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標題: | 含N6O2八牙配位基之三銅(II)錯合物之合成及結構鑑定 Synthesis and Characterization of Tricopper(II) Complexes with N6O2-Octadentate Ligands |
作者: | Chia-Ling Chang 張家綾 |
指導教授: | 陳竹亭(Jwu-Ting Chen) |
關鍵字: | 八牙配位基,三銅(II)錯合物, Octadentate Ligands,Tricopper(II) Complexes, |
出版年 : | 2011 |
學位: | 碩士 |
摘要: | 有一種酵素存在於甲烷菌內,其可以將甲烷氧化成甲醇,這類酵素是以金屬銅作為其活性的中心。其主要活性中心在近年來的研究中發現是三個金屬銅錯合物的形式。為了去模擬這一類的酵素,本實驗室合成出了一系列的八牙配位基衍生物(N6O2-octadentate ligands),可分為上半部為六環或七環的四牙配位基和下半部為對稱的不同取代基的吡啶胺或甲基咪唑胺(methyl imidazoleamine),(縮寫為6-PyR或7-PyR或6-ImR 或7-ImR;如下圖)。和過氯酸銅(Copper(II) perchlorate)合成出深藍色的三銅錯合物。此類的三銅錯合物可利用紫外光-可見光(UV-Vis)、電噴灑質譜儀(ESI-MS)、超導量子干涉磁化儀(SQUID)、電子自旋共振光譜(ESR)、導電度測量(conductivity measurement)、紅外線共振光譜(IR)、元素分析(elemental analysis)、循環伏安法(cyclic voltammetry measurement)與單晶結構對其物理性質與結構加以分析研究。
由單晶結構顯示,三銅錯合物可看成是由一單銅與一雙銅相輔相成平面三角形的架構;單核銅其金屬的結構是會有溶劑配位在金屬上形成方型椎體(square pyramidal)的配位模式,而雙核銅其兩個金屬銅是利用氫氧根離子(OH-),具有橋接兩個銅的作用,且都是以平面四邊形(square planar)作為其配位模式。比較特別的是,當上半部分為六環,下半部對稱的配位基中氮上為乙基取代的吡啶胺(pyridineamine),將這個八牙配位基合成出來的三銅金屬化合物置於空氣中養晶,所得到的晶體結構是包含有兩個八牙配位基的八銅錯合物,八牙配位基上面六環部分是呈現開環且是椅子的構型(chair form),且中間由碳酸根離子(CO32-)和氫氧根離子(OH-)作為橋接(bridge)。 There are considerable increasing interests of the interaction of redox-active transition metal ions, such as copper, and proradical ligands in metalloenzyme. As in methane oxidation (particulate methane monooxygenase, pMMO) of methanotrophs, it often requires copper for activation of molecular oxygen. The major reaction site has been ascribed to a trinuclear cluster. In order to model the enzyme, a series of tricopper(II) complexes with N6O2-octadentate ligand L which containing six member ring or seven member ring at A site and pyridineamine or imidazoleamine substituents at B site (abbreviated as 6-PyR or 7-PyR or 6-ImR or 7-ImR; see Chart I) from CuII(ClO4)2•6H2O and CuII(BF4)2 has been synthesised. These tricopper(II) complexes have been characterized by UV-Vis absorption spectroscopy, ESI mass spectra, conductivity measurement, electron paramagnetic resonance (ESR), IR spectrum, elemental analysis (EA) as well as Single-crystal X-ray diffractions. Based on Single-crystal X-ray diffraction, the tricopper(II) complexes were combined with mononuclear and dinuclear copper cofactors in triangular geometry by the octadetate ligands. The mononuclear copper was bonded in a square pyramidal environment with a N2O3-donor and the dinuclear copper were bridged by hydroxide ion. The structure will be compared with the known species with similar configurations. There was a result of Single-crystal X-ray diffraction beyond our expectations, a solution of tricopper(II) complex with octadentate ligand containing six-membering at A site and ethyl pyridineamine substituents at B site was explored to air after a few days a octanuclear copper(II) carbonate species was formed. The Single-crystal X-ray structure of octanuclear copper(II) carbonate complex was established. The structure of the octanuclear copper(II) carbonate species containing two octadentate ligands which were chair form at A site and bridged by hydroxide and carbonate ions. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/35196 |
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