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研究生：	郭晉廷 Kuo, Jing-Ting
論文名稱：	藉由硝酸鹽及亞硝酸鹽之還原反應合成含有一氧化氮配位基之鐵硫及釩硫錯合物 Syntheses of Iron and Vanadium Nitrosyl Thiolate Complexes via the Reduction of Nitrate/Nitrite
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：	2012
畢業學年度：	100
語文別：	英文
論文頁數：	84
中文關鍵詞：	一氧化氮、還原、鐵硫、釩硫、硝酸鹽、亞硝酸鹽
外文關鍵詞：	reduction, vanadium, iron, nitric oxide, Nitrate, Nitrite
相關次數：	點閱：144 下載：1
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一氧化氮在人體的生理以及病理上扮演著很重要的角色，並且在生物系統的脫氮作用中也是一個很重要的中間產物。為了在這方面了解更多重要的訊息，我們合成了兩種以一氧化氮為配位基的錯合物[V(PS3”)NO][PPh4] (1)以及[Fe(PS3”)NO][PPh4] (2)，他們分別為{V-NO}4以及{Fe-NO}7這兩種形式。錯合物1與2皆為五配位單金屬中心，其幾何結構為扭曲的雙三角錐。這兩個化合物皆是經由硝酸鹽以及亞硝酸鹽的還原反應而得到，並且經由核磁共振光譜、紫外光-可見光光譜、紅外光光譜、X-光單晶繞射儀以及電噴灑游離質譜來分析及鑑定。化合物1與2的電子結構經由X-光吸收光譜以及磁性數據的分析後，分別為V(III)-NO- 以及Fe(III)-NO- 的形式。另外一方面，化合物2也被發現可與氧氣進行反應，生成錯合物[Fe(PS3”)O2]-，其反應的過程使用核磁共振光譜、紫外光-可見光光譜以及電噴灑游離質譜來記錄。

Nitric oxide (NO) is not only an important small molecule in physiology and pathology but also an essential intermediate during the denitrifying process in bacteria. In order to understand fundamental information in these aspect, a novel vanadium nitrosyl complex, [V(PS3”)NO][PPh4] (1), and an iron nitrosyl complex, [Fe(PS3”)NO][PPh4] (2), have been obtained. The electronic structures are {V-NO}4 and {Fe-NO}7 species, respectively. These two complexes are both five-coordinated complexes with distorted trigonal bipyramidal geometry. They can be synthesized via the nitrate and nitrite reduction into nitric oxide. These complexes have been analyzed by X-ray crystallography, NMR, infrared spectrum, ultraviolet-visible spectrum and electrospray ionization (ESI) mass. The electronic structure identified by X-ray absorption spectroscopy and magnetic properties are V(III)-NO- and Fe(III)-NO- form, respectively. On the other hand, complex 2 can reacts with air/dioxygen and likelygenerated [Fe(PS3”)O2]- species. The reaction was observed by ESI-mass, NMR and UV-vis spectra.

Abstract................................................I
中文摘要...............................................II
誌謝..................................................III
Table of Content.......................................IV
List of Figures........................................VI
List of Tables.........................................IX
List of Schemes.........................................X
Chapter 1: Introduction.................................1
1-1 Biochemistry of Nitric Oxide........................2
1-2 Vanadium Nitrosyl Thiolate Complex..................6
1-3 Iron Nitrosyl Thiolate Complex.....................12
1-4 Iron-containing Oxygen Complexes...................20
Chapter 2: Experimental Section........................24
Chapter 3: Result & Discussions........................31
3-1 Synthesis and Characterization of [V(PS3”)NO][PPh4] (1)....................................................32
3-1.1 Synthesis of 1...................................32
3-1.2 Elemental Analysis of Complex 1..................33
3-1.3 X-ray Structural Determination of 1..............33
3-1.4 Uv-vis-NIR Spectroscopic characterization........38
3-1.5 Nuclear Magnetic Resonance Spectroscopic Characterization.......................................39
3-1.6 Infrared Spectra.................................41
3-1.7 Electrospray Ionization-Mass Spectrum............43
3-1.8 K-edge X-ray Absorption Spectrum.................46
3-1.9 Magnetic Properties..............................48
3-2 Synthesis and Characterization of [Fe(PS3”)NO][PPh4] (2)....................................................49
3-2.1 Synthesis of 2...................................49
3-2.2 Elemental Analysis of Complex 2..................50
3-2.3 X-ray Structural Determination of 2..............50
3-2.4 Uv-vis-NIR Spectroscopic Characterization........54
3-2.5 Nuclear Magnetic Resonsnce Spectroscopic Characterization.......................................55
3-2.6 Infrared Spectra.................................57
3-2.7 K-edge X-ray Absorption Spectrum.................58
3-2.8 Magnetic Properties..............................60
3-3 The Reactivity of [Fe(PS3”)NO][PPh4] (2)..........61
3-3.1 Electrospray Ionization-Mass Spectrum of Complex 2
.......................................................61
3-3.2 Uv-vis-NIR Spectrum of Complex 2 reacting with O2
.......................................................63
3-3.3 Nuclear Magnetic Resonance Spectroscopic Characterization.......................................65
Chapter 4: Conclusion..................................67
References.............................................71
Appendix...............................................75
                                    

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