本研究以1,1,4,7,10,10-Hexamethyltriethylenetetramine (HMTETA) 為配位基合成出一系列雙核 {Fe(NO)2}10-{Fe(NO)2}10與單核 {Fe(NO)2}9 DNICs，並且探討其反應性與應用性。
[(HMTETA)(Fe(NO)2)2] (1) 為雙核{Fe(NO)2}10-{Fe(NO)2}10 DNIC，將其氧化後可以得到具有pendant amine group之單核{Fe(NO)2}9 DNICs：[(HMTETA)Fe(NO)2][BF4] (3) 與[(HMTETA)Fe(NO)2][SbF6] (4)。[(HMTETA)Fe(NO)2][BF4] (3) 之pendant amine group可以進一步質子化，形成 [(H-HMTETA)Fe(NO)2][BF4]2 (6)，帶有ammonium salt之{Fe(NO)2}9 DNIC。
在反應性方面，將complex 1與HBF4反應，推測會形成intermediate [(HMTETA)(u-H)(Fe(NO)2)2] ，接著與H+ 反應放出H2(g)，形成complex 3。而將complex 1與O2(g) 反應，則會生成產物 [(HMTETA)Fe(NO)2]+ 與[(HMTETA)Fe(NO)(ONO)]+。
此外，本研究也將complex 3進行電化學實驗，發現在還原端與氧化端均具有電催化裂解水之效果。將complex 3以長時間電解所形成的固態電極，效果更是優於未沉積之complex 3，在產氫方面，complex 3-Re-electrode僅需-0.834 V(vs SHE)即可達到10 mA/cm2電流密度 ; 在產氧方面，complex 3-Ox-electode僅需過電位398 mV即可達到10 mA/cm2電流密度。 

In this study, a series of dinuclear {Fe(NO)2}10-{Fe(NO)2}10 and mononuclear {Fe(NO)2}9 dinitrosyl iron complexes using 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) as ligand were synthesized, and their reactivities were explored.
Oxidation of the dinuclear {Fe(NO)2}10-{Fe(NO)2}10 [(HMTETA)(Fe(NO)2)2] (1) afforded the nonclassical five-coordinate {Fe(NO)2}9 [(HMTETA)Fe(NO)2][BF4] (3) and [(HMTETA)Fe(NO)2][SbF6] (4). The pendant amine group of complex 3 could be protonated to form ammonium salt, which made complex 3 convert into [(H-HMTETA)Fe(NO)2][BF4]2 (6).
Reaction of complex 1 with O2(g) led to the oxidation of the dinuclear {Fe(NO)2}10-{Fe(NO)2}10 to dinuclear {Fe(NO)2}9-{Fe(NO)2}9 intermediate, [(HMTETA)(NO)2Fe(u-1,2-peroxo)Fe(NO)2], which could further convert into [(HMTETA)Fe(NO)2]+ and [(HMTETA)Fe(NO)(ONO)]+.
Furthermore, complex 3 was selected as a catalyst in electrocatalytic water splitting. The onset potential of water reduction and oxidation could be efficiently decreased by adding complex 3 in aqueous solution. Besides, after controlled potential electrolysis, complex 3 was able to deposit on the electrode to form active HER and OER working electrodes, which are more efficient than complex 3.

