本研究以1,3-bis(dimethylamino)propan-2-olate (Bdmap)為配位基合成出新系列之雙核結構雙亞硝基鐵錯合物(Dinuclear Dinitrosyl Iron Complexes, dDNICs)，並探討其反應性以及應用性。
　本文一開始利用配位基N,N,N’,N'-Tetramethyl-1,3-propanediamine(TMPDA)證明含氮類型的配位基無法以增長碳鏈的方式加強其立體結構上的穩定，形成穩定的單核四配位{Fe(NO)2}9 DNIC。之後改以異原子N-O-N三牙之配位基Bdmap成功合成出一系列新型態的dDNICs，並使用IR、UV、EPR、SQUID及X-ray等儀器鑑定結構。其中包含以烷氧基配位的{Fe(NO)2}9-{Fe(NO)2}9 (化合物2)、{Fe(NO)2}10-{Fe(NO)2}10 (化合物5) dDNIC、 {Fe(NO)2}9-{Fe(NO)2}9 Roussin's red ester (RRE) (化合物3)以及含有trans-[N2O2]2- (hyponitrito)的四核DNIC (化合物4)。
　　在過去發表的文獻中，含有Metal- Hyponitrite晶體結構的例子非常稀少，化合物4的發現表示雙亞硝基鐵錯合物可以作為生物模擬的模型，對探討自然界中一氧化氮還原酶(Nitric oxide reductase, NOR)的催化機制有很大的幫助。

In this work, 1,3-bis(dimethylamino)propan-2-olate (Bdmap) was used as ligand to synthesize a new series of alkoxide-bridged dinuclear Dinitrosyl Iron Complexes (dDNICs). Its reactivity and applicability were also investigated.
　　In the beginning, we used N,N,N’,N'-Tetramethyl -1,3-propanediamine(TMPDA) to prove that it’s also NOT stable for four-coordinated {Fe(NO)2}9 DNIC by enhancing the chelating effect. Then, 1,3-bis(dimethylamino)propan-2-olate (Bdmap) was employed as tridentate N-O-N ligand to synthesize a new type of dDNICs, including alkoxide-bridged {Fe(NO)2}9-{Fe(NO)2}9 and {Fe(NO)2}10-{Fe(NO)2}10 dDNICs, {Fe(NO)2}9-{Fe(NO)2}9 Roussin's red ester (RRE) and a novel μ-O,N-hyponitrite binding DNIC, complex 4.
　　In the previous study, there were only few crystal structures of metal-hyponitrite complexes. The discovery of complex 4 indicated that the DNICs could play a role in biomimetic modelling. It’s important to understand how Nitric Oxide Reductase work in nature. The study of reaction mechanism for complex 4 will be continued.

第一章 緒論 1
1-1. 一氧化氮 (Nitric oxide) 1
1-2. 一氧化氮(NO)與過渡金屬(M)鍵結之電子狀態 2
1-3. 雙亞硝基鐵錯合物 (Dinitrosyl Iron Complexes, DNICs) 4
1-4. 一氧化氮還原酶 (Nitric oxide reductase, NOR) 9
1-5. 連二次硝酸鹽與金屬之錯合物 (Hyponitrite complex) 12
1-6. 研究方向 17
第二章 實驗部分 19
2-1. 一般實驗 19
2-2. 儀器 19
2-2-1. 紅外線光譜儀 (Infrared spectrometer, IR) 19
2-2-2. 紫外光-可見光吸收光譜儀 (UV-Visible electronic absorption spectrometer) 19
2-2-3. 元素分析儀 (Elemental Analyzer, EA) 20
2-2-4. X-ray 單晶繞射解析 20
2-2-5. 循環伏安儀 (Cyclic Voltammetry, CV) 20
2-2-6. 電子順磁共振光譜儀 (Electron paramagnetic resonance, EPR) 20
2-2-7. 超導量子干涉儀 (Superconducting Quantum Interference Device Magenetometer, SQUID) 21
2-2-8. 氣相層析儀 (Gas Chromatography, GC) 21
2-3. 溶劑與藥品 21
2-3-1. 溶劑 21
2-3-2. 藥品 22
2-4. 化合物的合成與鑑定 23
2-4-1. 化合物 [K-18-crown-6-ether][Fe(CO)3(NO)] 的合成 23
2-4-2. 化合物 [(TMPDA)Fe(NO)2] (1) 的合成 (TMPDA : N,N,N',N'-tetramethyl-1,3-diaminopropane) 23
2-4-3. 化合物 [(μ-Bdmap)(μ-NO2)(Fe(NO)2)2] (2)的合成 (Bdmap : 1,3-bis(dimethylamino)propan-2-olate) 24
2-4-4. 化合物 [(TMEDA)Fe(NO)2] 的合成 (TMEDA : Tetramethylethylenediamine) 25
2-4-5. 化合物 [(μ-Bdmap)Fe(NO)2]2 (3)的合成 26
2-4-6. 化合物 [18-crown-6-ether-K][(Bdmap)(Fe(NO)2)2] (5)的合成 27
2-5. 化合物之反應性 29
2-5-1. 化合物 [(TMPDA)Fe(NO)2] (1)與Ferrocenium hexafluorophosphate (FcPF6)反應 29
2-5-2. 化合物 [18-crown-6-ether-K][(Bdmap)(Fe(NO)2)2] (5) 與Nitrosonium tetrafluoroborate (NOBF4)反應 29
2-5-3. 化合物 [18-crown-6-ether-K][(Bdmap)(Fe(NO)2)2] (5) 與Ferrocenium hexafluorophosphate (FcPF6)反應 30
2-5-4. 化合物[(μ-Bdmap)(μ-NO2)(Fe(NO)2)2] (2)與Potassium graphite (KC8)反應 30
2-6. 電化學方法 31
2-7. 晶體結構解析 32
第三章 結果與討論 38
3-1. [(TMPDA)Fe(NO)2] (1) 之合成與光譜分析 38
3-2. [(TMPDA)Fe(NO)2] (1) 與Ferrocenium hexafluorophosphate的反應 41
3-3. [(μ-Bdmap)(μ-NO2)(Fe(NO)2)2] (2) 之合成與光譜分析 42
3-4. [(μ-Bdmap)Fe(NO)2]2 (3) 之合成與光譜分析 50
3-5. [18-crown-6-ether-K][(Bdmap)(Fe(NO)2)2] (5) 之合成與光譜分析 57
3-6. [18-crown-6-ether-K][(Bdmap)(Fe(NO)2)2] (5) 之氧化反應 60
3-6-1. Complex 5 與Nitrosonium tetrafluoroborate (NOBF4)反應 60
3-6-2. Complex 5 與Ferrocenium hexafluorophosphate (FcPF6) 反應 61
第四章 結論 63
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