本研究主要以已知化合物[Fe4(C3H3N2)4(NO)8] (1)當作起始物，加入酚
基( phenoxide )和亞硝酸鹽( nitrite )合成O, N配位的雙亞硝基鐵錯合物[(C3H3N2)(OPh)Fe(NO)2]- (2)及[(C3H3N2)(NO2)Fe(NO)2]- (3’)，並探討其反應性。
化合物[(C3H3N2)(OPh)Fe(NO)2]- (2)的成功合成證實含Tyrosine和Histidine混合配位之protein-bound DNICs存在的可能性。將此化合物2與等當量的thiol或thiolate反應可以置換化合物2上的酚基形成硫和氮配位的DNICs；
硫氮配位的DNICs再多加一當量的thiol或thiolate則會置換掉咪唑基( Imidazolate )，形成兩個硫配位的DNICs。這一系列反應可以清楚說明S/N/O配位基與{Fe(NO)2}的鍵結能力；也間接證實為何生物體中DNICs較多由半胱胺酸當配位基。化合物[(C3H4N2)2(η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)的成功合成，又是6配位{Fe(NO)2}9 DNIC的另一例子，而其中間產物[(C3H3N2)(NO2)Fe(NO)2]- (3’)在[OPh]-的存在下，可轉換形成化合物2，在EPR光譜上，化合物3’的室溫光譜g值落在2.03附近，這也間接證實了化合物3’的存在。

In this research, reaction of [Fe4(C3H3N2)4(NO)8] (1) with phenoxide and nitrite led to the formation of [(C3H3N2)(OPh)Fe(NO)2]- (2) and [(C3H3N2)(NO2)Fe(NO)2]- (3’), respectively. Synthesis of the anionic {Fe(NO)2}9 [(C3H3N2)(OPh)Fe(NO)2]- (2) supports the existence of protein-bound NHis/OTyr-DNICs. Reaction of complex 2 and thiol or thiolate in 1:1 molar ratio led to the formation of [(C3H3N2)(SPh)Fe(NO)2]- with mixed imidazolate-/thiolate- coordinated ligands. Addition of another 1 equivalent of thiol or thiolate into imidazolate-/thiolate- coordinated DNIC yielded [(SPh)2Fe(NO)2]- . These reactions elucidate the binding ability of {Fe(NO)2} moiety toward thiolate, imidazolate and phenoxide.
The non-classical six-coordinated DNIC{Fe(NO)2}9 [(C3H4N2)2(η2-ONO)Fe(NO)2] [18-crown-6-ether]2 (3) was synthesized. The proposed precursor of complex 3, [(C3H3N2)(NO2)Fe(NO)2]- (3’) with EPR g value 2.03, transforms into complex 2 upon addition of 2 equivalent of phenoxide into it.

目錄
第一章：緒論 1
1-1 前言 1
1-2 一氧化氮在生物體內的重要性 2
1-3 NO結構及NO鍵結在過渡金屬上的電子狀態多樣性 4
1-4 一氧化氮在生物體的儲存及傳遞形式 6
1-5 Nitrite在體內的重要性 7
1-6 雙亞硝基鐵錯合物的特性及其重要性 10
1-7 含亞硝酸鹽之單/雙亞硝基鐵錯合物的特性及其重要性 14
1-8 生物擬態DNICs 15
1-9 實驗研究方向 18
第二章：實驗部份 19
2-1 一般實驗 19
2-2 儀器 19
2-3 藥品 20
2-4 化合物之合成與鑑定 21
2-4-1合成[Fe4(C3H3N2)4(NO)8] (1) 21
2-4-2合成[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2). 21
2-4-3合成[Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’). 22
2-5 化合物之反應 22
2-5-1 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)與HSPh和[Na-18-crown-6-ether][SPh]反應. 22
2-5-2 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2) 與[Na-18-crown-6-ether][OPh]和HOPh之反應 23
2-5-3 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2) 與 [Na-18-crown-6-ether][NO2]之反應 23
2-5-4 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)與MeOH之反應 23
2-5-5 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)與[H(2,6-lutidine)] [BF4]之反應 24
2-5-6 化合物[Na -18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)與[Na-18-crown-6-ether][OPh]之反應 24
2-5-7 化合物[Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)與Imidazole之反應 24
2-6 晶體結構解析( Crystallography ) 25
2-6-1 [Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2) 25
2-6-2 [(C3H4N2)2( η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3) 25
第三章：結果與討論 28
3-1化合物[Fe4(C3H3N2)4(NO)8] (1) 28
3-2 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)的合成、光譜及晶體結構 30
3-2-1 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)之合成 30
3-2-2 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)之光譜 30
3-2-3 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)之晶體結構 33
3-3 化合物[Na-18-crown-6-ether][(NO)2Fe(C3H3N2)(NO2)] (3’)的合成、光譜及[(C3H4N2)2(η2-ONO)Fe(NO)2] (3)的合成、光譜及晶體結構. 35
3-3-1 化合物[Na-18-crown-6-ether][(NO)2Fe(C3H3N2)(NO2)] (3’)之合成 35
3-3-2 化合物[Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)之光譜 36
3-3-3 化合物[(C3H4N2)2( η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)之合成 37
3-3-4 化合物[(C3H4N2)2( η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)之光譜 38
3-3-5 化合物[(C3H4N2)2( η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)之晶體結構 40
3-4 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)與[Na-18-crown-6-ether][(NO)2Fe(C3H3N2) (NO2)] (3’)之反應性探討 43
3-4-1 化合物[Na-18-crown-6-ether][(NO)2Fe(C3H3N2)(OPh)] (2)與HSPh或[Na-18-crown-6-ether][SPh]反應. 43
3-4-2 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)與[H(2,6-lutidine)] [BF4]之反應 46
3-4-3 化合物[Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)與[Na-18-crown-6-ether][OPh]之反應 46
第四章：結論 47
參考文獻 49