第一章 緒論 1
1-1. 雙亞硝基鐵錯合物 (Dinitrosyl Iron Complexes，DNICs) 1
1-2. DNICs 與氧氣反應 5
1-3. 金屬錯合物催化NO自身氧化還原 (Metal Complex-Mediated NO Disproportionation) 8
1-4. 電催化水裂解 (Electrocatalytic Water Splitting) 14
1-4-1. 產氫反應 (Hydrogen Evolution Reaction，HER) 15
1-4-2. 產氧反應 (Oxygen Evolution Reaction，OER) 20
1-5. 研究動機與方向 24
第二章 實驗部分 25
2-1. 一般實驗 25
2-2. 儀器 25
2-2-1. 紅外線光譜儀 (Infrared spectrometer，IR) 25
2-2-2. 紫外光-可見光吸收光譜儀 (UV-Visible absorption spectrometer) 25
2-2-3. 電子順磁共振光譜儀 (Electron paramagnetic resonance, EPR) 25
2-2-4. 循環伏安儀 (Cyclic Voltammetry, CV) 25
2-2-5. X-ray單晶繞射儀 26
2-2-6. 氣相層析儀 (Gas Chromatography, GC) 26
2-3. 藥品與溶劑 26
2-3-1. 藥品 26
2-3-2. 溶劑 27
2-4. 化合物的合成與鑑定 28
2-4-1. Complex [(HMTETA)(Fe(NO)2)2] (1) 的合成 28
2-4-2. 化合物Me2N(CH2)2NMe(CH2)3NMe(CH2)2NMe2 的合成 28
2-4-3. Complex [(Me2N(CH2)2NMe(CH2)3NMe(CH2)2NMe2)(Fe(NO)2)2](2)的合成 29
2-4-4. Complex [(HMTETA)Fe(NO)2][BF4] (3) 的合成 31
2-4-5. Complex [(HMTETA)Fe(NO)2][SbF6] (4) 的合成 31
2-4-6. Complex [(HMTETA)Fe(NO)(ONO)][SbF6] (5) 的合成 32
2-4-7. Complex [(BF4)(H-HMTETA)Fe(NO)2][BF4] (6) 的合成 32
2-5. 化合物之反應 33
2-5-1. Complex [(HMTETA)(Fe(NO)2)2] (1) 與PhSH之反應 33
2-5-2. Complex [(HMTETA)(Fe(NO)2)2] (1) 與HBF4之反應 33
2-5-3. Complex [(HMTETA)(Fe(NO)2)2] (1) 與O2(g) 之反應 34
2-5-4. Complex [(HMTETA)Fe(NO)2][BF4] (3) 與O2(g) 之反應 35
2-6. 電化學方法 35
2-6-1. 水相 35
2-6-2. 有機相 36
2-7. 晶體結構解析 36
第三章 結果與討論 42
3-1. 錯合物之合成、結構與光譜分析 42
3-1-1. Complex [(HMTETA)(Fe(NO)2)2] (1) 與 [(Me2N(CH2)2NMe(CH2)3NMe(CH2)2NMe2)(Fe(NO)2)2] (2) 的合成、結構與光譜分析 42
3-1-2. Complex [(HMTETA)Fe(NO)2][BF4] (3) 與 [(HMTETA)Fe(NO)2][SbF6] (4) 的合成、結構與光譜分析 45
3-1-3. Complex [(HMTETA)Fe(NO)(ONO)][SbF6] (5) 的合成、結構與光譜分析 48
3-1-4. Complex [(BF4)(H-HMTETA)Fe(NO)2][BF4] (6) 的合成、結構與光譜分析 51
3-2. Complex [(HMTETA)(Fe(NO)2)2] (1) 之反應性 57
3-2-1. Complex [(HMTETA)(Fe(NO)2)2] (1) 與PhSH之反應與光譜分析 57
3-2-2. Complex [(HMTETA)(Fe(NO)2)2] (1) 與HBF4之反應與光譜分析 58
3-2-3. Complex [(HMTETA)(Fe(NO)2)2] (1) 與O2(g) 之反應與光譜分析 61
3-2-4. Complex [(HMTETA)Fe(NO)2][BF4] (3) 與O2(g) 之反應性與光譜分析 65
3-3. Complex 3於電解之應用 66
3-3-1. Complex 3之電化學研究及分析 66
3-3-2. Complex 3於還原端電解之應用 (Reduction end) 67
3-3-3. Complex 3於氧化端電解之應用 (Oxidation end) 71
第四章 結論 76
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