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.

目錄
中文摘要………………………………………………………………………………i
Abstract………………………………………………………………………………ii
目錄…………………………………………………………………………………iii
Figure………………………………………………………………………………vi
Table………………………………………………………………………………ix
Scheme………………………………………………………………………………x
第一章：緒論…………………………………………………………………………1
1-1：前言…………………………………………………………………………1
1-2：一氧化氮……………………………………………………………………1
1-3：金屬亞硝基化合物之特性及電子結構……………………………………2
1-4：一氧化氮在生物體內的儲存及傳遞………………………………………4
1-5：腈水解酶的結構、性質與催化機制………………………………………5
1-5-1：腈水解酶的結構……………………………………………………6
1-5-2：腈水解酶的性質……………………………………………………7
1-5-3：腈水解酶的催化機制………………………………………………9
1-6：腈水解酶相關模型化合物之研究………………………………………11
1-6-1：Fe(III)中心配位飽和且含amine/imine N和thiolato S之模型化合物…………………………………………………………………12
1-6-2：Fe(III)中心配位飽和且含carboxamido N和thiolato S之模型化合物…………………………………………………………………13
1-6-3：Fe(III)中心配位未飽和且含amine/imine N和thiolato S之模型化合物………………………………………………………………14
1-6-4：Fe(III)中心配位未飽和且含carboxamido N和thiolato S之模型化合物………………………………………………………………15
1-6-5：Fe和NO鍵結且thiolato S修飾成sulfinate (SO2－)之模型化合物…………………………………………………………………16
1-6-6：具有催化功能之模型化合物……………………………………16
1-7：實驗方向…………………………………………………………………17

第二章：實驗部分……………………………………………………………………18
2-1：一般實驗…………………………………………………………………18
2-2：儀器………………………………………………………………………18
2-3：藥品………………………………………………………………………19
2-4：化合物的合成及鑑定……………………………………………………20
2-4-1：合成化合物[Fe(qt)2NO] (1)………………………………………20
2-4-2：合成化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)………………………20
2-4-3：合成化合物(NO)2Fe2(PyPepS)2 (3)………………………………21
2-5：化合物的反應性…………………………………………………………23
2-5-1：化合物1與O2(g)反應………………………………………………23
2-5-2：化合物1與trimethylamine N-oxide反應…………………………23
2-5-3：化合物1與pyridine N-oxide反應…………………………………23
2-5-4：化合物1與CO(g)反應……………………………………………23
2-5-5：化合物1與[PPN]2[Fe2(S,S-C6H4)4]反應…………………………23
2-5-6：化合物1與[(NO)2Fe(sparteine)]反應……………………………24
2-5-7：化合物1與[(NO)2Fe(sparteine)][BF4]反應………………………24
2-5-8：化合物2與[PPN][SPh]反應………………………………………24
2-5-9：化合物2與[Et4N][BH4]反應………………………………………24
2-5-10：化合物3與[PPN][SEt]反應………………………………………25
2-5-11：化合物3與[PPN][SPh]反應……………………………………25
2-6：晶體結構解析(Crystallography)…………………………………………25
第三章：結果與討論…………………………………………………………………30
3-1：化合物[Fe(qt)2NO] (1)的合成、光譜、晶體結構及反應性的探討………30
3-1-1：化合物[Fe(qt)2NO] (1)的合成………………………………………30
3-1-2：化合物[Fe(qt)2NO] (1)的光譜………………………………………30
3-1-3：化合物[Fe(qt)2NO] (1)的晶體結構…………………………………31
3-1-4：化合物[Fe(qt)2NO] (1)的反應性……………………………………39
3-2：化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)的合成、光譜、晶體結構及反應性的探討……………………………………………………………………43
3-2-1：化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)的合成……………………43
3-2-2：化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)的光譜……………………43
3-2-3：化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)的晶體結構………………43
3-2-4：化合物[(ON)Fe(qt)2Fe(NO)2][BF4] (2)的反應性…………………51
3-3：化合物(NO)2Fe2(PyPepS)2 (3)的合成、光譜、晶體結構及反應性的探討
3-3-1：化合物(NO)2Fe2(PyPepS)2 (3)的合成………………………………53
3-3-2：化合物(NO)2Fe2(PyPepS)2 (3)的光譜………………………………54
3-3-3：化合物(NO)2Fe2(PyPepS)2 (3)的晶體結構…………………………54
3-3-4：化合物(NO)2Fe2(PyPepS)2 (3)的反應性……………………………60

第四章：結論…………………………………………………………………………66

參考文獻(References)………………………………………………………………67

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