雙牙硫配位基之小分子{Fe(NO)2}9 DNIC [PPN][(S(CH2)3S)Fe(NO)2] (1) 與氧氣反應後會先形成 [PPN][(NO2)2Fe(NO)2]，之後 [PPN][(NO2)2Fe(NO)2] 會進一步地與氧氣反應，與此同時 [PPN][(NO2)2Fe(NO)2] 亦有可能與尚未和氧氣反應的complex 1生成 [(NO)2Fe(S(CH2)3S)Fe(NO)2]。[PPN][(NO2)2Fe(NO)2] 與氧氣反應後，推測先形成 [PPN][Fe(NO)4(NO2)2]，再轉變為 [PPN][Fe(NO)2(NO2)4] ，而最後會轉變為 [PPN][Fe(NO2)4] 。此研究結果與先前文獻報導單牙硫配位基之小分子{Fe(NO)2}9 DNIC與氧氣的反應性不同。
本研究亦藉由 [PPN][Fe(CO)3(NO)] 與diethylenetriamine合成出小分子{Fe(NO)2}10 DNIC [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2)。於THF下，complex 2 與氧氣反應後會形成 [(NO)2Fe(H2N(CH2)2NH(CH2)2NH2)2Fe(NO)2] (3)，於水相下complex 2 與氧氣反應則是形成[(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2]+。
Complex 2與[NO][BF4] 反應，會形成 [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5)。
在這能源需求越來越高、氣候變遷的世代中，尋求零碳的再生能源是當今重要的議題，裂解水產生出的氫氣可作為零碳的氫能源，符合上述需求，而設計出一便宜且效率高的催化劑協助降低還原反應的過電位是科學界一大挑戰， complex 5正可以符合需求。

The reaction of {Fe(NO)2}9 LMW-DNIC [PPN][(S(CH2)3S)Fe(NO)2] (1) bearing bidentate-thiolate ligand with oxygen yields [PPN][(NO2)2Fe(NO)2]. [(NO)2Fe(S(CH2)3S)Fe(NO)2] is generated via the reaction of [PPN][(NO2)2Fe(NO)2] and complex 1. [PPN][(NO2)2Fe(NO)2] may react with oxygen to result in the formation of [PPN][Fe(NO2)4] via the interaction of O2 and the proposed [PPN][Fe(NO)4(NO2)2] or [PPN][Fe(NO)2(NO2)4] intermediates. This reactivity is different from that previously reported for {Fe(NO)2}9 DNIC bearing monodentate-thiolate ligands.
The {Fe(NO)2}10 DNIC [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2) is synthesized from the reaction of [PPN][Fe(CO)3(NO)] with diethylenetriamine. Under the presence of O2, complex 2 is converted to [(NO)2Fe(H2N(CH2)2NH(CH2)2-
NH2)2Fe(NO)2] (3) in THF and into [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2]+ in aqueous solution, respectively. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5) can be obtained by the reaction of complex 2 with [NO][BF4].
Seeking for renewable energy and catalysts is an important challenge for scientists. Here, complex 5 meets the needs indeed.

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. 氫能源 15
1-6. 研究方向 22
第二章 實驗部分 23
2-1. 一般實驗 23
2-2. 儀器 23
2-3. 溶劑與藥品 24
2-3-1. 溶劑 24
2-3-2. 藥品 25
2-4. 化合物的合成與鑑定 25
2-4-1. complex [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2) 的合成 25
2-4-2. complex [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5) 的合成 26
2-5. 化合物的反應 27
2-5-1. [PPN][(S(CH2)3S)Fe(NO)2] (1) 與O2(g)的反應 27
2-5-2. [PPN][Fe(NO2)2(NO)2]與O2(g)的反應 28
2-5-3. [PPN][Fe(NO2)2(NO)2] 與 [PPN][(S(CH2)3S)Fe(NO)2] (1) 的反應 29
2-5-4. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2 ] (2) 與 O2(g) 的反應 29
2-5-5. [(H2N(CH2)2NHCOCH3)Fe(CO)(NO)2]與O2(g)的反應 30
2-6. 電化學方法 30
2-7. 晶體結構解析 31
第三章 結果與討論 39
3-1. [PPN][(S(CH2)3S)Fe(NO)2] (1) 對O2(g) 之反應 39
3-1-1. [PPN][(S(CH2)3S)Fe(NO)2] (1) 與O2(g) 的反應性與光譜分析 39
3-1-2. [PPN][Fe(NO2)2(NO)2] 與O2(g) 的反應與光譜分析 45
3-1-3. 探討 [PPN][(S(CH2)3S)Fe(NO)2] (1) 與O2(g) 的反應 46
3-2. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2) 的合成、結構與光譜分析 48
3-2-1. Complex 2 的合成 48
3-2-2. Complex 2 的光譜分析 48
3-3. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2) 對 O2(g) 之反應性 51
3-3-1. Complex 2 對氧氣的反應 51
3-3-2. 光譜分析 51
3-3-3. 探討[(NO)2Fe(H2N(CH2)2NH(CH2)2NH2)2Fe(NO)2] (3) 的生成 54
3-4. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5) 的合成、結構與光譜分析 55
3-4-1. Complex 5 的合成 55
3-4-2. 光譜分析 55
3-5. [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5) 的應用 58
第四章 結論 68
References 71

