本研究以Bis(2-pyridylmethyl)amine (BPA) 為配位基合成出單核與雙核結構之雙亞硝基鐵錯合物(Dinuclear Dinitrosyl Iron Complex, dDNICs)，並探討其反應性與應用性。
[(BPA)Fe(NO)2] (1) 為一單核{Fe(NO)2}10 DNIC，將其去質子化後，與另一個{Fe(NO)2}10 DNIC 反應可以形成以N橋接的雙核{Fe(NO)2}10-{Fe(NO)2}10 DNIC (dDNIC) [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3)，並且以IR、UV、EPR 及 X-ray等儀器鑑定結構。將[(BPA)Fe(NO)2] (1) 以NOBF4氧化可以形成穩定的單核五配位{Fe(NO)2}9 DNIC [(BPA)Fe(NO)2][BF4] (2) ，並且在小分子反應的實驗中，發現到BPA上的N-H 在反應中扮演重要的角色，既能夠提供質子與小分子反應又可以幫助穩定{Fe(NO)2} core，使[(BPA)Fe(NO)2] (1) 能與小分子氣體有特殊反應。
在過去發表的文獻中，以N橋接的dDNIC 是相當少見的，相較於其他dDNIC，complex 3 其雙核之距離較近，當小分子配位至{Fe(NO)2}上時，可以迅速提供兩個電子，並且雙核{Fe(NO)2}10-{Fe(NO)2}10也具有高電子密度與反應活性，在進行同一配位基單/雙核的反應性實驗，更是發現了其特殊的反應性與反應路徑。

In this work, Bis(2-pyridylmethyl)amine (BPA) was adopted as ligand to synthesize a mononuclear and dinuclear Dinitrosyl Iron Complexes (dDNICs). Their reactivity were also investigated.
A singling N-bridged dinuclear {Fe(NO)2}10-{Fe(NO)2}10 DNIC (dDNIC) [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) was successfully synthesized by reacting [(TMEDA)Fe(NO)2] with the deprotonated mononuclear {Fe(NO)2}10 [(BPA)Fe(NO)2] (1). In the previous study, only few single N-bridged dDNICs were synthesized. The distance between two iron cores of complex 3 is rather shorter than those of other dDNICs. Oxidation of [(BPA)Fe(NO)2] (1) by NOBF4 afforded a non-classical five-coordinated {Fe(NO)2}9 [(BPA)Fe(NO)2][BF4] (2) . In the study of the reactivity of [(BPA)Fe(NO)2] (1) reacting with small molecules, we discovered the N-H bond of the BPA played an important role in stabilizing the {Fe(NO)2} core and triggering small molecules activation.

第一章 緒論 1
1-1. 一氧化氮 (Nitric oxide) 1
1-2. 一氧化氮(NO)與過渡金屬(M)鍵結之電子狀態 3
1-3. 雙亞硝基鐵錯合物 (Dinitrosyl Iron Complexes, DNICs) 4
1-4. DNICs與氧氣的反應 8
1-5. 鐵錯合物催化NO自身氧化還原 (Iron complex-mediated NO disproportionation) 12
1-6. 低價數過度金屬錯合物還原二氧化碳 16
1-7. 研究動機與方向 19
第二章 實驗部分 20
2-1. 一般實驗 20
2-2. 儀器 20
2-2-1. 紅外線光譜儀 (Infrared spectrometer, IR) 20
2-2-2. 紫外光-可見光吸收光譜儀 (UV-Visible electronic absorption spectrometer) 20
2-2-3. X-ray 單晶繞射解析 20
2-2-4. 電子順磁共振光譜儀 (Electron paramagnetic resonance, EPR) 21
2-2-5. 循環伏安儀 (Cyclic Voltammetry, CV) 21
2-2-6. 氣相層析儀 (Gas Chromatography, GC) 21
2-3 溶劑與藥品 21
2-3-1.藥品 21
2-3-2 溶劑 22
2-4 化合物的合成與鑑定 23
2-4-1 錯合物 [(BPA)Fe(NO)2] (1)(BPA=Bis(2-pyridylmethyl)amine)的合成 23
2-4-2 錯合物 [(BPA)Fe(NO)2][BF4] (2) 的合成 24
2-4-3 錯合物 [(TMEDA)Fe(NO)2] 的合成 (TMEDA: Tetramethylethylenediamine) 25
2-4-4 錯合物 [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 的合成 25
2-5 化合物的反應性 26
2-5-1. 錯合物[(BPA)Fe(NO)2] (1) 與O2(g)反應 26
2-5-2. 錯合物[(deH-BPA)(Fe(NO)2)2][18-crown-6-ether-K] (3) 與O2(g)反應 27
2-5-3. 錯合物[(BPA)Fe(NO)2] (1) 與NO(g)反應 27
2-5-4. 錯合物[18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 與NO(g)反應 28
