成功地合成一些新的 alkyl chain-containing O-bound {Fe(NO)2}9 DNICs 以及 RREs，藉由測量 X-ray absorption spectroscopy 所得到的 Fe K-edge 之 pre-edge，發現 [18-crown-6-ether-K][(OMe)2Fe(NO)2] (2) 吸收位於 7114.2 eV，與過去的 {Fe(NO)2}9 DNICs 相比起來 (7113.4~7113.8 eV) 都還要來的高，從 CV 圖中也觀察到，complex 2 的氧化還原電位 (E1/2 = -1.3 V vs Fc/Fc+) 也比過去結構相類似的 thiolate-bound DNIC 都還要來的正電位，另外從反應性來來看，將 complex2 與一當量的 KC8 反應，還原一個電子後，其產物是 direduced form RRE，此外發現 complex 2 可以與 CO2 發生insertion 的反應，由以上的實驗結果，我們推測由於 methoxide是屬於比較 hard 的配位基，會極化{Fe(NO)2}9 的鐵中心，使Fe 的價數偏向正三價，當 CO2 靠近時，三價的鐵中心便會極化CO2，發生 CO2 insertion。

Anionic alkyl chain-containing O-bound {Fe(NO)2}9 DNIC [18-crown-6-ether-K][(OMe)2Fe(NO)2] (2) and dianionic OMe-bridged {Fe(NO)2}10-{Fe(NO)2}10 RRE [18-crown-6-ether-K][Fe(-OMe)(NO)2]2 (4) were synthesized and characterized by CV, FT-IR, UV-Vis, XAS, EPR spectroscopy and single crystal X-ray diffraction. On the base of electrochemistry, the {Fe(NO)2}9/ {Fe(NO)2}10 redox couple of complex 2 is E1/2= -1.3 V (vs Fc/Fc+), more positive potential than that (E1/2= -1.6 V (vs Fc/Fc+)) of the reported four coordinate S-bound {Fe(NO)2}9 DNICs. In comparison with the Fe K-edge energy of the published {Fe(NO)2}9 DNICs, Fe K-edge pre-edge energy 7114.2 eV of complex 2, implicate that the contribution of {FeⅢ(NO-)2}9 electronic structure is dominant. For complex 2, it is presumed that the hard ligand [OMe]- may polarize Fe center of {Fe(NO)2}9 motif to enhance {FeⅢ(NO-)2}9 contribution. Since {FeⅢ(NO-)2}9 contribution predominates in complex 2, the ferric center of complex 2 may polarize the incoming CO2 molecule and trigger CO2 1,2-insertion to yield the proposed methylcarbonate-bound {FeⅢ(NO-)2}9 DNIC at -50oC, demonstrated by FT-IR spectroscopy.

