本研究中成功的合成出FeIII與[HS]－鍵結，具有[FeIII-SH] motif的DNIC ([K-18-crown-6-ether][(HS)2Fe(NO)2] (1) 及[PPN][(HS)2Fe(NO)2] (1-PPN))、MNIC ([PPN][(HS)3Fe(NO)] (3))以及dimerize成[PPN]2[(μ-S)Fe(SH)(NO)]2 (4) (Scheme 1)，其中complex 1 溶於水中會釋放出H2S並生成RRS，代表DNIC在hydrophobic的環境之下或許可以當作H2S的儲存和傳遞者，並且在hydrophilic的環境下再將其釋放出來，原因可能跟NO本身non-innocent的性質有關，NO扮演了調控電子的角色而讓生物體內的[HS]－有機會鍵結到Fe上，而且鍵結到Fe上之後藉由NO供給電子給Fe，讓FeIII不會被thiolate還原成FeII。
從實驗上EPR、IR、XAS、XRD綜合比較後，可以決定出含有[FeIII-SH] motif的complex 1, 1-PPN的電子結構應為high-spin FeIII (SFe = 5/2)與兩個NO－(SNO = 1)以antiferromagnetically coupled，而熱不穩定的complex 3會自然的dimerize成complex 4，其電子結構可以描述成兩個{FeIII(NO－)}7以antiferromagnetic coupled形成diamagnetic complex，從理論計算也可以輔助這一點。
另外與本實驗室最近發表的文獻提到[PPN][Fe(SH)4] (5)和[PPN]2[(μ-S)Fe(SH)]2 (6)的合成及穩定性，由實驗結果得知穩定性為1 > 3 > 5，釋放出H2S形成dimer form之穩定度為2 > 4 > 6，說明了NO越多穩定性越高，並且用理論計算和氧化還原電位去輔助說明為何有此現象。

The formation of hydrosulfide-bound {Fe(NO)2}9 dinitrosyl iron complex (DNIC), [K-18-crown-6-ether][(HS)2Fe(NO)2] (1) ([PPN][(HS)2Fe(NO)2] (1-PPN)) and the precursor mononitrosyl iron complex (MNIC), [PPN][(HS)3Fe(NO)] (3), were synthesized and characterized. Transformation of complex 1 into Roussin’s red salt (RRS) along with release of H2S in protic solvent was probed by NBD-SCN. It may suggest that DNIC can be a role for H2S storage and transport in hydrophobic environment. This phenomenon is attributed to the characteristic of non-innocent NO to regulate electron transfer among [FeIII-SH] core, which inhibited the reduction of FeIII into FeII and prevent reductive elimination of Fe-SH bond,
The electronic structure containing [FeIII-SH] motif of complex 1, 1-PPN, 4 was determined by EPR, IR, XAS, and XRD. Complex 1 and 1-PPN can be described as high-spin FeIII (SFe = 5/2) and two NO－(SNO = 1) antiferromagnetically coupled. The thermally unstable complex 3 spontaneously dimerize into the first structurally characterized FeIII-hydrosulfide complex [PPN]2[(μ-S)Fe(SH)(NO)]2 (4). The electronic structure can be described as two {FeIII(NO－)}7 antiferromagnetic coupled to yield S = 0 diamagnetic complex.
From recently published paper, the thermally unstable [PPN][Fe(SH)4] (5) spontaneously dimerizes to form [PPN]2[(SH)Fe (μ-S)]2 (6). According to the experiment, the stability of complex 1, 3, and 5 is 1 > 3 > 5. The stability of the dimerized-form is 2 > 4 > 6. On the basis of DFT computation and reduction potential, NO serves as strong electron-donating ligand (compared to thiolate), which reduces the effective nuclear charge(Zeff) of the iron center and prevent complex 1 from dimerization. That is, the stability increases accompanied with the larger NO-coordinate ligands bound to the [FeIII-SH] motif.

