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研究生：	吳忻璇 Wu, Hsin-Hsuan
論文名稱：	含多硫配位基之釩化合物的合成與鑑定及砷硫化合物與硒之反應探討 Syntheses and Characterization of Vanadium Complexes with Thiolate Ligands and Chemistry of Arsenic Thiolate Complexes Reacting with Selenium
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：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	185
中文關鍵詞：	釩硫化合物、砷硫化合物
外文關鍵詞：	vanadium-thiolate complexes, arsenic-thiolate complexes
相關次數：	點閱：134 下載：0
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在本篇論文中，主要著重在於探討釩硫化合物的釩化學和砷硫化合物與硒化物的相關化學反應。在釩化學的研究中，因釩金屬會抑制蛋白質酪氨酸磷酸脂酵素 (PTP) 的活性，其可能原因是釩金屬與 PTP 的半胱胺酸 (Cysteine) 作用，而產生抑制的效果，因此我們對釩硫之間的作用頗感興趣。而在砷硫化合物的研究中，我們主要動機是為了瞭解砷化物對人體的毒性。
在研究中，我們以RSiS3 [Tris(2-thiophenyl)silane] 為主要配位基，來探討釩金屬在多硫配位環境下的相關釩化學反應。我們獲得了二個雙核含氧釩四價的化合物，分別為 [VIV2O2(PhSiS2”O)2][PPh4]2 (1) 和 [VIV2O2(PhSiS2”O)2][Bu4N]2 (2) ，其結構中 {VO(μ2-OR)2VO}2+ 的二個 V=O 鍵的相對位置不相同，化合物 (1) 屬於syn-orthogonal 的組態，而化合物 (2) 屬於anti-orthogonal 的組態。此外，我也獲得釩三價化合物 [VIII2(μ-NNH)(N2H2)2(PhSiS2”O)2][PPh4]2Br (3)、[VIII2{[HNC(Me)]2C(CN)}2 (MeSiS2O2)][PPh4]2 (4) 和[VIII2{[HNC(Me)]2C(CN)}2(PhSiS2”O2)][PPh4]2 (5)。化合物 (3) 包含二種二氮烯鍵結於釩金屬上，分別為作為架橋基和末端取代基。化合物 (4) 和 (5) 結構中含有三個乙腈分子所組成的配位基。
在探討砷化物的研究中，我們著重在於研究生物系統中砷硫化合
物與硒化物之間的作用性，其有助於了解攝取適量的硒可有效地降低砷對於人體的傷害。因此為了瞭解砷硫化合物與硒之間的反應性以及鍵結方式，我們選用砷硫化合物 (AsS3, AsS3’) 與硒化合物反應，並藉由氫核和硒核的核磁共振光譜 (1H-NMR 和77Se-NMR) 和X光原子吸收光譜 (XAS) 來分析反應後的產物。

At this work, two themes were focused: the chemistry of vanadium-thiolate complexes and the chemistry of arsenic-thiolate complexes reacting with selenium species. The former was inspired by the protein-tyrosine phosphatese (PTP) which is inhibited by vanadate through the interaction with the Cys residue in the enzyme. The latter was motivated by understanding the toxicity of arsenic.
In our continuing efforts to study vanadium sulfur chemistry, Tris(2-thiophenyl)silane, [RSiS3], was utilized to react with vanadium ion at this particular project. Two dinuclear oxovanadium(IV) thiolate complexes, [VIV2O2(PhSiS2”O)2][PPh4]2 (1) and [VIV2O2(PhSiS2”O)2][Bu4N]2 (2), were isolated and characterized. Complexes 1 and 2 both contain the {VO(μ2-OR)2VO}2+ core unit. The arrangement of two V=O bonds are different for these two complexes, syn-orthogonal for 1 and anti-orthogonal for 2. In addition, three dinuclear vanadium(III) thiolate complex, [VIII2(μ-NNH)(N2H2)2(PhSiS2”O)2][PPh4]2Br (3), [VIII2{[HNC(Me)]2 C(CN)}2(MeSiS2O2)][PPh4]2 (4), and [VIII2{[HNC(Me)]2C(CN)}2 (PhSiS2”O2)][PPh4]2 (5) were also isolated. Complex (3) contains a bridged and terminal diazene ligands and complexes (4)-(5) have moiety obtained from the activation of CH3CN.
