex. Because of no relative reports in the previous references, it would become a new template compound of mimicking natural enzymes of metal complexes.In the sixth chapter, three binuclear Fe(III) complexes were synthesized. 2, 6-(N, jV-biscarboxymethyl)aminomethyl-4-phenylphenol (5-Ph-HXTA) was firstly synthe -sized from 4-phenylphenol and iminodiacetic acid via Mannich reaction. In the synthetic procedure, we gained three different bridged Fe(III) complexes by changing carboxylate bridges. All of them were characterized by EA, IR, UV-Vis and CV. The similar UV-Vis and IR spectra of these three diiron complexes reflect that they have similar structures. The results of cyclic voltammetry shows their oxidize-reduce waves of Fe(III)Fe(III) and Fe(III)Fe( II) couple. In the last part their catalysis was determined by catalyzing the epoxidation of styrene by H2O2, and the results show Fe(III) complex...