在本篇論文中，我們藉由合成含硫醇希夫鹼鋅化物[ZnL1]2(L1=o-C6H4(SH)(CH=NC6H4SH-o))，探討在合成含希夫鹼化合物時各起始物之間的反應順序關係，我們也確認了在反應中是否生成金屬-醛基中間物與2-胺基硫醇進行模板合成是生成[ZnL1]2的必要條件。我們藉由加入TMEDA與[ZnL1]2反應，得到Zn(L1)(TMEDA)，並對其進行結構分析。我們也將[ZnL1]2透過金屬交換的方式，以不同且較簡易的方法製備[NiL1]2。最後我們將[ZnL1]2與Zn(L1)(TMEDA)透過NaBH4對L1中的亞胺基進行還原並得到[ZnL2]2(L2=o-C6H4(SH)(CH2NHC6H4SH-o))與Zn(L2)(TMEDA)，並從1H NMR與質譜對其進行鑑定。

In this article, we examined different synthetic approaches with varying adding starting materials for the thiol containg schiff-base complex [ZnL1]2(L1=o-C6H4(SH)(CH=NC6H4SH-o)). We found that the key step for successful synthesis of [ZnL1]2 is the formation of zinc aldehyde intermediate. We also break the [ZnL2]2 dimer by adding chelating agent, TMEDA, to obtain the Zn(L1)(TMEDA) monomer. It’s single crystal X-ray structure confirmed, the structure of the target ligand L1. We also synthesized [NiL1]2 by transmetalation of [ZnL1]2 - an easier synthetic approach. We further reduced the imine part on L1 of [ZnL1]2 and Zn(L1)(TMEDA) to get [ZnL2]2(L2=o-C6H4(SH)(CH2NHC6H4SH-o)) and Zn(L2)(TMEDA) respectively for future reactivity studies.

題要..........................................................................................i
目錄........................................................................................iii
圖目錄.....................................................................................iv
表目錄......................................................................................v
附錄目錄.................................................................................vi
壹、緒論.................................................................................1
一、希夫鹼(Schiff-base)……………………......................1
二、含氮氧配子之希夫鹼化合物相關研究.........................3
三、配位原子的改變：當氧換成硫.....................................7
四、含氮硫配子之希夫鹼化合物相關研究.........................7
五、希夫鹼配子與化合物的設計.........................................9
貳、實驗部分.......................................................................11
一、試藥及純化...................................................................11
二、儀器設備.......................................................................13
三、合成反應.......................................................................14
1. 2-mercaptobenzaldehyde的合成與鑑定....................14
2. 2-(E)-(2-mercaptobenzylimino)benzenethiolatozinc(II) ([ZnL1]2))的合成與鑑定................................................14
3. (N,N-dimethylethylenediamine)(2-(E)-(2-mercaptobenzylimino)benzenethiolato)zinc(II) (Zn(L1)(TMEDA)) 合成與鑑定.........................................................15
4.2-(E)-(2-mercaptobenzylimino)benzenthiolatoniclel(II) ([NiL1]2)合成與鑑定......................................................15
5. 2-(2-mercaptobenzylamino)benzenethiolatozinc(II) ([ZnL2]2)合成與鑑定...........................................................16
6. (N,N-dimethylethylenediamine)(2-(2-mercaptobenzylamino)benzenethiolato)zinc(II) (Zn(L2)(TMEDA))合成與鑑定..........................................................16
參、結果與討論...................................................................17
一、[ZnL1]2的一鍋化合成反應探討.................................18
1.路徑1：先合成含希夫鹼配子再與金屬反應形成化合物...........................................................................................19
2.路徑2：金屬-胺類化合物所造成的反應障礙...........................................................................................21
3.路徑3：生成Zn-MBA再藉由模板合成得到[ZnL1]2…….....................................................................................23
4.[ZnL1]2以及子產物Zn(L1)(TMEDA) ……….................24
二、[ZnL1]2與溴化鎳的金屬交換反應.............................26
三、[ZnL1]2與Zn(L1)(TMEDA)之氫化反應.....................28
四、結晶結構探討論...........................................................29
1.Zn(AT)2晶體結構介紹.....................................................29
2.[NiL1]2晶體結構介紹......................................................30
3.Zn(L1)(TMEDA)晶體結構介紹.......................................31
肆、結論..............................................................................34
伍、參考文獻......................................................................36
陸、附錄..............................................................................39

