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| 研究生： |
楊立柏 Li-Bo Yang |
|---|---|
| 論文名稱： |
雙核鐵亞硝基化合物之合成與反應性：腈水解酶及雙亞硝基鐵化合物之模型研究 Synthesis and Reactivity of Dinuclear Iron Nitrosyl Complexes : Model Study of Nitrile Hydratase and DNICs |
| 指導教授： |
廖文峯
Wen-Feng Liaw |
| 口試委員: | |
| 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： | 2006 |
| 畢業學年度： | 94 |
| 語文別： | 中文 |
| 論文頁數： | 71 |
| 中文關鍵詞： | 腈水解酶 、雙亞硝基鐵化合物 、雙核鐵亞硝基化合物 、一氧化氮 |
| 外文關鍵詞： | Nitrile Hydratase, DNICs, Dinuclear Iron Nitrosyl Complexes, nitric oxide |
| 相關次數： | 點閱：2 下載：0 |
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中文摘要
以Fe(CO)2(NO)2為起始物，加入8,8′-diquinolyl disulfide在THF溶劑下反應可得到一個雙三角錐結構、單亞硝基含鐵的化合物[Fe(qt)2(NO)] (1)。化合物1的νNO = 1681 cm-1 (KBr)，Fe-N(NO)鍵長1.685 Å，N-O鍵長1.18 Å，Fe-N-O角度為157.8度。從NMR (paramagnetic shift)、EPR (S = 1/2)、SQUID (□eff = 1.63 □B)等光譜及實驗反應性得知，化合物1為順磁性分子且鐵和一氧化氮的電子組態依照Feltham-Enemark notation，可視為{FeII(NO•)}7。
化合物1在THF溶劑下和[NO][BF4]反應可得到一個EPR silent的雙核鐵亞硝基化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)。化合物2由雙三角錐的[(NO)Fe(1)N2S2]和四面體的[S2Fe(2)(NO)2]架構而成，Fe(1)-Fe(2)鍵長2.661 Å，平均Fe-N(NO)鍵長1.660 Å，平均N-O鍵長1.155 Å。
同樣以Fe(CO)2(NO)2為起始物，加入(PyPepS)2，[(PyPepS)2 = N-2-mercapto- phenyl-2′-pyridinecarboxamide disulfide]在THF溶劑反應，則得到一個典型的Roussin′s Red Ester化合物：(NO)4Fe2(□-SPyPep)2 (7)。化合物7加入氧氣之後，反應生成另一個EPR silent的雙核鐵亞硝基化合物(NO)2Fe2(PyPepS)2 (3)。化合物3由二個扭曲的四面型角錐架構而成，Fe-Fe鍵長2.625 Å，平均Fe-Ncarboxamide鍵長1.949 Å，平均Fe-S鍵長2.243 Å，每個鐵上鍵結了一個NO分子，且有一個carboxamido的氮、一個pyridine的氮和二個thiolato的硫作為配位。我們希望藉由合成此類腈水解酶的模型化合物，來更了解此酵素，不僅是在結構、配位環境、光譜甚至是反應性上的資訊。
Abstract
Reaction of Fe(CO)2(NO)2 and 8,8′-diquinolyl disulfide in THF afforded the trigonal bipyramidal, mononitrosyl iron complex [Fe(qt)2(NO)] (1) with NO occupying the equatorial position. For 1, a νNO stretching frequency of 1681 cm-1 (KBr) is observed. X-ray data reveals that Fe-N(NO) and N-O bond distances are 1.685 Å and 1.18 Å, respectively. Also, complex 1 contains a notably bent Fe-N-O bond, 157.8°.□□1H NMR (paramagnetic shift), EPR (S = 1/2), magnetic moment data (□eff = 1.63 □B) and the chemical reactivity of complex 1 agree with a electronic configuration of {FeII(NO•)}7 according to the Feltham-Enemark notation.
Reaction of [Fe(qt)2(NO)] (1) and [NO][BF4] in THF afforded a EPR-silent, homodinuclear iron thiolate nitrosyl complex [(ON)Fe(1)(qt)2Fe(2)(NO)2][BF4] (2). The geometry of Fe(1) of complex 2 is trigonal bipyramidal [(ON)FeN2S2] core with a NO ligand occupying the equatorial position and the Fe(2) center has a regular tetra- hedral [S2Fe(NO)2] coordination environment. The Fe(1)-Fe(2) distance of 2.661 Å implicate the existence of Fe-Fe interaction. The average Fe-N(NO) and N-O bond distances of complex 2 are 1.660 Å and 1.155 Å , respectively.
Complex (NO)4Fe2(□-SPyPep)2 (7) was afforded by reaction of Fe(CO)2(NO)2 and (PyPepS)2 [(PyPepS)2 = N-2-mercapto-phenyl-2′-pyridinecarboxamide disulfide] in THF. Complex 7 was oxidized by O2 to yield the EPR-silent, homodinuclear iron thiolate nitrosyl complex (NO)2Fe2(PyPepS)2 (3). Complex 3 consists of two distorted square pyramidal structure with a Fe(1)-Fe(2) bond distance of 2.625 Å. The average Fe-Ncarboxamide and Fe-S bond distances of complex 3 are 1.949 Å and 2.243 Å, respectively. Each iron center of complex 3 is ligated by one carboxamido N, one pyridinyl N, two bridged thiolato S and a NO molecule. This unique coordination environment of 3 may provide important clues (structure, spectroscopy, reactivity, etc.) relating to the nitrile hydratase.
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