臺灣博碩士論文加值系統

三銅(II)化合物和單核鋅(II)化合物使用希夫鹼配位基tris(5-benzyl-amineazafulvene-2-methyl)amine (H3TPANBz; 1a) 與 tris(5-phenylethyl-amineazafulvene-2-methyl)amine (H3TPANPEA; 1b)合成和鑑定。H3TPANBz和H3TPANPEA在使用不同當量的鹼去質子化後並與五水硫酸銅或氯化銅反應得到兩種不同的三核銅(II)配合物。[TPANBzCu3(μ3-SO4)(μ3-OH)](3a)和[TPANPEACu3(μ3-SO4)(μ3-OH)](3b)，它們具有三重橋接的氫氧根和硫酸根陰離子。另一方面，[TPANBz2Cu3] (2a) 和[TPANPEA2Cu3](2b)沒有氫氧根和硫酸根陰離子結合。晶體學研究表明三銅化合物2a有一個空腔，可以讓我們研究陰離子包覆。
為了模擬碳酸酐酶的催化中心，使用之前合成的配位基H3TPANBz，一個具有第二個配位圈的概念配配位基，富有氫鍵系統的配位基可以穩定小分子並提供質傳的功能。所以合成了一系列的鋅化合物。晶體學研究表明，配合物 [H3TPANBzZn(ClO4)](ClO4)(5a)具有鋅和陰離子最長的鍵長，未來將更容易做取代反應合成出帶有Zn-OH2核心的目標產物。

The trinuclear copper(II) complexes and the mononuclear zinc(II) complexes were synthesized from the Schiff-base ligands tris(5-benzyl-amineazafulvene-2-methyl)amine (H3TPANBz; 1a) and tris(5-phenylethyl-amineazafulvene-2-methyl)amine (H3TPANPEA; 1b) and structurally characterized. Deprotonation by different base the H3TPANBz and H3TPANPEA following treat CuSO4∙5H2O or CuCl2 will obtain two different kinds of trinuclear copper(II) complexes. Complexes [TPANBzCu3(μ3-SO4) (μ3-OH)] (3a) and [TPANPEACu3(μ3-SO4) (μ3-OH)] (3b), both have hydroxide and sulfate anions triply bridging to three copper(II) ions. On the other hand, complex [TPANBz2Cu3] (2a) and [TPANPEA2Cu3] (2b) without hydroxide and sulfate anions binding. Crystallographic study reveals the tri-copper complex 2a has an empty cavity which may allow us to study the anion encapsulation.
In order to mimic the carbonic anhydrase catalytic center of the enzyme, the ligand H3TPANBz with a second coordination sphere concept ligand could stabilize small molecules binding and provide diverse activations. Several zinc complexes were synthesized. Crystallographic study reveals that complex [H3TPANBzZn(ClO4)](ClO4) (5a) has the longest bond length between zinc and anion, and it will be easier to change other anions in the future.

目錄
第一章、緒論 1
1-1前言 1
1-2含有鋅的生物體酵素 1
1-3碳酸酐酶 2
1-4三銅錯合物 3
1-5第二層配位圈概念 4
1-6第二層配位圈扮演氫鍵接受者 5
1-7第二層配位圈扮演氫鍵接受者 5
1-8配位基的設計 9
第二章、結果與討論 11
2-1化合物H3TPANPEA (1b)的合成與鑑定 11
2-2化合物TPANBz2Cu3 (2a)的合成與鑑定 13
2-3化合物TPANPEA2Cu3 (2b)的合成與鑑定 17
2-4化合物TPANPEACu3(μ3-SO4)(μ3-OH) (3b)的合成與鑑定 23
2-5化合物2a、2b、3a、3b的Click reaction催化反應 30
2-6化合物PPN[TPANBz Cu3(μ3-SO4)(μ3-OH)(NO2)] (4a)的合成與鑑定 31
2-7化合物[H3TPANBzZnCl]Cl (5a)的合成與鑑定 33
2-8化合物[H3TPANBzZn(ClO4)](ClO4) (6a)的合成與鑑定 34
2-9化合物[H3TPANBzZnF](BF4) (7a)的合成與鑑定 37
2-10化合物[H3TPANBzZn(SCN)](ClO4) (8a)的合成與鑑定 40
2-11化合物[H3TPANBzZnOH]ClO4 (9a)的合成與鑑定 41
第三章、結論 44
第四章、實驗部分 45
4-1試藥及使用前處理 45
4-2儀器設備 47
4-3實驗步驟 48
4-3-1化合物H3TPANPEA (1b)的合成 48
4-3-2化合物TPANBz2Cu3 (2a)的合成 48
4-3-3化合物TPANPEA2Cu3 (2b)的合成 48
4-3-4化合物TPANPEA Cu3(μ3-SO4)(μ3-OH) (3b)的合成 48
4-3-5化合物PPN[TPANBzCu3(μ3-SO4)(μ3-OH)(NO2)] (4a)的合成 49
4-3-6化合物[H3TPANBzZnCl]Cl (5a)的合成 49
4-3-7化合物[H3TPANBzZn(ClO4)](ClO4) (6a)的合成 49
4-3-8化合物[H3TPANBzZnF](BF4) (7a)的合成 49
4-3-9化合物[H3TPANBzZn(SCN)](ClO4) (8a)的合成 50
4-3-10化合物[H3TPANBzZn(OH)](ClO4) (9a)的合成 50
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