2-5-5. 錯合物[18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3)與CO2(g)反應 28
2-6 電化學 28
2-7 晶體結構解析 29
第三章 實驗結果與討論 32
3-1 錯合物之合成、結構與光譜分析 32
3-1-1錯合物 [(BPA)Fe(NO)2] (1) 之合成、結構與光譜分析 32
3-1-2錯合物[(BPA)Fe(NO)2][BF4] (2) 之合成、結構與光譜分析 35
3-1-3錯合物[18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 之合成、結構與光譜分析 37
3-2 [(BPA)Fe(NO)2] (1) 與[(deH-BPA)(Fe(NO)2)2][18-crown-6-ether-K] (3) 的氧化與光譜分析 41
3-2-1 [(BPA)Fe(NO)2] (1) 與NOBF4反應 41
3-2-2 [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 與NOSbF6反應 42
3-2-3 [(BPA)Fe(NO)2] (1) 與O2(g)反應 43
3-2-4 [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 與O2(g)反應 47
3-3 [(BPA)Fe(NO)2] (1) 與 [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 的氣體反應性與光譜分析 49
3-3-1. [(BPA)Fe(NO)2] (1) 與NO(g)反應 49
3-3-2. [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 與NO(g) 反應 52
3-3-3. [(BPA)Fe(NO)2] (1) 與CO2(g)的反應性與光譜分析 52
3-3-4. [18-crown-6-ether-K][(deH-BPA)(Fe(NO)2)2] (3) 與CO2(g)的反應性與光譜分析 53
3-4. [(deH-BPA)Fe(NO)2] (A) 的反應性與光譜分析 55
第四章 結論 57
Reference 60

1. Furchgott, R.F.; Zawadzki, J.V. Nature 1980, 288, 373.
2. Ignarro, L. J.; Buga, G. M.; Wood, K. S.; Byrns, R. E.; Chaudhuri, G. Proc. Natl. Acad. Sci. 1987, 84, 9265.
3. (a) Wang, P. G.;Xian, M.; Tang, X.; Wu, X.; Wen, Z.; Cai, T.; Janczuk, A. J. Chem. Rev. 2002, 102, 1091. (b) Lee, J.;Chen, L.; West, A. H.; Richter-addo, G. B.Chem. Rev. 2002, 102, 1091. (c) Stamler, J. S.; Single, D. J.;Loscalzo. J. Science 1992, 258, 1898
4. Koshland, D. E. Science 1992, 258, 1861.
5. (a)Gary, L. M.; Donald, A. T., Inorganic Chemistry, 2nd ed., Upper Saddle River, New Jersey: Prentice Hall International, Inc., 1999, 44.
(b)Ke, C. H.,Chen, C. H., Tsai, M. L., Wang, H. C., Tsai, F. D., Chiang, Y. W. Shih W. C., Bohle, D. S., Liaw, W. F. J. Am. Chem. Soc.2017, 139, 1, 67-70
6. Enemark, J. H.; Feltham, R. D. Coord. Chem. Rev. 1974, 13, 339.
7. (a) Butler, A. R.; Megson, I. L. Chem. Rev. 2002, 102, 1155. (b) Ueno, T.; Susuki, Y.; Fujii, S.; Vanin, A. F.; Yoshimura, T. Biochem. Pharmacol. 2002, 63, 485. (c) Frederik., A. C.; Wiegant, I. Y.; Malyshev, I. Y.; Kleschyov, A. L.; van Faassen, E.; Vanin, A. F. FEBS Lett. 1999, 455, 179. (d) McCleverty, J. A. Chem. Rev. 2004, 104, 403. (e) Hayton, T. W.; Legzdins, P.; Sharp, W. B. Chem. Rev. 2002, 102, 935.
8. (a) Kharitonov, V. G.; Sundquist, A. R.; Sharma, V. S. J. Biol. Chem. 1995, 270, 2815. (b) Goldstien, S.; Czapski, G. J. Am. Chem. Soc. 1996, 118, 3419.
9. McDonald, C. C.; Phillips, W. D.; Mower, H. F. J. Am. Chem. Soc. 1965, 87, 3319.
10. Cesareo, E.; Parker, L. J.; Pedersen, J. Z.; Nuccetelli, M.; Mazzetti, A. P.; Pastore, A.; Federici, G.; Caccuri, A. M.; Ricci, G.; Adams, J. J.; Parker, M. W.; Bello, M. L. J. Biol. Chem. 2005, 280, 42172.
