在生物體中，將NO轉換為N2O可以透過含有heme的Nitric oxide reductases (NORs) 以及non−heme Flavo−diiron NO reductases (FNORs)。對於其反應機構仍有許多爭論，但在許多推測的路徑中，兩個NO經由耦合後會形成hyponitrite intermediate。
　　本研究以1,3−bis(dimethylamino)propan−2−olate (Bdmap) 為配位基，合成出雙核結構雙亞硝基鐵錯合物 (dinuclear Dinitrosyl Iron Complexes, dDNICs)，使用IR、UV、EPR、SQUID、XAS及X−ray等儀器鑑定結構，並且探討其反應性以及應用性。
　　一開始先合成化合物 [Fe(NO)2(μ−bdmap)Fe(NO)¬2(THF)] (2)，其電子結構為localized {Fe(NO)2}9−{Fe(NO)2}10，在室溫下打入等當量的NO(g) 攪拌反應，會生成以trans−hyponitrite橋接的化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3)。接著進一步進行質子化反應，在嘗試過數種酸後，最合適的是Hbdmap，除了能當量反應釋放出N2O，其共軛鹼也能配位產生化合物 [Fe(NO)2(bdmap)]2 (1)。
　　過去發表metal−hyponitrite晶體結構的文獻非常稀少，由上述的結果說明DNIC可以做為模板，誘使NO還原產生N2O，過程中產生trans−hyponitrite橋接的化合物，對於探討NOR的催化機制有很大的幫助。

　　In biological systems, nitric oxide reduction is carried out by non−heme/heme NO reductases (NORs) and non−heme flavo diiron NO reductases (FNORs). However, there is still much dispute about the catalytic routes. Hyponitrite moiety is proposed as a common intermediate among these mechanisms.
　　In this study, a series of dinuclear Dinitrosyl Iron Complexes (dDNICs) using 1,3−bis(dimethylamino)propan−2−olate (Bdmap) as ligand were synthesized and characterized by spectroscopic references. Their reactivity and applicability were also investigated.
　　The electronic structure of [Fe(NO)2(μ−bdmap)Fe(NO)¬2(THF)] (2) is localized {Fe(NO)2}9−{Fe(NO)2}10. Complex 2 react with NO(g) at room temperature to yield tetranuclear quadridentate {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) that the trans−hyponitrite ligand bridges the four Fe metal centers. Subsequently, adding Hbdmap could transfer complex 3 into [Fe(NO)¬2(μ−bdmap)]2 and release N2O.
　　There were only few crystal structures of metal−hyponitrite complexes reported. Utilizing dDNIC as a model to reduce NO is beneficial to provide a distinct insight into the mechanism of NO reduction.

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) 之鍵結 2
1−3. 雙亞硝基鐵錯合物 (Dinitrosyl Iron Complexes, DNICs) 4
1−4. 一氧化氮還原酶 (Nitric oxide reductase, NOR) 8
1−5. 連二次硝酸鹽與金屬之錯合物 (Hyponitrite complex) 14
1−6. 研究方向 21
第二章 實驗部分 22
2−1. 一般實驗 22
2−2. 儀器 22
2−2−1. 紅外線光譜儀 (Infrared spectrometer, IR) 22
2−2−2. 紫外光−可見光吸收光譜儀 (UV−Visible electronic absorption spectrometer) 22
2−2−3. X−ray 單晶繞射解析 23
2−2−4. 電子順磁共振光譜儀 (Electron paramagnetic resonance, EPR) 23
2−2−5. 超導量子干涉儀 (Superconducting Quantum Interference Device Magenetometer, SQUID) 23
2−2−6. X−ray 吸收光譜儀 (X−ray absorption spectroscopy, XAS) 23
2−3. 溶劑與藥品 24
2−3−1. 溶劑 24
2−3−2. 藥品 24
2−4. 化合物的合成與鑑定 25
2−4−1. 化合物 [Fe(NO)2(bdmap)]2 (1) 的合成 25
2−4−2. 化合物 [Fe(NO)2(μ−bdmap)Fe(NO)2(THF)] (2)的合成 26
2−4−3. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 的合成 26
2−4−4. 化合物 [(μ−Bdmap)(μ−NO2)(Fe(NO)2)2] (4) 的合成 27
2−5. 化合物之反應性 27
2−5−1. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與Methanol (MeOH) 反應 27
2−5−2. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與Ethanol (EtOH) 反應 28
2−5−3. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與tert−Butyl alcohol (TBA) 反應 28
2−5−4. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與Phenol反應 29
2−5−5. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與Acetic acid (HOAc) 反應 29
2−5−6. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與2,4−Pentanedione (Hacac)反應 30
2−5−7. 化合物 {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 與Hbdmap反應 30
2−6. 晶體結構解析 31
第三章 結果與討論 35
3−1. [Fe(NO)2(bdmap)]2 (1) 之合成與光譜分析 35
3−2. [Fe(NO)2(μ−bdmap)Fe(NO)2(THF)] (2) 之合成與光譜分析 37
3−3. {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 之合成與光譜分析 40
3−4. [(μ−Bdmap)(μ−NO2)(Fe(NO)2)2] (4) 之合成與光譜分析 47
3−5. 化合物1−3之X−ray吸收光譜分析 49
3−6. {[Fe(NO)2]2(bdmap)}2(κ4−N2O2) (3) 之質子化反應 51
3−6−1. Complex 3 與Methanol (MeOH) 反應 51
3−6−2. Complex 3 與Ethanol (EtOH) 反應 54
3−6−3. Complex 3 與tert−Butyl alcohol (TBA) 反應 56
3−6−4. Complex 3 與Phenol反應 57
3−6−5. Complex 3 與Acetic acid (HOAc) 反應 58
3−6−6. Complex 3 與2,4−Pentanedione (Hacac) 反應 59
3−6−7. Complex 3 與Hbdmap反應 61
第四章 結論 64
Reference 66

1.Furchgott, R.F.; Zawadzki, J.V. Nature 1980, 288, 373.
