本研究合成出金屬錯合物[(TETA)(Fe(NO)2)2] (1)，並藉由紅外線光譜儀、循環伏安儀、氣相層析儀、核磁共振儀、粉末X-ray繞射儀、以及X-ray吸收光譜來了解雙亞硝基鐵錯合物的反應性。此錯合物可和鈉、鎂、鋅金屬在THF中或是水中反應，而生成碳酸金屬鹽以及一氧化碳。碳酸金屬鹽的鑑定由紅外線光譜儀、粉末X-ray繞射儀、以及X-ray單晶繞射來確認，而一氧化碳的生成由GC確認，且在此反應中，鈉、鎂、鋅金屬作為還原劑。並且也發現碳酸鋅加熱至350 0C時會得到氧化鋅。

In this study, Dinitrosyl Iron Complexes (DNIC) [(TETA)(Fe(NO)2)2] (1) was synthesized and characterized by IR, UV, CV, and EA. Its reactivity was investigated. Reaction of Complex 1 and Na/Mg/Zn in THF/aqueous solution results in the formation of metal carbonate identified by IR, pXRD and single-crystal X-ray diffraction, and carbon monoxide characterized by GC. In these reactions, Na/Mg/Zn act as reducing agents. Also, zinc carbonate heated to 350 0C yielded zinc oxide.

目錄
第一章 緒論 1
1-1. 一氧化氮 (Nitric oxide) 1
1-2. 一氧化氮 (Nitric oxide) 的生成 4
1-3. 一氧化氮在體內的運送與儲存 6
1-4. 雙亞硝基鐵錯合物 (DNIC) 8
1-5. 二氧化碳的還原 15
1-6. 研究方向 21
第二章 實驗部分 22
2-1. 一般實驗 22
2-2. 儀器 22
2-3. 溶劑與藥品 25
2-3-1. 溶劑 25
2-3-2. 藥品 25
2-4. 化合物的合成與鑑定 26
2-5. 化合物的反應 27
2-5-1. Complex 1對CO2(g) 之反應 27
2-5-2. Complex 1與CO2(g) 和Na(s)之反應 27
2-5-3. Complex 1和CO2(g) 與Mg(s) 的反應 28
2-5-4. Complex 1和CO2(g) 與Zn(s) 的反應 28
2-5-5. Complex 1和CO2(g) 與Li(s) 的反應 29
2-5-6. Complex 1和CO2(g) 與Fe(s) 的反應 29
2-5-7. Complex 1和CO2(g) 與Ca(s) 的反應 30
2-5-8. Complex 1與不斷供應的CO2(g) 及Zn(s)反應 30
2-5-9. Complex 1與供應量固定的CO2(g) 及Zn(s)反應 31
2-5-10. Complex 1與CO2(g) 和H2(g)之反應 31
2-6. 電化學方法 32
2-7. 晶體結構解析 32
第三章 結果與討論 35
3-1. [(TETA)(Fe(NO)2)2] (1) 之結構與性質 35
3-2. [(TETA)(Fe(NO)2)2] (1) 對CO2(g) 之反應 38
3-3. [(TETA)(Fe(NO)2)2] (1) 與CO2(g) 和Na(s)之反應 40
3-4. [(TETA)(Fe(NO)2)2] (1) 與CO2(g) 和各種不同還原劑之反應 42
3-4-1. Complex 1和CO2(g) 與Mg(s) 的反應 42
3-4-2. Complex 1和CO2(g) 與Zn(s) 的反應 43
3-4-3. Complex 1和CO2(g) 與Li(s) 的反應 46
3-4-4. Complex 1和CO2(g) 與Fe(s) 的反應 47
3-4-5. Complex 1和CO2(g) 與Ca(s) 的反應 48
3-5. [(TETA)(Fe(NO)2)2] (1) 的催化效果探討 49
3-5-1. CO2(g)不斷供應的開放系統 49
3-5-2. CO2(g)供應量固定的密閉系統 52
3-6. [(TETA)(Fe(NO)2)2] (1) 與CO2(g) 和H2(g)之反應 54
3-7. [(TETA)(Fe(NO)2)2] (1) 的催化反應機構討論 60
第四章 結論 62
References 63