In the second part of this research, we focus on the synergy of arsenic-thiolate complexes and selenium in biosystem. Appropriate selenium intake could decrease the arsenic toxicity to human body efficiently. To understand the reactivity and bonding between arsenic-thiolate complexes and selenium, tris(thiolato)arsenic complexes (AsS3, AsS3’) were explored to react with Selenium species. The reaction mixtures were analyzed with the techniques of 1H-NMR, 77Se-NMR and X-ray absorption spectroscopy (XAS).

摘要 ....................................................................................................................... I
Abstract ................................................................................................................. II
誌謝....................................................................................................................... III
目錄....................................................................................................................... IV
表目錄................................................................................................................ VIII
圖目錄............................................................................................................. X
附圖目錄...................................................................................................... XV
附表目錄..................................................................................................... XVI
符號縮寫.................................................................................................. XVIII
Part I  含多硫配位基之釩化合物的合成與鑑定 ........................... 1
第一章  前言  .............................................................................................. 2
1-1  簡介 .................................................................................................. 2
1-2  固氮酵素的介紹 .............................................................................. 3
1-3  釩化合物與蛋白質酪氨酸磷酸酯酵素 (Protein-tyrosine 
        phosphatase, PTP) 的作用 ............................................................ 4
1-4  釩鹵素過氧化酵素 (Vanadium Haloperoxidase) ............................ 6
1-5  研究動機與相關文獻的探討 .......................................................... 8
第二章  實驗結果與討論 .......................................................................... 13
2-1  釩金屬化合物 ............................................................................... 13
2-1.1 化合物 [VIV2O2(PhSiS2”O)2][PPh4]2 (1) 和[VIV2O2(PhSiS2”O)2][Bu4N]2 (2) .................................................. 13
2-1.2 化合物 [VIII2(μ-NNH)(N2H2)2(PhSiS2”O)2][PPh4]2Br (3) .......... 34
2-1.3 化合物 [VIII2{[HNC(Me)]2C(CN)}2(MeSiS2O2)][PPh4]2 (4) 和[VIII2{[HNC(Me)]2C(CN)}2(PhSiS2”O2)][PPh4]2 (5) ................... 41
2-2  新一代配位基的發展 ................................................................... 54
2-2.1 化合物[P(SNHR)3] ...................................................................... 54
2-2.2 化合物[P(SNH2)3]‧DMF............................................................. 60
第三章 結論.................................................................................................. 63
第四章 實驗部分.......................................................................................... 66
4-1  實驗條件.......................................................................................... 66
4-2  金屬化合物的合成 ........................................................................ 66
4-2.1 化合物 [VIV2O2(PhSiS2”O)2][PPh4]2  (1) .................................. 66
4-2.2 化合物 [VIV2O2(PhSiS2”O)2][Bu4N]2  (2) ................................. 67
4-2.3 化合物 [VIII2(μ-NNH)(N2H2)2(PhSiS2”O)2][PPh4]2Br (3) ...........67
4-2.4 化合物 [VIII2{[HNC(Me)]2C(CN)}2(MeSiS2O2)][PPh4]2 (4)........68
4-2.5化合物 [VIII2{[HNC(Me)]2C(CN)}2(PhSiS2”O2)][PPh4]2 (5)........69
4-3  配位基的合成步驟 ........................................................................ 70
4-3.1  RSiS3 配位基的合成步驟 ...................................................... 70
       (a) Tris(2-thiophenyl)methylsilane ([MeSiS3]H3)的合成 ............... 70
       (b) Tris(2-thiophenyl)phenylsilane ([PhSiS3]H3)的合成.................. 72
       (c) Tris(5-methyl-2-thiophenyl)phenylsilane ([PhSiS3’]H3)的
          合成 .......................................................................................... 74
       (d) Tris(3-trimethylsilyl-2-thiophenyl)phenylsilane ([PhSiS3”]H3)   
          的合成........................................................................................ 76
