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研究生：	朱偉正 Chu, Wei-Cheng
論文名稱：	合成與描述以tristhiolatephosphine為配位基的V(III)化合物當成釩固氮酵素釩部位的模型 Synthesis and Characterization of V(III) Complexes of tristhiolatephosphine Ligands as Models of the Vanadium site in V-nitrogenase
指導教授：	許鏵芬 Hsu, Hua-Fen
學位類別：	碩士 Master
系所名稱：	理學院 - 化學系 Department of Chemistry
論文出版年：	2003
畢業學年度：	91
語文別：	中文
論文頁數：	83
中文關鍵詞：	固氮酵素、固氮作用
外文關鍵詞：	nitrogenase, Mo-nitrogenase, FeMo-cofactor, V-nitrogenase, FeV-cofactor, capped octahedral
相關次數：	點閱：81 下載：1
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固氮酵素(nitrogenase)的催化作用是在常溫常壓下將N2還原成NH3並伴隨還原2H+變成H2，根據一些光譜顯示，V-nitrogenase的活化部位是一個metal sulfide cluster，由釩和鐵鍵結在多肽鍊而組成，然而，氮氣如何鍵結與催化的機制到目前仍然還不清楚。
我們合成一系列的釩的化合物想去探索與研究V-nitrogenase的反應機制，特別的，我們著重在獲得一些釩化合物在多硫的配位環境下與固氮作用的受質(N2)，中間產物(N2H2、N2H4)及產物(NH3)鍵結的情形。因此利用PS3系列的配位基，我們得到了V(III)和N2H4鍵結的化合物﹝V(PS3”)( N2H4)3﹞，除此之外，我們也得到了一系列V(III)的七配位和五配位的化合物，﹝V(PS3’)( Im)3﹞、﹝V(PS3)(1-Me- Im)3﹞、﹝V(PS3’)(1-Me- Im)3﹞、﹝V(PS3’)(Py)﹞、﹝V(PS3)(1-Me-Im)﹞和﹝V(PS3’)(1-Me-Im)﹞，這類化合物提供了我們對V(III)配位化學一些新的認識。

Nitrogenases catalyze the reduction of N2 into NH3 at ambient temperature and pressure with the concomitant reduction of 2H+ to H2. According to the spectroscopic studies, it has been know that the active site of V-nitrogenase is a metal sulfide cluster that consists of iron and vanadium ligated to the polypeptide. However, the mechanism for dinitrogen binding and activation in active site is still obscure.
We are thus exploring a range of synthetic vanadium complexes that provide insights into the mechanism for V-nitrogenase. In particular, we are aiming on obtaining dinitrogen adduct of vanadium complexes with S-rich ligation environment relevant to the enzyme. With tris(thiolate) phosphine ligand and its derivatives as title ligand, we have obtained a novel V(III)-N2H4 complex, [V(PS3”)( N2H4)3].In addition, we have also isolated and characterized several seven- and five-coordinate V(III) complexes, [V(PS3’)( Im)3]、[V(PS3)(1-Me- Im)3]、[V(PS3’)(1-Me- Im)3]、[V(PS3’)(Py)]、[V(PS3)(1-Me-Im)] and [V(PS3’)(1-Me-Im)]. The coordination chemistry of these complexes has provided great insights for the role of vanadium in V-nitrogenase.

中文摘要.......................................................I
Abstract......................................................II
圖目錄........................................................VI
表目錄.........................................................X
附圖目錄.....................................................XII
縮寫(Abbreviations).........................................XIII
第一章  前言...................................................1
1-1 簡介.......................................................1
1-2 固氮酵素的介紹.............................................3
1-3 V-nitrogenase活化中心的探討................................7
1-4 研究動機與目標.............................................9
1-5 研究方法..................................................14
第二章  三價釩化合物的合成與探討..............................17
2-1 實驗結果..................................................17
2-1.1﹝V(PS3”)( N2H4)3﹞(1)的探討............................17
2-1.2﹝V(PS3’)(Im)3﹞(2)的探討...............................24
2-1.3 ﹝V(PS3)( 1-Me-Im)3﹞(3)的探討..........................28
2-1.4 ﹝V(PS3’)( 1-Me-Im)3﹞(4)的探討........................31
2-1.5 ﹝V(PS3’)(Py)﹞(5)的探討...............................32
2-1.6 ﹝V(PS3)(1-Me-Im)﹞(6)的探討............................37
2-1.7﹝V(PS3’)(1-Me-Im)﹞(7)的探討...........................41
2-2 討論......................................................44
2-2.1 X-ray繞射結構的探討.....................................44
2-2.2 SQUID數據的探討.........................................48
2-2.3 1H NMR光譜的探討........................................50
2-2.4UV-Vis光譜的探討.........................................52
2-3 結論......................................................54
2-4 一般實驗條件..............................................57
2-4.1溶劑的準備...............................................57
2-4.2配位基與三價釩起始物的合成...............................58
2-4.3所使用的儀器與樣品準備方法...............................58
IR吸收光譜....................................................58
X-ray繞射結構.................................................58
SQUID.........................................................59
1H NMR光譜....................................................60
UV-Vis光譜....................................................60
2-5實驗部分...................................................61
2-5.1﹝V(PS3”)( N2H4)3﹞(1)的合成............................61
2-5.2﹝V(PS3’)( Im)3﹞(2)的合成..............................61
2-5.3﹝V(PS3)( 1-Me-Im)3﹞(3)的合成...........................62
2-5.4﹝V(PS3’)( 1-Me-im)3﹞(4)的合成.........................63
2-5.5﹝V(PS3’)(Py)﹞(5)合成..................................63
2-5.6﹝V(PS3)(1-Me-Im)﹞(6)合成...............................64
2-5.7﹝V(PS3’)(1-Me-Im)﹞(7)合成.............................64
附註一：配位基的合成..........................................71
PS3H3(tris(2-thiophenyl)phosphoine)的合成.....................71
PS3’H3 (tris(5-methyl-2-thiophenyl)phosphoine)的合成.........72
PS3”H3 (tris(3-trimethylsilyl-2-thiophenyl)phosphoine)
的合成........................................................74
附註二：三價釩金屬起始物的合成................................76
  參考文獻....................................................78
                                    

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