 
圖表目錄

Figure 1-1. 一氧化氮分子軌域圖 2
Figure 1-2. Metal與NO間的鍵結關係 3
Figure 1-3. 藉由NOS催化 L-arginine 的反應 4
Figure 1-4. NO於生物體內的化學反應 7
Figure 1-5. Cys-NO 和 GS-NO 的結構 7
Figure 1-6. 第一個Protein-bound DNIC的合成及晶體結構 9
Figure 1-7. Classical DNICs之分類與結構 12
Figure 1-8. [(1-MeIm)2(2-ONO)Fe(NO)2] 的結構 12
Figure 1-9. Peptide-bound DNIC和RRE與小分子之間的轉換 14
Figure 1-10. 過去400,000年二氧化碳濃度和氣溫的關係 15
Figure 3-1. IR spectrum of complex 1 in THF 36
Figure 3-2. Complex 1 UV-vis (CH2Cl2) : 382 nm (ε = 1612) 36
Figure 3-3. 2mM complex 1於0.1 M [n-Bu4N][PF6]，MeCN溶劑下之CV圖 36
Figure 3-5. IR spectrum of complex 1 bubble CO2(g) 30 minutes (THF) 38
Figure 3-6. Complex 1通入CO2(g) 30分鐘的固態IR光譜圖 38
Figure 3-7. Complex 1催化合成的Na2CO3 40
Figure 3-8. Na2CO3 standard 41
Figure 3-9. Single-crystal X-ray structure of Na2CO3 41
Figure 3-10. 催化合成的MgCO3和標準品的IR光譜圖 42
Figure 3-11. 催化合成的ZnCO3和Na2CO3標準品的IR光譜圖 43
Figure 3-12. PXRD pattern of synthetic ZnCO3 44
Figure 3-13. TGA patterns of synthetic ZnCO3 44
Figure 3-14. 鋅粉、鋅標準品、碳酸鋅、及鹼式碳酸鋅的X-ray吸收光譜圖 45
Figure 3-15. 合成的ZnCO3與FeCO3的比較圖 45
Figure 3-16. 催化合成的Li2CO3 IR光譜圖 46
Figure 3-17. 催化合成的FeCO3 IR光譜圖 47
Figure 3-18. 催化合成的CaCO3 和標準品的IR光譜圖 48
Figure 3-19. 五天中Zn變成ZnCO3的PXRD變化圖 51
Figure 3-20. 以Zn當還原劑，六天的催化結果 53
Figure 3-21. 以氫氣當還原劑，四天的催化效果 55
Figure 3-22. Tube 1，反應溶劑為H2O，未額外加D2O 57
Figure 3-23. Tube 2，反應溶劑為H2O，有額外加D2O 57
Figure 3-24. Tube 3，反應溶劑為ACN，未額外加D2O 58
Figure 3-25. Tube 4，反應溶劑為ACN，有額外加D2O 58
Figure 3-26. TMEDA-DNIC通入CO2(g)後的IR光譜圖 60

Table
Table 1-1. 一氧化氮合成酶的類型及功能 6
Table 1-2. Protein-bond DNICs的配位環境及其EPR訊號 10
Table 1-3. 化學催化使二氧化碳還原成一氧化碳的相關數據 19
Table 1-4. 電催化使二氧化碳還原成一氧化碳的相關數據 20
Table 2-1 實驗溶劑的處理 25
Table 2-3. Crystal data and structure refinement for synthetic Na2CO3 34
Table 3-1. 不同比例的Zn / complex 1 反應之ZnCO3產率 50
Table 3-2. 以Zn當還原劑，催化結果詳細data 53
Table 3-3. 以氫氣當還原劑，催化結果詳細data 55


Scheme
Scheme 3-1. 41
Scheme 3-2. 49
Scheme 3-3. 54
Scheme 3-4. 61

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