Figure
Figure 1-1 一氧化氮分子軌域圖 2
Figure 1-2金屬與 NO 的鍵結關係 3
Figure 1-3 金屬與一氧化氮的 dπ-π* 鍵結分子軌域形式 4
Figure 1-4 一氧化氮合成酶催化示意圖 5
Figure 1-5 Nitrate 和 nitrite 以及一氧化氮的生成路徑 6
Figure 1-6細胞產生 ATP 的過程與受 NO 干擾導致細胞凋亡的機制 7
Figure 1-7 guanylate cyclase 與一氧化氮間的反應及訊號傳遞 8
Figure 1-8 (a) Cys-NO、GS-NO的結構. (b) RSNO 的生成機制 9
Figure 1-9 RSNO 產生一氧化氮的反應機制 10
Figure 1-10 GST P1-1 protein-bond DNIC 合成過程與晶體結構 12
Figure 1-11 Classical LMW DNIC之分類與結構 15
Figure 1-12 non-classical DNICs 與 Se-containing DNICs 之結構 16
Figure 1-14 Heat shock 致使 heat shock protein 製造途徑 18
Figure 1-15 Glutathione reductase 亞硝基化去活化機制 18
Figure 1-16 RRE 結構與 EPR 訊號 20
Figure 1-17 常見的亞硝基鐵錯合物 20
Figure 3-1 [18-crown-6-ether-K][(OMe)2Fe(NO)2] (2) 之IR光譜 (THF) 34
Figure 3-2 [18-crown-6-ether-K][(OMe)2Fe(NO)2] (2) 之IR光譜 (KBr) 35
Figure 3-3 [18-crown-6-ether-K][(OtBu)2Fe(NO)2] (3) 之IR光譜 (THF) 35
Figure 3-4 ORTEP drawing and labeling scheme of [18-crown-6-ether-K][(OMe)2Fe(NO)2] 36
Figure 3-5 complex 2 之 UV-Vis 吸收光譜 39
Figure 3-6室溫 EPR 光譜 (a) complex 2 (THF), aNO = 2.44 G; (b) complex 3 (Ether), aNO = 2.46 G 40
Figure 3-7 complex 2 之 4K EPR 光譜 (THF) 41
Figure 3-8 complex 2 與過去所合成DNIC 之 Fe K-edge比較 42
Figure 3-9 complex 2 之 CV 圖 44
Figure 3-10 [18-crown-6-ether-K]2[Fe(μ-OMe)(NO)2]2 (4) 之IR光譜 (KBr) 45
Figure 3-11 [18-crown-6-ether-K]2[Fe(μ-OMe)(NO)2]2 (4) 之IR光譜 (MeCN) 46
Figure 3-12 [18-crown-6-ether-K]2[Fe(μ-OtBu)(NO)2]2 (5) 之IR光譜 (KBr) 47
Figure 3-13 ORTEP drawing and labeling scheme of [18-crown-6-ether-K]2[Fe(μ-OMe)(NO)2]2 (4) 48
Figure 3-14 OMe-bound DNIC (black line) 與 SEt-bound DNIC (red line) 之IR 比較圖 52
Figure 3-15 OMe-bound DNIC (black line) 與 OPh-bound DNIC (red line) 之IR 比較圖 53
Figure 3-16 complex 2 與 CO2 反應 IR 光譜 55
Figure 3-17 Complex 2 與 CO2 反應後之 IR 光譜 (THF) 56
(black line) room temperature (red line) -50oC 56
Figure 3-18 Complex 2 與 CO2 在 -50oC 下反應後之 EPR 圖譜(77K) in THF 56
Figure 3-19 {Fe(NO)2}9/{Fe(NO)2}10 DNICs 氧化還原半電位之比較 59





Table
Table 1-1 不同氧化態之一氧化氮性質整理 3
Table 1-2 不同類型 NOS 之性質與功能 8
Table 1-3 protein-bound DNICs 與其 EPR 訊號 12
Table 3-1 含硫或含氧配位基 {Fe(NO)2}9 DNIC 之鍵長鍵角比較 38
Table 3-2 Fe K-edge之pre-edge吸收峰位置整理 42
Table 3-3 DNIC 之氧化還原半電位比較 44
Table 3-4 alkoxide-bound DNIC與RRE之IR光譜吸收峰整理 48
Table 3-5 含硫或含氧配位基 di-reduced Roussin’s red esters 之鍵長比較 49













Scheme
Scheme 3-1. [18-crown-6-ether-K][(OMe)2Fe(NO)2] (2)的合成步驟……………...32
Scheme 3-2 [18-crown-6-ether-K][(OtBu)2Fe(NO)2] (3)的合成步驟.......................33
Scheme 3-3 [18-crown-6-ether-K]2[Fe(μ-OMe)(NO)2]2 (4) 的合成步驟…….....44
Scheme 3-4 [18-crown-6-ether-K]2[Fe(μ-OtBu)(NO)2]2 (5)的合成步驟…………46
Scheme 3-5 complex 2 與 KC8 反應示意圖............................................................50
Scheme 3-6 complex 2 與 KSEt 反應示意圖……………………………………..51
Scheme 3-7 complex 2 與 KOPh 反應示意圖…………………………………….53
Scheme 3-8 complex 2 與CO2 反應示意圖.............................................................55

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