第一章:緒論: 1
1-1一氧化氮(nitric oxide, NO) 1
1-2一氧化氮與雙亞硝基鐵錯合物之電子結構 3
1-3一氧化氮在生物體內的儲存和傳遞 6
1-4硫化氫(Hydrogen sulfide, H2S) 9
1-5 H2S和NO的交互作用 13
1-6研究方向 18
第二章:實驗 19
2-1一般實驗 19
2-2儀器 19
2-3藥品 21
2-4化合物的合成、反應與鑑定 21
2-4-1合成[K][StBu]和[K][SEt] 21
2-4-2合成[PPN][(Cl)3Fe(NO)] 22
2-4-3合成[PPN][ (tBuS)3Fe(NO)]與[PPN][(EtS)3Fe(NO)] 22
2-4-4合成[K-18-crown-6-ether][(HS)2Fe(NO)2] (1) 及[PPN][(HS)2Fe(NO)2] (1-PPN) 23
2-4-5合成[PPN][(HS)3Fe(NO)] (3)並轉換成[PPN]2[Fe2S2(SH)2(NO)2] (4) 23
2-4-6[K-18-crown-6-ether][(HS)2Fe(NO)2] (1)與水反應轉換成Roussin’s Red Salt (RRS, 2)並以H2S probe NBD-SCN (NBD = nitrobenzofurazan) 偵測 24
2-4-7[K-18-crown-6-ether][(HS)2Fe(NO)2] 與HSPh反應並以H2S probe NBD-SCN (NBD = nitrobenzofurazan) 偵測 25
2-4-8 Roussin’s Red Salt (2) 與硫化氫反應 25
2-5晶體結構解析(Crystallography) 26
第三章:結果與討論 30
3-1[K-18-crown-6-ether][(HS)2Fe(NO)2] (1) 及[PPN][(HS)2Fe(NO)2] (1-PPN)的光譜比較、晶體結構及反應性之探討 30
3-1-1[K-18-crown-6-ether][(HS)2Fe(NO)2] (1) 和[PPN][(HS)2Fe(NO)2] (1-PPN)之結構與光譜 30
3-1-2 Complex 1和1-PPN之EPR光譜比較與電子結構 34
3-1-3 Complex 1在極性溶劑(以NBD-SCN偵測)下釋放H2S和complex 1-PPN在真空以及其逆向的反應性 36
3-2[PPN][(HS)3Fe(NO)] (3)及[PPN]2[(μ-S)Fe(SH)(NO)]2 (4)的光譜比較、晶體結構及反應性之探討 39
3-2-1[PPN][(HS)3Fe(NO)] (3)之光譜和電子結構探討 39
3-2-2[PPN]2[(μ-S)Fe(SH)(NO)]2 (4)之結構與光譜 41
3-3 Complex 1, 2與complex 4的S K-edge比較 47
3-4穩定度比較 49
3-4-1 Rubredoxin [Fe(SH)4]－(5) 與Ferredoxin [(HS)2Fe(μ-S)]22- (6) 49
3-4-2 Complex 2, 4, 6之穩定度比較 51
3-4-3 Complex 1, 3, 5之穩定度比較 52
3-5從理論計算看穩定度 53
3-5-1[(NO)(HS)Fe(μ-S)2]22－ (H)之電子結構計算 54
3-5-2[(NO)2Fe(μ-S)2]22－(G)，[(NO)(HS)Fe(μ-S)2]22－(H)，
[(HS)2Fe(μ-S)2]22－(I)之電子結構計算 55
3-5-3從氧化還原電位說明NO對穩定度的幫助 56
3-5-4氧化數和自由能的理論計算 57
第四章:結論 62
參考資料 65