Figure
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. 一氧化氮合成酶類型及功能 6
Figure 1-5. NO於生物體內的化學反應 7
Figure 1-6. Cys-NO 和 GSNO 的結構 7
Figure 1-7. 第一個Protein-bound DNIC的合成及晶體結構 9
Figure 1-8. Classical DNICs之分類與結構 12
Figure 1-9. [(1-MeIm)2(2-ONO)Fe(NO)2] 的結構 12
Figure 1-10. Peptide-bound DNIC和RRE與小分子之間的轉換 14
Figure 1-11. 以鈷、鎳、鐵金屬作為活性中心之催化劑的結構 16
Figure 1-12. 推測催化劑電催化質子還原氫氣之反應途徑 18
Figure 1-13. 各種工作電極對於 10 mM 醋酸之overpotential 19
Figure 1-14. CV實驗 20
Figure 1-15. CPE實驗 21
Figure 1-16. Chang教授推測其催化劑協助裂解水之反應機制 21
Figure 3-1. ORTEP drawing and labeling scheme of [PPN][Fe(NO2)2(NO)2] with thermal ellipsoids at 50% probability. 40
Figure 3-2. 推測產物 [(NO)2Fe(S(CH2)3S)Fe(NO)2] 的IR光譜圖 41
Figure 3-3. Complex 1與氧氣反應 5 小時後的IR光譜圖 41
Figure 3-4. ORTEP drawing and labeling scheme of [PPN][Fe(NO)4(NO2)2] with thermal ellipsoids at 50% probability 42
Figure 3-5. ORTEP drawing and labeling scheme of [PPN][Fe(NO2)4] with thermal ellipsoids at 50% probability. 42
Figure 3-6. Complex 1 與氧氣反應 6 小時後的IR光譜圖 43
Figure 3-7. ORTEP drawing and labeling scheme of [PPN][Fe(NO)2(NO2)4] with thermal ellipsoids at 50% probability. 44
Figure 3-8. [PPN][Fe(NO2)2(NO)2] 與氧氣反應的IR光譜轉變圖 45
Figure 3-9. Complex 2 IR光譜圖 49
Figure 3-10. Complex 2 UV-Vis 光譜圖 49
Figure 3-11. ORTEP drawing and labeling scheme of complex 2 with thermal ellipsoids at 50% probability. 50
Figure 3-12. Complex 2 與氧氣反應之 IR光譜圖 51
Figure 3-13. ORTEP drawing and labeling scheme of (NO)2Fe(HN(CH2)2NHCOCH3)2Fe(NO)2]‧THF with thermal ellipsoids at 50% probability. 52
Figure 3-14. Complex 2 於-80。C下與氧氣反應之 UV-Vis光譜圖 53
Figure 3-15. Complex 2 於 -80。C下與氧氣反應後回至室溫之 UV-Vis 光譜圖 53
Figure 3-16. Complex 5之 IR光譜圖 56
Figure 3-17. Complex 5之 UV-Vis光譜圖 56
Figure 3-18. Complex 5之 EPR光譜圖於77 K 57
Figure 3-19. ORTEP drawing and labeling scheme of Complex 5 with thermal ellipsoids at 50% probability 57
Figure 3-20. 0.1 M Na2SO4 H2O solution 之 CV 及加入1 mM Complex 5 59
Figure 3-21. 0.1 M Na2SO4 H2O solution 之 CV 及加入各種濃度的Complex 5 59
Figure 3-22. 於 -1.4 V vs SCE電位下，Complex 5添加的濃度 vs 電流 60
Figure 3-23. CPE experiments. 3 mM complex 5 in 0.1 M Na2SO4 H2O solution 61
Figure 3-24. 3 mM complex 5 in 0.1 M Na2SO4 H2O solution 於200秒內，不同的電位 vs 所累計的電量 61
Figure 3-25. 不同電位下所增益的累積電量 62
Figure 3-26. CPE實驗，於 -1.54 V vs SCE電位、0.1 M Na2SO4 H2O solution 63
Figure 3-27. 判定法拉第效率 (Faradaic efficiency) 64
Figure 3-28. 氫氣檢量線 64
Figure 3-29. Complex 2 於D2O 溶液下，與O2反應的IR光譜轉變圖 67

Table
Table 1-1. Protein-bond DNICs的配位環境及其EPR訊號 10
Table 1-2. 催化劑催化產氫之相關數據 10
Table 2-1. Crystal data and structure refinement for [PPN][Fe(NO2)2(NO)2] 32
Table 2-2. Crystal data and structure refinement for [PPN][Fe(NO2)4] (62%) and [PPN][Fe(NO)4(NO2)2] (38%) 33
Table 2-3. Crystal data and structure refinement for [PPN][Fe(NO2)4] (59%) and [PPN][Fe(NO)2(NO2)4] (41%) 34
Table 2-4. Crystal data and structure refinement for [PPN][Fe(NO2)４] (40%) and [PPN][Fe(NO)2(NO2)4] (60%) 35
Table 2-5. Crystal data and structure refinement for [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2] (2) 36
Table 2-6. Crystal data and structure refinement for [(H2N(CH2)2NH(CH2)2NH2)Fe(NO)2][BF4] (5) 37
Table 2-7. Crystal data and structure refinement for [NO2Fe(HN(CH2)2NHCOCH3)2Fe(NO)2]‧THF 38

Scheme
Scheme 1-1 15
Scheme 3-1 39
Scheme 3-2 47
Scheme 3-3 47
Scheme 3-4 54
Scheme 3-5 65
Scheme 3-6 67

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