Copper Complexes of Monoanionic N,N,S-Scorpionate Ligand：Model Study of 2-His-1-Cys Non-Heme Metalloproteins and Silver Complexes of Monoanionic N,N,O-Scorpionate Ligand

• Main Author: 朱紹翔
• Other Authors: 洪政雄
• Format: Others
• Language: zh-TW
• Published: 2007
• Online Access: http://ndltd.ncl.edu.tw/handle/31643477245914124044

碩士 === 國立彰化師範大學 === 化學系 === 95 === In order to mimic the function and active site structure of copper proteins such as：nitrite reductase, nitrous oxide reductase, amine oxidase, dopamine ß-monooxygenase and peptidylglycine α-hydroxylating monooxygenase, the N2S scorpionate ligand with methyl as substituents [{Li(bdmpzdta)(H2O)}4] (bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate) and with t-butyl as substituents bdtbpzdta have been synthesized. Three copper complexes , Cu(Ⅱ)(bdmpzdta)2 (1), [Cu(Ⅰ)(bdtbpzdta)Br]2 (2) and {Cu(Ⅰ)2[µ-S-(bdtbpzdta)2]}2 (3) have been obtained . During the characterization of copper complexes we found an exchange reaction that the dithioacetate moiety has been slowly converted to acetate group in the presence of carbon dioxide. There is no precedent example on the C-C bond cleavage in either [{Li(bdmpzdta)(H2O)}4] or mental complex of N2S ligand . Our observation represents an unique example of CC bond activation promoted by metal ion and, more importantly, this type of compound might be able to carry out the CO2 fixation reaction. In the second part of research, multidentate N2O ligands are used to bridge metal centers to form clusters or polymeric structures via coordination bonds. The N2O scorpionate ligand bdmpza (= bis(3,5-dimethylpyrazol-1-yl) has been used because carboxylate group can bridge to metal centers. The silver complexes, K4{[Ag(bdmpza)2]2}(ClO4)2(Acetone)2 (4), [Ag4(bdmpza)3]2(OH)(ClO4) (5), and ({Na[Ag(bdmpza)]2BF4(H2O)}2)n (6) have been synthesized and structure characterized. These silver complexes demonstrate the importance of cation and anion on controlling the three dimensional structure. In the case of complex (6) linear chain structure forms. It is optimistic that other two dimensional or three dimensional supramolecular structures can be constructed using this type of N2O coordinating ligand.