臺灣博碩士論文加值系統

含氮原子配位的後過渡金屬錯合物無論在生物科技或是在工業觸媒上都具有相當程度的應用。而咪唑分子在金屬酵素上具有重要的地位，因為大量含金屬酵素具有含咪唑的組胺酸與金屬配位，咪唑在生物方面的重要性便不言可喻。
因此我們設計了兩種相似而含有咪唑及吡啶基的三牙配位基4-(2-Pyridylmethyliminomethyl)imidazole（ImPyI）及4-(2-Pyridylmethyl aminomethyl)imidazole（ImPyA），並與鋅、銅、與鎳金屬離子形成金屬錯合物，以進行生化模擬的研究。我們利用了不同的方式養晶得到錯合物(2)、(6)、(8)、(9)、(10)、(17)與(18)。有趣的是在鋅金屬錯合物中，雖然都為ML2鋅金屬錯合物，但我們得到兩種不同立體位向的金屬錯合物（錯合物(8)及(9)），而在鎳金屬錯合物(17)與(18)均是具有中心對稱的錯合物(17)與(18)，而在銅金屬錯合物(2)與(10)則是形成MLX2的金屬錯合物，我們對於其所生成的金屬錯合物之結構有極高的興趣，在相同配位基中因為三個氮原子donor的特性不同，而在結構上也會有所差異，我們也嘗試在咪唑上加一拉電子溴基（錯合物(19)），並擴充至四牙配位基（錯合物(20)），也都有得到其晶體結構。大部分的金屬錯合物都存在分子間弱氫鍵去穩定其結構。

Late transition metal complexes bearing nitrogen-containing ligands may act as catalyst in biotechnology or industrial catalysis. Imidazole is one of the most common biofunctional ligands that play critical roles in meta1loenzymes, since the imidazole moiety of the histidyl residues often constitutes all or part of the binding sites of various transition metal centers.
In this work, some new zinc(II), copper(II) and nickel(II) complexes containing the imidazolate and pyridyl moieties incorporated in the imine (ImPyI) and amine (ImPyA) ligands were obtained. Different methods of crystallization yield crystals of complexes (2), (6), (8), (9), (10), (17) and (18). Subsequent structural analyses revealed their interesting structures. In zinc(II) and nickel(II) complexes, facial isomers were isolated while none of the meridional isomers were observed. Particularly interesting is the zinc(II) complexes where two facial complexes with different geometries were identified. The mixture of the different nitrogen donor groups in the same ligand provides handy comparison of these structural variations due to the different nature of these donor groups. One tridentate ligand with bromide substitution on the imidazolate and a tetradentate ligand with an additional pyridyl group were synthesized as an extension of this work. One crystal structure of each of the corresponding metal complex bearing these ligands is also discussed here. Most metal complexes are consolidated by extensive weak hydrogen bonds among them in the crystal lattices.

提要………………………………………………………………………… i
目錄………………………………………………………………………… iv
表目錄………………………………………………………………………… vii
圖目錄………………………………………………………………………… vii
附錄目錄…………………………………………………………………… x
壹、緒論…………………………………………………………………… 1
一、前言………………………………………………………………… 1
二、含氮多牙配位基之鋅錯合物在生化領域的應用……………… 1
三、含氮多牙配位基之銅錯合物在生化領域的應用……………… 3
四、含氮多牙配位基之鎳錯合物在生化領域的應用……………… 4
五、含氮多牙配位基之多核錯合物在生化領域的應用…………… 6
六、咪唑（Imidazole）之介紹………………………………………… 9
七、本文配位基之介紹……………………………………………… 14
貳、實驗部分……………………………………………………………… 16
一、儀器……………………………………………………………… 16
二、藥品及純化……………………………………………………… 18
三、實驗步驟………………………………………………………… 21
參、結果與討論…………………………………………………………… 36
一、配位基之合成及鑑定…………………………………………… 36
二、錯合物之合成及鑑定…………………………………………… 38
(1) 銅錯合物Cu(ImPyI)X2的合成與結構探討………………… 38
(2) 鎳錯合物Ni(ImPyI)X2的合成與結構探討………………… 42
(3) 鋅錯合物Zn(ImPyA)2X2的合成與結構探討……………… 45
(4) 銅錯合物Cu(ImPyA)X2的合成與結構探討………………… 52
(5) 鎳錯合物Ni(ImPyA)X2的合成與結構探討………………… 55
三、不同養晶方式之探討…………………………………………… 55
(1) 錯合物[Ni(ImPyA)2]Cl2．2H2O(17)的結構探討…………… 57
(2) 錯合物[Ni(ImPyA)2]Br2．2H2O(18)的結構探討…………… 59
四、不同配位基之金屬錯合物比較………………………………… 62
五、溴化後配位基與四牙配位基之金屬錯合物合成及鑑定……… 63
(1) 鎳錯合物[Ni(BrImPyI)(μ-Br)(H2O)]2Br(19)的合成與結構
探討…………………………………………………………… 63
(2) 銅錯合物[Cu(Im1,2Py)Cl]2CuCl4(20)的合成與結構探討…… 66
六、ImPyI與ImPyA配位基金屬反應整理及補充說明…………… 69
(1) 不同金屬（鎳、銅與鋅）對金屬錯合物之影響…………… 70
(2) 不同配位基（ImPyI及ImPyA）對金屬錯合物之影響…… 70
(3) Counter ion對金屬錯合物之影響…………………………… 70
(4) 鋅金屬錯合物合成反應補充說明…………………………… 71
肆、結論…………………………………………………………………… 72
伍、參考文獻……………………………………………………………… 74
陸、附錄…………………………………………………………………… 78

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