在本篇論文中，我們用不同方式合成具掌性、Schiff base部分的雙硫雙氮四配位之鋅、鎳錯合物N,N'-Bis(2-thiobenzylidene)- l,2-(R,R)cycholhexylenediaminatozinc(II) (1)、N,N'-Bis(2-thioben- zylidene)-l,2-(R,R)cycholhexylenediaminatonickel(II) (2)，也得到了錯合物2以及吡啶與錯合物1加成產物(1．Py)之晶體結構。之後，將我們得到的這些雙硫雙氮金屬錯合物與已發表在文獻上的雙氧雙氮類似物作結構的比較與探討。爾後，期盼這些具掌性的錯合物能夠對酵素模型研究有所幫助。

In this study, we used different ways to synthetize four-coordinate
zinc(II) and nickel(II) complexes with optically active Schiff base offering N2S2 coordination, i.e. N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexyl- enediaminatozinc(II) (1) and N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cychol-
hexylenediaminatonickel(II) (2). We obtained the crystal structure of 2 and
the pyridine adduct of 1, N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexylenediaminopyridylzinc(II) (1．Py). Coordination geometry around Zn atom in 1．Py is a distorted trigonal bipyramid. These structures were compared with the N2O2 stuctural analogues reported in the literature. We hope these chiral complexes can make contribution to the enzyme model studies in the future.

提要….i
目錄….iii
式目錄…iv
表目錄…v
圖目錄…v
附錄目錄…vi
壹、緒論…1
一、前言…1
二、含硫多牙配位基之鋅錯合物在生化上之介紹與應用…2
三、含硫多牙配位基之鎳錯合物在生化上之介紹與應用…4
四、超氧化物歧化酶及其含鎳金屬之模擬酵素模型之介紹…6
五、不對稱催化之介紹…8
六、 Darensbourg實驗室所作雙硫雙氮錯合物之介紹…10
七、研究動機…13
貳、實驗部分…16
一、試藥…16
二、儀器設備…18
三、實驗步驟…20
1. Thiosalicylaldehyde的合成與鑑定…20
2. N,N'-l,2-(R,R)cycholhexylenebis(thiosalicykimine) 配位基L1的合成與鑑定…21
3. N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexylenediaminatozinc(II) 錯合物1的合成與鑑定…21
4. N,N'-Bis(2-thiobenzylidene)-l,2-(R,R)cycholhexylenediaminatonickel(II) 錯合物2的合成與鑑定…23
參、結果與討論…25
一、起始物thiosalicylaldehyde的合成…27
二、Schiff base配位基及錯合物的合成… 28
三、錯合物1．Py的結構討論.…31
四、錯合物2的結構討論…38
五、錯合物1、1．Py與錯合物2的光譜與結構討論…45
5-1. 1H-NMR光譜之討論…45
5-2. 晶體結構之討論…47
5-2-1. M(N2S2)與M(N2O2)之晶體結構比較…47
5-2-2錯合物1．Py與錯合物2之晶體結構比較…51
六、未來展望…54
肆、結論…55
伍、參考文獻…57
陸、附錄…59

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