4-3.2  新一代配位基的合成步驟....................................................... 80
       (a) Tris(2-thiophenyl)phosphine ([PS3]H3)的合成......................... 80
       (b) Tris(S-(N-tert-butylacetamido)-2-thiophenyl)phosphine 
          [P(SNHR)3] 的合成.................................................................... 82
       (c) Tris(S-acetamido-2-thiophenyl)phosphine 
          [P(SNH2)3]的合成 ..................................................................... 85
4-4  釩金屬起始物的合成步驟 ............................................................ 87
     4-4.1 三價釩金屬化合物的合成步驟 .............................................. 87
     4-4.2 五價釩金屬化合物的合成步驟 .............................................. 87
4-5  所使用的儀器及樣品準備的方法 ................................................ 88
4-6  溶劑的準備...................................................................................... 91
Part II  砷硫化合物與硒之反應探討 ............................................... 92
第一章  前言  ............................................................................................ 93
1-1  簡介 ................................................................................................ 93
1-2  砷與硒相互作用的文獻探討.......................................................... 95
1-3  研究動機 ........................................................................................ 98
第二章  實驗結果...................................................................................... 100
2-1  砷化合物 (AsS3, AsS3’) 的製備與鑑定.................................... 100
2-1.1砷化合物 Tris(thiophenyl)arsenite (AsS3) ............................... 100
2-1.2砷化合物 Tris(thiophenyl)arsenite (AsS3’).............................. 105
2-2  砷化合物 (AsS3) 與硒元素 (Selenium) 反應的製備與鑑定.. 106
2-2.1砷化合物 Tris(thiophenyl)arsenite (AsS3) 與硒元素 (Selenium) 加熱迴流一天 (乙醚作為溶劑) .............................................. 106
2-2.2　砷化合物 Tris(thiophenyl)arsenite (AsS3) 與硒元素 (Selenium) 加熱迴流一天 (四氫呋喃作為溶劑) .................. 107
2-3 砷化合物 (AsS3) 與硒酸 (Selenic acid) 反應的製備與鑑定.... 108
2-3.1砷化合物 Tris(thiophenyl)arsenite (AsS3) 與硒酸 (H2SeO4) 加熱迴流一天............................................................................... 108
2-3.2砷化合物 Tris(thiophenyl)arsenite (AsS3) 與硒酸 (H2SeO4) 加熱迴流二天............................................................................... 112
2-4 砷化合物 (AsS3’) 與硒酸 (Selenic acid) 反應的製備與鑑定... 116
2-4.1砷化合物Tris(4-methylthiophenyl)arsenite (AsS3’) 與硒酸 (H2SeO4) 加熱迴流一天.......................................................... 116
2-4.2砷化合物Tris(4-methylthiophenyl)arsenite (AsS3’) 與硒酸 (H2SeO4) 加熱迴流二天.......................................................... 117
2-4.3砷化合物Tris(4-methylthiophenyl)arsenite (AsS3’) 與硒酸 (H2SeO4) 加熱迴流三天.......................................................... 119
第三章  結論 ............................................................................................ 123
第四章  實驗部分...................................................................................... 125
4-1  實驗條件 ...................................................................................... 125
4-2  砷化合物 (AsS3, AsS3’) 的合成步驟........................................ 125
4-2.1砷化合物Tris(thiophenyl)arsenite (AsS3) 的合成步驟........... 125
4-2.2砷化合物Tris(4-methylthiophenyl)arsenite (AsS3’)的合成步驟................................................................................................ 125
4-3  砷化合物AsS3 與硒元素 (Selenium) 反應的合成步驟........... 126
4-3.1  化合物 AsS3 與硒元素加熱迴流一天 (乙醚作為溶劑) 的合成步驟...................................................................................... 126
4-3.2  化合物 AsS3 與硒元素加熱迴流一天 (四氫呋喃作為溶劑) 的合成步驟 ............................................................................ 126
4-4  砷化合物AsS3 與硒酸 (H2SeO4) 反應的合成步驟................. 127
4-4.1  化合物 AsS3 與硒酸加熱迴流一天的合成步驟 ............... 127
4-4.2  化合物 AsS3 與硒酸加熱迴流二天的合成步驟 ............... 127
4-5  砷化合物AsS3’ 與硒酸 (H2SeO4) 反應的合成步驟................ 128
4-5.1  化合物 AsS3’ 與硒酸加熱迴流一天的合成步驟 ............. 128
4-5.2  化合物 AsS3’ 與硒酸加熱迴流二天的合成步驟 ............. 128
4-5.3  化合物 AsS3’ 與硒酸加熱迴流三天的合成步驟 ............. 129
4-6  所使用的儀器及樣品準備的方法 .............................................. 130
4-7  溶劑的準備.................................................................................... 131
參考文獻...................................................................................................... 132
                                    

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