Figure
Figure 1-2. NO的分子軌域圖 4
Figure 1-3. 金屬與一氧化氮分子軌域中dπ-π*的交互作用 5
Figure 1-4. Cys-NO和GS-NO的結構 7
Figure 1-5. 由mtALDH催化之GTN的活化機制 9
Figure 1-6. protein-bound DNICs：GST P1-1的合成及晶體結構 11
Figure 1-7. 高電位含鐵硫蛋白質( HiPIP )和一氧化氮反應的生成物 12
Figure 1-8. 生物體中iron-surfer Cluster的降解應與修復 13
Figure 3-1. [Fe4(C3H3N2)4(NO)8] (1)為四核之鐵亞硝基化合物 28
Figure 3-2-1. [Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)在THF下之紅外光譜。 31
Figure 3-2-2. [Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)在THF下之電子吸收光譜。 31
Figure 3-2-3. [Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)在THF下之電子順磁共振光譜 (a)室溫( g = 2.026, aN(NO) =2.42 G, aN(Im) = 4.15 G ) (b) 77 K ( g1 =2.046, g2 = 2.020, g3 = 2.01, gav = 2.025) 32
Figure 3-2-5. 化合物[Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)的ORTEP圖 34
Figure 3-3-1. [Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)在THF下之紅外光譜 36
Figure 3-3-2. [Na-18-crown-6-ether][(C3H3N2) (NO2)Fe(NO)2] (3’)在THF下之電子 吸收光譜 37
Figure 3-3-3. [(C3H4N2)2( η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)在THF下之紅外光譜 38
Figure 3-3-4. [Na-18-crown-6-ether][(C3H3N2)(NO2)Fe(NO)2] (3’)在THF下之電子順磁共振光譜 (a)室溫 (b) 220 K (c) 180 K (d) 160 K (e) 120 K (f) 77 K 39
Figure 3-3-7. 化合物[(C3H4N2)2(η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)的3D圖. 41
Figure 3-3-8. 化合物[(C3H4N2)2(η2-ONO)Fe(NO)2][18-crown-6-ether]2 (3)的ORTEP圖. 41
Figure 3-4-1. [Na-18-crown-6-ether][(SPh)(C3H3N2)Fe(NO)2]之紅外光譜 45
Figure 3-4-2. [Na-18-crown-6-ether][(SPh)2Fe(NO)2]之紅外光譜 45


Table
Table 2-1： [Na-18-crown-6-ether][(C3H3N2)(OPh)Fe(NO)2] (2)之晶體參數 26
Table 2-2： [(C3H4N2)2( η2-ONO)Fe(NO)2] (3)之晶體參數 27
Table 3-2-1. 化合物2的重要鍵長[ Å ]及鍵角[ o ]. 34
Table 3-2-2. 一些Anionic/Neutral/Cationic {Fe(NO)2}9 DNICs的Fe-N(O)和N-O的 鍵長. 35
Table 3-3-1. 化合物3的重要鍵長[ Å ]及鍵角[ o ]. 42



Scheme
Scheme 1 ……………. 9
Scheme 2 合成含O, N之雙亞硝基鐵錯合物( DNICs )之反應路徑 29
Scheme 3 ..................... 44
Scheme 4 ……………. 44

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