2.(a) Ignarro, L. J.; Adams, J. B.; Horwitz, P. M.; Wood, K. S. J. Bioinorg. Chem. 1986, 261, 4997. (b) Ignarro, L. J.; Buga, G. M.; Wood, K. S.; Byrns, R. E.; Chaudhuri, G. Proc. Natl. Acad. Sci. 1987, 84, 9265.
3.Koshland, D. E. Science 1992, 258, 1861.
4.Gary, L. M.; Donald, A. T., Inorganic Chemistry, 2nd ed., Upper Saddle River, New Jersey: Prentice Hall International, Inc., 1999, 44.
5.Pierri, A. E.; Muizzi, D. A.; Ostrowski, A. D., Photo-Controlled Release of NO and CO with Inorganic and Organometallic Complexes, Berlin, Heidelberg: Springer Berlin Heidelberg, 2015, 1-45.
6.Enemark, J. H.; Feltham, T. 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) Goldstein, 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.Wang, X.; Sundberg, E. B.; Li, L.; Kantardjieff, K. A.; Herron, S. R.; Lim, M.; Ford, P. C. Chem. Commum. 2005, 477.
14.(a) Albano, V. G.; Areneo, A.; Bellon, P. L.; Ciani, G.; Manassero, M. J. Organomet. Chem. 1974, 67, 413. (b) Chau, C.-N.; Wojcicki, A.; Calligaris, M.; Nardin, G. Inorg. Chim. Acta. 1990, 168, 105. (c) Reginato, N.; McCrory, C. T. C.; Pervitsky, D.; Li, L. J. Am. Chem. Soc. 1999, 168, 105. (d) Hung, M.-C.; Tsai, M.-C.; Lee, G.-H.; Liaw, W.-F. Inorg. Chem. 2006, 45, 6041.
15.Shih, W. C.; Lu, T.-T., Yang,L.-B.; Tsai, F.-T.; Chiang, M.-H.; Lee, J.-F.; Chiang,Y.-W.; Liaw, W.-F. J. Inorg. Biochem. 2012, 113, 83.
16.Tsai, F.-T.; Kuo T.-S.; Liaw, W.-F. J. Am. Chem. Soc. 2009, 131,1.
17.Tsai, M.-L., Tsou, C.-C., Liaw, W.-F. Acc. Chem. Res. 2015, 48, 1184.
18.(a) Tsou, C.-C.; Lu, T.-T.; Liaw, W.-F. J. Am. Chem. Soc. 2007, 129, 12626. (b) Chen, Y.-J.; Ku, W.-C.; Feng, L.-T.; Tsai, M.-L.; Hsieh, C.-H.; Hsu, W.-H.; Liaw, W.-F.; Hung, C.-H.; Chen, Y.-J. J. Am. Chem. Soc. 2008, 130, 10929. (c) Tsai, F.-T.; Kuo, T.-S.; Liaw, W.-F. J. Am. Chem. Soc. 2009, 131, 3426. (d) Tsai, M.-C.; Tsai, F.-T.; Lu, T.-T.; Tsai, M.-L.; Wei, Y.-C.; Hsu, I. J.; Lee, J.-F.; Liaw, W.-F. Inorg. Chem. 2009, 48, 9579. (e) Lu, T.-T.; Chen, C.-H.; Liaw, W.-F. Chem. Eur. J. 2010, 16, 8088. (f) Tsai, F.-T.; Chen, P.-L.; Liaw, W.-F. J. Am. Chem. Soc. 2010, 132, 5290. (g) Tsou, C.-C.; Liaw, W.-F. Chem. Eur. J. 2011, 17, 13358. (h) Shih, W. C.; Lu, T. T.; Yang, L. B.; Tsai, F. T.; Chiang, M. H.; Lee, J. F.; Chiang, Y. W.; Liaw, W. F. J. Inorg. Biochem. 2012, 113, 83. (i) Tsai, F.-T.; Lee, Y.-C.; Chiang, M.-H.; Liaw, W.-F. Inorg. Chem. 2013, 52, 464. (j) Yeh, S.-W.; Lin, C.-W.; Li, Y.-W.; Hsu, I. J.; Chen, C.-H.; Jang, L.-Y.; Lee, J.-F.; Liaw, W.-F. Inorg. Chem. 2012, 51, 4076. (k) Tsou, C.-C.; Chiu, W.-C.; Ke, C.-H.; Tsai, J.-C.; Wang, Y.-M.; Chiang, M.-H.; Liaw, W.-F. J. Am. Chem. Soc. 2014, 136, 9424. (l) Yeh, S.-W.; Tsou, C.-C.; Liaw, W.-F. Dalton Trans. 2014, 43, 9022. (m) Reginato, N.; McCrory, C. T. C.; Pervitsky, D.; Li, L. J. Am. Chem. Soc. 1999, 121, 10217.
