研究生: |
蔡秀緣 Shiou-Yuan Tsai |
---|---|
論文名稱: |
銅蛋白質模型錯合物研究:雙苯咪三牙配位基銅錯合物之合成及性質研究 |
指導教授: |
蘇展政
Su, Chan-Cheng |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2002 |
畢業學年度: | 90 |
語文別: | 中文 |
論文頁數: | 118 |
中文關鍵詞: | 血青素 、銅蛋白質 、苯咪 |
英文關鍵詞: | copper, benimidazole, Tyrosinase |
論文種類: | 學術論文 |
相關次數: | 點閱:345 下載:0 |
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本研究合成具有π-鍵結能力的含雙苯咪三牙基配子:雙苯咪-2-氧丙(bbmo)、雙(N-甲基)苯咪-2-氧丙(bbMemo)、雙苯咪-2-硫丙(bbms)、雙(N-甲基)苯咪-2-硫丙(bbMems),合成了兩系列的錯合物,(1)[Cu(L2)](ClO4)2或[Cu(L)(NN)](ClO4)2 ,NN為2,2’-聯啶(bipy)、1,10-二氮雜菲(phen)、N,N,N’,N’-四甲基乙二胺(tmen)等雙牙配子;(2)[Cu(L)X2]或[Cu(L)(N)](ClO4)2,X為氯離子或醋酸根,N為單牙配子。利用X-光結構解析、紅外光光譜、電子順磁共振光譜、電子吸收光譜及可見光高斯交疊解析等,完成錯合物的鑑定及鍵結性質的探討。
目前已完成X-光單晶結構解析的二價銅錯合物有十個,其中
trans-fac-[Cu(bbmo)2](ClO4)2(DMF)2(H2O)2、trans-fac- [Cu(bbMemo)2]-(ClO4)2(DMF)、fac-[Cu(bbMemo)(bipy)(H2O)](ClO4)2- (H2O)、fac-[Cu(bbMems)(bipy)](ClO4)2(DMF)(CH3OH)、mer- [Cu(bbms)(CH3CN)(H2O)](ClO4)2屬於單斜晶系(Monoclinic);fac-[Cu(bbMems)2](ClO4)2(CH3CN)、mer-[Cu(bbMemo)(Cl)(ClO4)] 屬於斜方晶系(Orthorhombic); 而fac-[Cu(bbmo)(bipy)]- (ClO4)2(DMF)、fac-[Cu(bbMemo)(phen)](ClO4)2(CH3CN)、fac- [Cu(bbms)(bipy)](ClO4)2(DMF)2屬於三斜晶系(Triclinic)。
從結果得知,所合成的含雙苯咪三牙基配子bbmo、bbMemo為π-donor的配位基。由系列(1)錯合物的可見光光譜高斯解析結果,得知二價銅錯合物結構為拉長八面體或方形角錐的d軌域順序:
dxy >> dx2-y2 > dz2 > dyz > dxz
在研究中,探討所合成之三牙配子(bbmo、bbMemo)室溫下與一價銅形成錯合物後與氧反應,同時也探討二價銅錯合物[Cu(bbMemo)(Cl)(ClO4)](H2O)與[Cu(bbMemo)(CH3COO)2](H2O)2室溫中與雙氧水的反應,以電子吸收光譜判斷反應產物,得知二價銅錯合物與雙氧水反應可能形成m-h2:h2-peroxo鍵結型式的錯合物。
另外也初步鑑定此類型三牙配子合成的銅錯合物,具有與酪胺酸相似的催化能力,可將2,4-雙第三丁基苯酚或3,5-雙第三丁基鄰苯二酚催化成3,5-雙第三丁基雙,推斷其反應過程中銅錯合物可能形成m-h2:h2-peroxo鍵結型式。
Two types of Copper(II) complexes of bis(benzimidazolyl-2-yl)- 2-oxopropane (bbRmo) and bis(benzimidazolyl-2-yl)-2-thiopropane (bbRms), where R=H, CH3, [Cu(L2)](ClO4)2 or [Cu(L)(NN)](ClO4)2 ( NN=2,2-Bipyridine(bipy), 1,10-Phenanthroline (phen), N,N,N’,N’- tetramethlyenediamine(tmen)) and [Cu(L)X2] or [Cu(L)(N)](ClO4)2 ( N=chloridehave) have been synthesized and characterized by X-ray crystal structure, elemental analyses, infrared, electronic, and EPR spectra.
By single-crystal X-ray diffraction methods, the crystal and molecular structure of Cu(II) complexes have been determined. The crystal data of these complexes are described below:
trans-fac-[Cu(bbmo)2](ClO4)2(DMF)2(H2O)2、trans-fac-[Cu(bbMemo)2]- (ClO4)2(DMF)、fac-[Cu(bbMemo)(bipy)(H2O)]- (ClO4)2(H2O)、fac- [Cu(bbMems)(bipy)](ClO4)2(DMF)(CH3OH)、mer-[Cu(bbms)(CH3CN)- (H2O)](ClO4)2 are Monoclinic; fac-[Cu(bbMems)2](ClO4)2(CH3CN)、mer-[Cu(bbMemo)(Cl)(ClO4)] are Orthorhombic; and fac-[Cu(bbmo)- ipy]](ClO4)2(DMF)、fac-[Cu(bbMemo)(phen)](ClO4)2(CH3CN)、fac- Cu(bbms)(bipy)]- (ClO4)2(DMF)2 are Triclinic.
In conclusion, both bbmo and bbMemo tridentate ligand bind to copper d orbital as π-donor. The Gassian component band of electronic spectra, the sequences of the d orbitals were assigned as dxy >> dx2-y2 > dz2 > dyz > dxz for elongated Oh and square pyramidal complexes.
The reactions of the corresponding Cu(I) complexes (bbmo、bbMemo) with O2 at room temperature and [Cu(bbMemo)(Cl)(ClO4)](H2O) or [Cu(bbMemo)(CH3COO)2](H2O)2 with H2O2 have been investigated. Based on the electronic spectral data at room temperature are likely forming m-h2:h2-peroxo complexes.
Preliminary studies on oxidation of 3,5-di-t-butylcatechol and 2,4-di-t-butylphenol catalyzed by Cu(bbmo)+or Cu(II) complexes exhibit Tyrosinase-like activities.
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