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研究生：	彭婉瑜 Peng, Wan-Yu
論文名稱：	以tristhiolatophosphine 為配位基的鉬金屬化合物之合成與鑑定 Synthesis and characterization of molybdenum complexes containing tristhiolatophosphine ligands
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：	2004
畢業學年度：	92
語文別：	中文
論文頁數：	82
中文關鍵詞：	鉬金屬化合物
外文關鍵詞：	tristhiolatophosphine
相關次數：	點閱：82 下載：1
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金屬鉬在生物系統上扮演著極重要的角色，最主要是在兩種催化酵素上被
發現，一種為固氮酵素，其作用是在催化氮氣還原成氨；另一種為氧轉移酶，
主要作用是在轉移氧原子，從一個受質到另一個受質。而這兩種酵素的配位環
境都是多硫的，因此我希望可以利用多硫的配位基去模擬它們的配位環境。在
這裡，我使用了兩種多硫的四螯合配位基，PS3H3 及PS3”H3 *，與三價金屬鉬反
應之後，因為受到了空氣氧化的影響，得到了兩種截然不同的高價鉬化合物。
[Mo2(PS3)2(PS3H)] (1)為鉬四價雙核化合物，是由兩個金屬及三個PS3 配位
基所組成，包含了一個未配位的SH，其幾何結構為七配位的雙五角雙錐，共用
了一個三角平面。而兩個鉬金屬之間也有鍵結存在。[Mo(PS3”)2] (2)為鉬六價化
合物，由一個金屬及兩個PS3”配位基所組成，形成八配位、正十二面體的結構。

The chemistry of molybdenum-sulfur complexes has been drawn much attention
due to its significance in biological and catalytic aspects. Molybdenum has been
found in two classes of enzymes, nitrogenase and oxotransferases. The former
catalyzes the reduction of dinitrogen and the latter plays an important role for
oxygen-atom transfer reaction to or from a substrate. The molybdenum sites in both
enzymes have S-rich ligation environment. To understand the roles of molybdenum
sites in these enzymes prompts my laboratory to explore the basic coordination
chemistry of molybdenum, particularly, binding with S donor atoms. In this
research, I utilize trisbenzenethilatophosphines, PS3 and PS3” as title ligands (PS3 =
[P(C6H4-2-S)3]3- and PS3” = [P(C6H3-3-Me3Si-2-S)3]3-). With these tetradentate
ligands, I have obtained two unique high valent molybdenum complexes,
[Mo2(PS3)2(PS3H)] (1) and [Mo(PS3”)2] (2). Compound 1 is a dimeric Mo(IV)
compound ligated by three PS3 ligands with an uncoordinated thiol group and
compound 2 is an eight-coordinate Mo(VI) complex binding with two PS3” ligands.
I detail my results in this thesis.