11. Gwost, D.; Caulton, K. D. Inorg. Chem. 1973, 12, 2095.
12. (a) Baltusis, L. M.; Karlin, K. D.; Rabinowitz, H. N.; Dewan, J. C.; Lippard, S. J. Inorg. Chem. 1980, 19, 2627. (b) Strasdeit, H.; Krebs, B.; Henkel, G. Z. Naturforsch. 1986, 41b, 1357. (c) Bryar, T. R.; Eaton, D. R. Can. J. Chem. 1992, 70, 1917. (d) Osterloh, F.; Saak, W.; Haase, D.; Pohl, S. Chem. Commun. 1997, 979. (e) Liaw, W.-F.; Chiang, C.-Y.; Lee, G.-H.; Peng, S.-M.; Lai, C.-H. Inorg. Chem. 2000, 39, 480. (f) Davies, S. C.; Evans, D. J.; Hughes, D. L.; Konkol, M.; Richards, R. L.; Sanders, J. R.; Sobota, P. J. Chem. Soc., Dalton Trans. 2002, 2473. (g) Chiang, C.-Y.; Miller, M. L.; Reibenspies, J. H.; Darensbourg, M. Y. J. Am. Chem. Soc. 2004, 126, 10867. (h) Tsai, M.-L.; Chen, C.-C.; Hsu, I.-J.; Ke, S.-C.; Hsieh, C.-H.; Chiang, K.-A.; Lee, G.-H.; Wang, Y.; Liaw, W.-F. Inorg. Chem. 2004, 43, 5159. (i) Tsai, F.-T.; Chiou, S.-J.; Tsai, M.-C.; Tsai, M.-L.; Huang, H.-W.; Chiang, M.-H.; Liaw, W.-F. Inorg. Chem. 2005, 44, 5872. (j) Lu, T.-T.; Chiou, S.-J.; Chen, C.-Y.; Liaw, W.-F. Inorg. Chem. 2006, 45, 8799. (k) Tsai, M.-L.; Hsieh, C.-H.; Liaw, W.-F. Inorg. Chem. 2007, 46, 5110. (l) Huang, H.-W.; Tsou, C.-C.; Kuo, T.-S.; Liaw, W.-F. Inorg. Chem. 2008, 47, 2196.
13. Hung, M.-C.; Tsai, M.-C.; Lee, G.-H.; Liaw, W.-F. Inorg. Chem. 2006, 45, 6041.
14. Wang, X.; Sundberg, E. B.; Li, L.; Kantardjieff, K. A.; Herron, S. R.; Lim, M.; Ford, P. C. Chem. Commum. 2005, 477.
15. (a) Tsai, M. L.; Tsou, C. C.; Liaw, W. F., Acc. Chem. Res. 2015, 48, 1184-1193 (b) Tran, C. T.; Skodjt, K. M.; Kim, E. Prog. Inorg. Chem. 2014, 59, 339-379
16. Tran, N. G.; Kalyvas, H.; Skodje, K. M.; Hayashi, T.; Moenne-Loccoz, P.; Callan, P. E.; Shearer, J.; Kirschenbaum, L. J.; Kim, E., J. Am. Chem. Soc. 2011, 133, 1184-1187
17. Banerjee, A. B.; Sen, S.; Paul, A., Chem. Eur. J, 2018, 24, 3330-3339
18. Skodje, K. M.; Williard, P. G.; Kim, E., Dalton. Trans. 2012, 41, 7849-7851
19. Tonzetich, Z. J.; Do, L. H., Lippard, S. J., J. Am. Chem. Soc, 2009, 131, 7964- 7965
20. Fitzpatrick, J.; Kalyvas, H.; Shearer, J.; Kim, E., Chem. Commun., 2013, 49, 5550-5552
21. Zumft, W. G.: Cell biology and molecular basis of denitrification. Microbiology and Mololecular Biology Reviews. Bd. 61, 1997, 533-616
22. Shiro, Y.; Sugimoto, H.; Tosha, T.; Nagano, S.; Hino, T., Phil. Trans. R. Soc. B 2012, 367, 1195-1203
23. Pierre, M.-L. Nat. Prod. Rep., 2007, 24, 610.
24. Khatua, S.; Majumdar, A. Flavodiiron nitric oxide reductases: Recent developments in the mechanistic study and model chemistry for the catalytic reduction of NO. J. Inorg. Biochem. 2015, 142, 145– 153
25. Zheng, S.; Berto, T. C.; Dahl, E. W.; Hoffman, M. B.; Speelman, A. L.; Lehnert, N., J. Am. Chem. Soc.2013, 135, 13, 4902-4905
26. Stappen, C. V.; Lehnert, N., Inorg. Chem. 2018, 578, 4252-4269
27. Confer, A. M.; McQuilken, A. C.; Matsumura, H.; Moenne-Loccoz, P.; Goldberg, D. P., J. Am. Chem. Soc. 2017, 139, 10621-10624
28. Jeoung, J-H.; Dobbek, H., Science. 2007, 318, 1461 
29. Saouma, C. T.;Lu, C. C.; Day, M. W.; Peters, J. C., chem. Sci. 2013, 4, 4042-4051
30. Lee, C. H.; Laiter, D. S.; Mueller, P.; Sadighi, J. P., J. Am. Chem. Soc. 2007, 129, 45, 13802-13803
31. Viasus, C. J.; Alderman, N. P.; Gabidullin, B.; Gambarotta, S., Angew. Chem. Int. Ed. 2018, 57, 10928
32. Wang, R.; Wang, X; Sundberg E. B.; Nguyen, P.; Grant, G. P, G.; Sheth, C.; Zhao, Q.; Herron, S.; Kantardjieff K. A.; Li, L., Inorg. Chem. 2009, 48, 20, 9779-9785
33. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds, 4th ed., Hoboken, New Jersey: John Wiley & Sons, Inc., 2009, ch.1