含銅蛋白質活性中心之擬態化合物研究—含氮硫不對稱三牙基之一價和二價銅錯合物之合成、結構及反應性探討

Synthesis, Structures, and Reactivity of Asymmetric Tridentate N/S Ligand of Copper(I) and Copper(II) Complexes—Mimics for the Active Site of Copper Containing Proteins

林育生(YU-SENG LIN)

指導教授 ： 李位仁 ； 蘇展政

國立臺灣師範大學/理學院/化學系/碩士(2007年)

摘要

為?模擬?銅蛋白以及胜?甘胺酸α-羥化氧化?(Peptidylglycine
α-hydroxylating monooxygenase，簡稱PHM)的活性中心，我們合成出一
個含氮??對稱之三牙配位基(MBMAS)，並成功地合成出一系?具有
MBMAS 二價和一價銅錯合物：Cu(MBMAS)Cl2 (1)、Cu(MBMAS)(NO3)2
(2) 、[Cu(MBMAS)2](CF3SO3)2 (3) 、[Cu4(MBMAS)4](CF3SO3)4 (4) 和Cu(MBMAS)Cl (8)。再將錯合物1 和2 分別與?同的?醇化合物反應以模擬氧化態的?銅蛋白活性中心，發現二價銅錯合物皆會被還原成無色
的一價銅錯合物。因此我們嘗試模擬還原態的?銅蛋白活性中心，將錯
合物4 分別與去質子化的?醇化合物2-(trimethylsilyl)benzenethiolate 與2-(benzoylamino)benzenethiolate 反應，由產物之核磁共振氫譜推測，有[Cu(MBMAS)((CH3)3SiC6H4S)]和[Cu(MBMAS)(C13H10NOS)]的生成。?將四核結構的錯合物4 與PPh3、tBuNC、CO 等小分子反應可形成並鑑定出一系?單核一價銅錯合物：[Cu(MBMAS)(PPh3)](CF3SO3) (5)、[Cu(MBMAS)(CNBut)](CF3SO3) (6)和[Cu(MBMAS)CO](CF3SO3) (7)，顯示錯合物4 具有?好的反應性。?氧氣與錯合物4 在甲醇下反應以紫外-可?光光譜偵測其產物，可發現?組電荷轉移吸收峰411 nm(ε = 25471)及617 nm (ε = 3940)?似於Cu(II)-superoxo 錯合物的吸收光譜。

關鍵字

含銅蛋白質活性中心 ； 含氮硫不對稱三牙基

並列摘要

In order to mimic the active site of blue copper protein and
peptidylglycine α-hydroxylating monooxygenase (PHM), we synthesize an asymmetric N2S(thioether) ligand, 1-methyl benzimidazolyl-2-methyl anilinoethyl sulfide (MBMAS). A series of Cu(II) and Cu(I) complexes of MBMAS, Cu(MBMAS)Cl2 (1), Cu(MBMAS)(NO3)2 (2), [Cu-(MBMAS)2](CF3SO3)2 (3), [Cu4(MBMAS)4](CF3SO3)4 (4), and Cu(MBMAS)Cl (8), have been successfully synthesized and fully characterized. Complexes 1 and 2 were futher reacted with a series of thiolate ligands to mimic the active site of oxidized form of blue copper protein. However, the Cu(II) complexes were reduced to form colorless Cu(I) complexes. Therefore, we aimed to model the active site of the reduced form of blue copper protein by reacting complex 4 with 2-(trimethylsilyl)benzenethiolate and 2-(benzoylamino)benzenethiolate, respectively. 1H-NMR spectra of the isolated products have suggested the formation of [Cu(MBMAS)((CH3)3SiC6H4S)] and [Cu(MBMAS)(C13H10NOS)]. The tetranuclear complex 4 exhibits excellent reactivities toward small molecules, such as PPh3, tBuNC, and CO. A series of mononuclear Cu(I) complexes, [Cu(MBMAS)(PPh3)](CF3SO3) (5),[Cu(MBMAS)(CNBut)](CF3SO3) (6), and [Cu(MBMAS)CO](CF3SO3)(7), were formed and spectroscopically and structurally characterized.
Reaction of dioxygen with complex 4 in methanol solution monitored by UV-vis spectroscopy exhibited two charge transfer absorption bands at 411 nm (ε = 25471) and 617 nm (ε = 3940). The UV-vis spectrum of the resulting species is similar to that of copper(II) superoxo complex.

並列關鍵字

The Active Site of Copper Containing Proteins ； Asymmetric Tridentate N/S Ligand

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