圖目錄
圖一、希夫鹼合成反應機構................................................1
圖二、(a)維他命B6及磷酸吡哆醛PLP，(b)PLP藉由與酵素上賴胺酸(Lysine)形成希夫鹼而連結.............................2
圖三、(a)Grubbs的含鎳希夫鹼化合物，(b)烯類聚合催化反應路徑................................................................................3
圖四、Salen合成方式及其結構.........................................4
圖五、修飾後Salen化合物.................................................4
圖六、Jacobsen epoxidation催化劑作用示意圖............5
圖七、thiosalicylaldimine通式..........................................7
圖八、氫化酵素DesulfoVibrio gigas的活性中心............8
圖九、Stenson設計的鎳鐵氫化酵素的模擬模型.............9
圖十、論文中所合成得到的化合物結構(a)[ZnL1]2 (b)Zn(L1)(TMEDA) (c) [NiL1]2 (d) [ZnL2]2 (e)Zn(L2)(TMEDA)..............................................................................10
圖十一、含thiosalicylaldiminate的硫氮配子之希夫鹼化合物的合成方法(a)階段式(step by step)反應，(b)一步驟反應(one-pot reaction)......................................................17
圖十二、(a)2-醛基硫酚及(b)2-胺基硫酚.........................17
圖十三、[ZnL1]2合成反應路徑設計...........................................................................................19
圖十四、混合HMBA與HAT得到未知Product A而非H2L1....................................................................................19
圖十五、thiosalicylaldimine形成後受硫原子攻擊使分子中的亞胺遭破壞...................................................................20
圖十六、H2L1分子內重排反應.........................................21
圖十七、路徑1得到混合產物[ZnL1]2與Zn(AT)2的反應式...........................................................................................21
圖十八、路徑(2)：Zn(AT)2的生成以阻斷後續反應示意圖...........................................................................................22
圖十九、路徑(3)：生成Zn-MBA後再與HAT反應得到[ZnL1]2.................................................................................23
圖二十、 [ZnL1]2的可能生成反應機構...........................24
圖二十一、二聚體[ZnL1]2與TMEDA反應生成單體Zn(L1)(TMEDA)…...........................................................................25
圖二十二、[ZnL1]2與溴化鎳進行反應生成[NiL1]2........27
圖二十三、[ZnL1]2與Zn(L1)(TMEDA)之氫化.................28
圖二十四、Zn(AT)2晶體結構............................................30
圖二十五、[NiL1]2晶體結構.............................................30
圖二十六、Zn(L1)(TMEDA)分子結構..............................32
圖二十七、Addison等人所提出的雙三角錐¬-四方錐判定方式模型..............................................................................33
圖二十八、[ZnL1]2的合成探討結果................................34

表目錄
表一、Jacobsen epoxidation催化結果.............................5
表二、Salen系列錯合物相關催化反應..............................6
表三、Bluhm所合成的硫氮希夫鹼鉻化合物催化劑在乙烯催化上的成果.........................................................................8
表四、Zn(AT)2部分鍵長鍵角資料.....................................30
表五、Ni(SNS) 部分鍵長鍵角資料...................................31
表六、Zn(L1)(TMEDA)部分鍵長鍵角資料.......................32

附錄目錄
附錄6-1-1. 2-mercaptobenzaldehyde的1H NMR(CDCl3)光譜........................................................................39
附錄6-1-2. 2-mercaptobenzaldehyde與2-aminothiolphenol混合反應得到Product A的1H NMR(CDCl3)光譜........................................................................40
附錄6-1-3. 由路徑(1)所得到的[ZnL1]2與Zn(AT)2之混合物1H NMR(CDCl3)光譜...........................................................................................41
附錄6-1-4. 由路徑(3)所得到的[ZnL1]2與Zn(AT)2之混合物1H NMR(CDCl3)光譜.....................................................42
附錄6-1-5. [ZnL1]2的1H NMR(DMSO-d6)光譜..............43
附錄6-1-6. Zn(AT)2的1H NMR(DMSO-d6)光譜.............44
附錄6-1-7. Zn(L1)(TMEDA)的1H NMR(CDCl3)光譜.....45
附錄6-1-8. [ZnL2]2的1H NMR(DMSO-d6)光譜..............46
附錄6-1-9. Zn(L2)(TMEDA)的1H NMR(CDCl3)光譜.....47
附錄6-2-1. [NiL1]2之MALDI-TOF光譜，metrix：CHC，Positive mode.....................................................................48
附錄6-2-2. [NiL1]2之MALDI-TOF光譜，metrix：CHC，Negtive mode......................................................................49
附錄6-2-3. [ZnL2]2之MALDI-TOF光譜，metrix：SA，Positive mode.....................................................................50
附錄6-2-4. [ZnL2]2之MALDI-TOF光譜，metrix：SA，Negtive mode......................................................................51
附錄6-2-5. Zn(L2)(TMEDA)之MALDI-TOF光譜，metrix：SA，Positive mode............................................................52
附錄6-2-5. Zn(L2)(TMEDA)之MALDI-TOF光譜，metrix：SA，Negitive mode............................................................53
附錄6-3. Zn(o-SC6H4NH2)2之繞射實驗條件................54
附錄6-4. Zn(L1)(TMEDA)之繞射實驗條件.......................60

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