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研究生: 王維鈴
Wang Wei-Ling
論文名稱: 酪胺酸酶之含氮硫三牙基二價銅錯合物的合成、結構及反應性之研究
Synthesis, Structure and Reactivity of Copper(II) Complexes with N2S Tridentate Ligands Relevant to Tyrosinase
指導教授: 李位仁
Lee, Way-Zen
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2011
畢業學年度: 99
語文別: 中文
論文頁數: 86
中文關鍵詞: 酪胺酸酶二價銅錯合物含氮硫三牙基
英文關鍵詞: Tyrosinase, Copper(II) Complexes, N2S Tridentate Ligands
論文種類: 學術論文
相關次數: 點閱:157下載:3
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  • 本研究使用兩個N2S三牙基的配位基,1,5-Bis(N-propylbenzimidazol-2-yl)-3-thiapentane (BBPrES)以及1,3-Bis(N-propylbenzimidazol-2-yl)-2-thiapropane (BBPrMS),並且利用這兩個N2S三牙基的配子與水合過氯酸銅反應,得到三個五配位正二價銅錯合物,包含[Cu(BBPrES)(CH3CN)2](ClO4)2 (1)、 [Cu(BBPrMS)(CH3CN)(η1-ClO4)](ClO4) (2)、[Cu(BBPrES)(CH3CN)- (tBuCN)](ClO4)2 (3)。將錯合物1和錯合物3分別與丁醇鉀反應,分別得到雙核正二價銅錯合物[Cu2(BBPrES)2(OMe)2](ClO4)2 (4)和[Cu2(BBPrMS)2(OH)2](ClO4)2 (5),五個錯合物皆得到X-光結構解析的晶體結構。我們以錯合物4及錯合物5在30ºC下催化2-萘酚的氧化反應,結果得到以dinol化合物的產物為主而不是binol的產物為主,產率分別為65%和74%。同時我們利用錯合物4及錯合物5在30ºC下催化3-羥基-2-萘甲酸甲酯進行氧化的反應,結果發現以雙苯環化合物的產物為主,產率皆為35%。

    In this work, two N2S tridentate ligands, 1,5-Bis(N-propyl- benzimidazol-2-yl)-3-thiapentane (BBPrES) and 1,3-Bis- (N-propyl- benzimidazol-2-yl)-2-thiapropane (BBPrMS) were employed to synthesize a series of copper(II) complexes. Three five-coordinate mononuclear complexes of [Cu(BBPrES)(CH3CN)2](ClO4)2 (1), [Cu(BBPrMS)(CH3CN)(η1-ClO4)](ClO4) (2) and [Cu(BBPrES)(CH3CN)- (tBuCN)](ClO4)2 (3), were obtained by the reactions of copper(II) perchlorate hexahydrate with BBPrES or BBPrMS. Interestingly, the reactions of potassium tert-butoxide with complexes 1 and 2 in a methanol/tetrahydrofuran mixed solution lead gave a dicopper(II) to bis(μ-methanolato) complex (4), [Cu2(BBPrES)2(OMe)2](ClO4)2 and a dicopper(II) bis(μ-hydroxo) complex (5), [Cu2(BBPrMS)2(OH)2](ClO4)2. Complexes 1-5, were characterized by X-ray crystallography. Naphthalen-2-ol was selected to be the testing substrate for oxidative reaction catalyzed by complex 4 and 5 at 30ºC. The major product of the reaction was a dione compound 2'-hydroxy- 1,1'-binaphthalene-3,4-dione with a yield up to 65% and 74%, respectively. Only little product was observed. The product 2'-hydroxy- 1,1'-binaphthalene-3,4-dione was characterized by NMR and X-ray crystallography. Another substrate, we proceed methyl 3-hydroxy-2-naphthoate was also employed for oxidative reaction catalyzed by complex 4 and 5 at 30ºC. Confrastely, the major product of this substrate was binol in a yield of 35% for both reactions.

    中文摘要………………………………………………………………...Ι 英文摘要...................................................................................................II 圖索引………………………………………………………………….III 表索引…………………………………………………………………..V 附錄索引………………………………………………………………..VI 第一章 緒論 第一節 研究動機與的………………………..….………………….1 第二節 生物體內的含銅蛋白………………………………………5 第三節 含銅蛋白之模型化合物…………………………………..10 第四節 正二價銅錯合物基本結構的性質……………………… .19 第二章 實驗部分 第一節 第一節實驗儀器、藥品及件……………..…………...….23 第二節 配位基的合成與鑑定……………..………………………30 第三節 金屬錯合物的成……………………...………………….. 35 第四節 羥基二價銅催化劑對雙芳香環的氧化偶和反應…...…...39 第三章 結果與討論 第一節 配子的合成討論……………………………………...…..43 第二節 正二價銅錯合物的結果與討論………………………….46 第三節 正二價銅錯合物的電子吸收光譜討論………………….64 第四節 羥基二價銅催化劑對雙芳香環的氧化偶和反應……….67 第四章 結論與展望………...…………………………………….…....82 參考文獻…………………………………………………………….….84 附錄

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