目錄
摘要………………………………………………………………………..…….I
Abstract………………………………………………………………………....II
目錄………………………………………………………………………..…..IV
圖目錄…………………………………………………………………..……..VI
表目錄………………………………………………………………….……..VII
附圖目錄………………………………………………………………………X
第一章 前言..............................................................................................1
1-1 鉬在生物系統的角色..............................................................................1
1-1.1 氧移轉酶的介紹...................................................................................2
1-1.2 固氮酵素的介紹...................................................................................6
1-2 金屬鉬的配位化學................................................................................10
1-2.1 PS3 系列配位基和金屬的配位探討.................................................10
1-2.2 鉬雙核化合物的介紹.........................................................................12
1-3 研究動機與目標....................................................................................15
第二章 結果與討論.............................................................................. 18
2-1 合成探討................................................................................................18
2-1.1 [Mo(IV)2(PS3)2(PS3H)](1)的合成探討.............................................18
2-1.2 [Mo(PS3”)2](2)的合成探討...............................................................19
IV
2-2 X-ray 繞射與幾何結構的探討.............................................................21
2-2.1 [Mo2(PS3)2(PS3H)] X-ray 繞射與幾何結構的探討.........................21
化合物1 的幾何結構的探討.........................................................................26
2-2.2 [Mo(PS3”)2] X-ray 繞射與幾何結構的探討.....................................28
化合物2 的幾何結構探討.............................................................................32
元素分析及光譜的探討.................................................................................37
[Mo2(PS3)2(PS3H)] 1H NMR 光譜的探討.....................................................39
[Mo2(PS3)2(PS3H)] 31P NMR 光譜的探討....................................................42
[Mo(PS3”)2]1H NMR 光譜的探討.................................................................44
[Mo(PS3”)2] 31P NMR 光譜的探討................................................................45
[Mo2(PS3)2(PS3H)] UV-Vis 吸收光譜的探討...............................................46
[Mo(PS3”)2] UV-Vis 吸收光譜的探討..........................................................47
[Mo2(PS3)2(PS3H)] IR 光譜的探討...............................................................48
第三章 實驗部分............................................................................…..51
3-1 一般實驗條件........................................................................................51
3-2 溶劑的準備............................................................................................51
3-3 配位基的合成........................................................................................52
PS3H3 (tris(2-thiophenyl)phosphoine)的合成................................................52
PS3’H3 (tris(5-methyl-2-thiophenyl)phosphoine)的合成...............................53
V
PS3”H3 (tris(3-trimethylsilyl-2-thiophenyl)phosphoine)的合成....................55
3-4 三價鉬金屬起始物的合成....................................................................57
[Mo2(PS3)2(PS3H)]及[Mo(PS3”)2]的合成.....................................................58
[Mo2(PS3)2(PS3H)]的合成方法.....................................................................58
[Mo(PS3”)2]的合成方法.................................................................................59
3-5 所使用儀器與樣品的準備方法............................................................60
元素分析數據.................................................................................................60
IR 吸收光譜....................................................................................................60
X-ray 繞射結構...............................................................................................61
1H NMR、31P NMR 光譜...............................................................................61
UV-Vis 光譜....................................................................................................62
參考文獻………………………………………...…………………………..63
VI
表目錄
表1-1 Mo hydroxylase 及DMSO reductase family 的催化反應式…..5
表2-1 化合物1 的X-ray 繞射結構的參數........................................ 23
表2-2 [Mo2(PS3)2(PS3H)]的鍵長(Å) .................................................. 25
表2-3 [Mo2(PS3)2(PS3H)]的鍵角 (°)………………………………..25
表2-4 化合物2 的X-ray 繞射結構的參數........................................ 29
表2-5 [Mo(PS3”)2] 的鍵長(Å)............................................................ 31
表2-6 [Mo(PS3”)2] 的鍵角(°)……………………………………….31
表2-7 [Mo2(PS3)2(PS3H)]元素分析數據............................................ 37
表2-8 [Mo2(PS3)2(PS3H)]•H2O 元素分析數據............................... 38
表2-9 [Mo(PS3”)2]元素分析數據……………………………………38
VII
圖目錄
圖1-1 Molybdenum hydroxylase 活化中心.......................................... 3
圖1-2 DMSO reductase family 活化中心............................................. 3
圖1-3 pterin-dithiolene cofactor............................................................. 3
圖1-4 推測 sulfite oxidase 的催化機制.............................................. 5
圖1-5 FeMo-cofactor 的結構................................................................. 7
圖1-6 推測Mo-nitrogenase 切斷氮-氮三鍵......................................... 9
圖1-7 將N≡N 三鍵打斷的例子.......................................................... 9
圖1-8 PS3 系列配位基的金屬化合物結構………………………….11
圖1-9 GMo2(CO)6 的結構.................................................................... 13
圖1-10 Mo-Mo 四鍵的例子................................................................ 13
圖1-11 Mo-Mo 三鍵的例子................................................................ 14
圖1-12 四價鉬雙核以thiolate 當橋的例子……………………….…14
圖1-13 氮氣鍵結在Mo 模型化合物.................................................. 16
圖1-14 催化N2H4 還原成氨的模型化合物....................................... 17
圖1-15 所使用的PS3H3 系列的配位基……………………………..17
圖2-1 [Mo2(PS3)2(PS3H)]的合成........................................................ 20
圖2-2 [Mo(PS3”)2]的合成……………………………………………20
圖2-3 [Mo2(PS3)2(PS3H)]的ORTEP 結構…………………………..24
VIII
圖2-4 [Mo2(PS3)2(PS3H)] 中心金屬的配位環境.............................. 27
圖2-5 七配位雙五角雙錐幾何結構.................................................... 27
圖2-6 [Mo2(PS3)2(PS3H)] 中心配位polyhedron 結構……………..28
圖2-7 [Mo(PS3”)2] 的ORTEP 結構………………………………….30
圖2-8 [Mo(PS3”)2]中心金屬的配位環境........................................... 33
圖2-9 常見的八面體結構.................................................................... 34
圖2-10 化合物2 所對應的十二面體圖.............................................. 34
圖2-11 兩個tetrahedron〈Td〉結構.................................................. 35
圖2-12 文獻中鉬八配位的例子.......................................................... 36
圖2-13 文獻中鉬八配位的例子，以η2-CS3 作為配位基…………..36
圖2-14 [Mo2(PS3)2(PS3H)] 1H NMR 光譜......................................... 40
圖2-15 [Mo2(PS3)2(PS3H)] 1H NMR 光譜(和31P 去偶合)................ 40
圖2-16 [Mo2(PS3)2(PS3H)] 1H NMR 二維光譜……………………..41
圖2-17 [Mo2(PS3)2(PS3H)]的31P NMR 光譜..................................... 43
圖2-18 [Mo2(PS3)2(PS3H)]的31P NMR 放大圖光譜 ……………….43
圖2-19 [Mo(PS3”)2] 1H NMR 光譜 …………………………………44
圖2-20 [Mo(PS3”)2] 31P NMR 光譜 …………………………………45
圖2-21 [Mo2(PS3)2(PS3H)] UV-Vis 吸收光譜……………………...46
圖2-22 [Mo(PS3”)2] UV-Vis 吸收光譜…………………………..…47
IX
圖2-23 PS3H3 配位基的IR 圖………………………………………49
圖2-24 [Mo2(PS3)2(PS3H)]的IR 圖………...……………………....49
圖2-25 [Os(PS3H)2]化合物結構…………………………………….50
圖2-26 [Ni(PS3H)(Seph)]化合物結構………………………………50
X
附圖目錄
附圖一 PS3H3 的1H NMR(CDCl3)光譜圖………………………….66
附圖二 PS3’H3 的1H NMR(CDCl3)光譜圖…………………………67
附圖三 PS3”H3 的1H NMR(CDCl3)光譜圖…………………………68
                                    

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