Figure

Fig. 1-1. 一氧化氮合成酶之催化機制 1
Fig. 1-2. NO分子軌域圖 3
Fig. 1-3. NO與金屬的各種共振型態 4
Fig. 1-4. Cys-NO和GS-NO之結構 6
Fig. 1-5. 兩種一氧化氮儲存模式轉換圖 7
Fig. 1-6. 各種類的DNICs模型 8
Fig. 1-7. 內生性H2S在人體各部位的主要功能 9
Fig. 1-8. 硫化氫之生物合成 11
Fig. 1-9. H2S與不同氧化態的NO可能發生的反應 13
Fig. 1-10. HSNO的反應性和異構物 14
Fig. 1-11. H2S和GSNO的反應 14
Fig. 1-12. H2S和SNP的反應。上：S-nitrosothiol產生(Moore)；中：HNO產生(Bian)；下：直接與SNP反應(Olabe) 16
Fig. 1-13. 利用Fe3+(P)模擬粒線體內heme-iron center當作催化劑，H2S將NO2─還原之反應機構 17
Fig. 3-1.Structure of 50% [K-18-crown-6-ether] [(HS)2Fe(NO)2] (1) 31
Fig. 3-2. Complex 1之IR光譜(THF) 32
Fig. 3-3. Complex 1之UV-Vis光譜(THF) 32
Fig. 3-4. Structure of 50% [PPN][(HS)2Fe(NO)2] (1-PPN) 33
Fig. 3-5. Complex 1-PPN 之IR光譜(MeCN) 34
Fig. 3-6. X-band EPR spectra of (a) complex 1 in THF at 298 K with gav = 2.028 and (b) complex 1-PPN in THF at 298 K with gav = 2.029, aN = 2.8 G. 34
Fig. 3-7. X-band EPR spectra of (a) complex 1 in THF at 77 K with g1 = 2.039, g2 = 2.026, g3 = 2.013, and (b) complex 1-PPN in THF at 77 K with g1 = 2.040, g2 = 2.027, g3 = 2.014. 36
Fig. 3-8. Fe K-edge spectrum of (a) complex 1 and (b) Complex 1-PPN. 36
Fig. 3-9. (a) UV-vis spectrum of the produced NBD-SH (b) Standard curve 37
Fig. 3-10. Complex 1-PPN和RRS在真空下的轉換 38
Fig. 3-11. Complex 3之IR光譜(THF) 40
Fig. 3-12. Complex 3之EPR光譜(4K, THF)，” * ” (g = 2.025)為complex 1-PPN 40
Fig. 3-13. Structure of 50% [PPN]2[(μ-S)Fe(SH)(NO)]2 (4) 41
Fig. 3-14. Structure of 50% [PPN]2[(μ-S)Fe(SH)(NO)]2 (4) (another set) 42
Fig. 3-15. Complex 4之IR光譜(MeCN) 43
Fig. 3-16. Complex 4之IR光譜(KBr) 43
Fig. 3-17. Complex 4之UV-Vis光譜 44
Fig. 3-18. 1H NMR spectrum of [PPN]2[(SH)(NO)Fe(μ-S)]2 (4) in d7-DMF. 45
Fig. 3-19. Complex 4的Fe K-edge pre-edge. 46
Fig. 3-20. Cyclic voltammogram of complex 4 46
Fig. 3-21. Complex 1的S K-edge 48
Fig. 3-22. Complex 4的S K-edge 48
Fig. 3-23. X-band EPR spectrum of complex 5 (g = 9.30 and 4.29) in DMF at 4 K. 49
Fig. 3-24. Structure of 50% [PPN]2[(μ-S)Fe(SH)2]2 (6) 50
Fig. 3-25. (a) 1H NMR spectrum of [PPN]2[(SH)2Fe(μ-S)]2 (6) in d7-DMF. (b) 1H NMR spectrum of [PPN]2[(SH)2Fe(μ-S)]2 (6) and [PPN]2[Fe4S4(SH)4] in d7-DMF. 51
Fig. 3-26. Broken-symmetry Ms = 0 spin density (isovalue = 0.01) of conformation H. 54
Fig. 3-27. Cyclic voltammogram of [(EtS)3Fe(NO)]– 56
Fig. 3-28. Cyclic voltammogram of complex 1-PPN 57

Table
1-1.NO氧化態、鍵數、鍵長及IR吸收範圍 4
2-1. Crystal data and structure refinement for complex 1. 27
2-2. Crystal data and structure refinement for 1-PPN. 28
2-3. Crystal data and structure refinement for complex 4. 29
3-1. Selected Metric Data for [iPr4N]2[(NO)2Fe(μ-S)]2 (2), [PPN]2[(NO)(HS)Fe(μ-S)]2 (4) and [PPN]2[(HS)2Fe(μ-S)]2 (6). 52
3-2. The comparisons of experimental and computational reduction potential. 55
3-3. Selected computational geometry parameters, natural charge, Mulliken spin density, NO vibrational frequencies, Heisenberg J coupling constant and reaction free energy for [(NO)2Fe(μ-S)2Fe(NO)2]2– (G), [(NO)(HS)Fe(μ-S)2Fe(SH)(NO)]2– (H) and [(HS)2Fe(μ-S)2Fe(SH)2]2– (I). 58
3-4. Selected experimental, computational geometry parameters, bond order, natural charge, Mulliken spin density and NO vibrational frequencies for [(HS)2Fe(NO)2]– (1 (experiment)), [(HS)2Fe(NO)2]– (A (computation)) and [(HS)2Fe(NO)2]2– (B (computation)). 59
3-5. Selected computational geometry parameters, bond order, natural charge, Mulliken spin density and NO vibrational frequencies for [(HS)3Fe(NO)]– (C) and [(HS)3Fe(NO)]2– (D). 60
3-6. Selected computational geometry parameters, bond order, natural chrage and Mulliken spin density for [Fe(SH)4]– (E) and [Fe(SH)4]2– (F). 61






Scheme

1-1. RSNO藉由自由基反應產生一氧化氮 6
3-1. Formation of complex 1 30
3-2. (a) complex 1釋放H2S並生成complex 2. (b)由complex 2逆向反應生成complex 1. 37
3-3. NBD-SCN和H2S反應之proposed reaction scheme 38
3-4. Complex 1-PPN在真空下放出H2S以及由RRS逆向反應 38
3-5. Formation of complex 3 and complex 4 39
3-6. Formation of complex 5 and complex 6 49

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