19.Tsou, C.-C.; Tsai, F.-T.; Chen, H.-Y.; Hsu, I. J.; Liaw, W.-F. Inorg. Chem. 2013, 52, 1631.
20.(a) Lin, Z.-S.; Lo, F.-C.; Li, C.-H.; Chen, C.-H.; Huang, W.-N.; Hsu, I. J.; Lee, J.-F.; Horng, J.-C.; Liaw, W.-F. Inorg. Chem. 2011, 50, 10417. (b) Lu, T.-T.; Lai, S.-H.; Li, Y.-W.; Hsu, I. J.; Jang, L.-Y.; Lee, J.-F.; Chen, I. C.; Liaw, W.-F. Inorg. Chem. 2011, 50, 5396.
21.Ravishankara, A. R. ; Daniel, J. S. ; Portmann, R.W. Science 2009, 326, 123.
22.Pierre, M.-L. Nat. Prod. Rep., 2007, 24, 610.
23.Hino, T.; Matsumoto, Y.; Nagano, S.; Sugimoto, H.; Fukumori, Y.; Murata, T.; Iwata, S.; Shiro, Y. Science, 2010, 330, 1666.
24.Matsumoto, Y.; Tosha, T.; Pisliakov, A. V.; Hino, T.; Sugimoto, H.; Nagano, S.; Sugita, Y.; Shiro, Y. Nat. Struct. Mol. Biol., 2012, 19, 238.
25.Schopfer, M. P.; Wang, J.; Karlin, K. D. Inorg. Chem. 2010, 49, 6267.
26.Kumita, H.; Matsuura, K.; Hino, T.; Takahashi, S.; Hori, H.; Fukumori, Y.; Morishima, I.; Shiro, Y. J. Biol. Chem., 2004, 279, 55247.
27.(a) Ye, R. W.; Averil, B. A.; Tiedje, J. M. Appl. Environ. Microbiol., 1994, 60, 1053. (b) Bryar, T. R.; Eaton, D. R. Can. J. Chem., 1992, 70, 1917. (c) Wang, X.; Sundberg, E. B.; Li, L.; Kantardjieff, K. A.; Herron, S. R.; Lim, M.; Ford, P. C. Chem. Commun., 2005, 477.
28.(a) Frazao, C.; Silva, G.; Gomes, C. M.; Matias, P.; Coelho, R.; Sieker, L.; Macedo, S.; Liu, M. Y.; Oliveira, S.; Teixeira, M.; Xavier, A. V.; Rodrigues-Pousada, C.; Carrondo, M. A.; Le, G. J. Nat. Struct. Mol. Biol., 2000, 7, 1041. (b) Silaghi-Dumitrescu, R.; Kurtz, D. M.; Ljungdahl, L. G.; Lanzilotta, W. N. Biochemistry, 2005, 44, 6492. (c) Hayashi, T.; Caranto, J. D.; Wampler, D. A.; Kurtz, D. M.; Moenne-Loccoz, P. Biochemistry, 2010, 49, 7040. (d) Arkenberg, A.; Runkel, S.; Richardson, D. J.; Rowley, G. Biochem. Soc. Trans., 2011, 39, 1876.
29.Kurtz, D. M. Dalton Trans., 2007, 4115.
30.Blomberg, L. M.; Blomberg, M. R. A.; Siegbahn, P. E. M. J. Biol. Inorg. Chem., 2007, 12, 79.
31.Caranto, J. D.; Weitz, A.; Hendrich, M. P.; Kurtz, D. M. J. Am. Chem. Soc. 2014, 136, 7981.
32.Van Stappen, C.; Lehnert, N. Inorg. Chem. 2018, 57, 4252.
33.Wijeratne, G. B.; Hematian, S.; Siegler, M. A.; Karlin, K. D. J. Am. Chem. Soc. 2017, 139, 13276.
34.Arikawa, Y.; Asayama, T.; Moriguchi, Y.; Agari, S.; Onishi, M. J. Am. Chem. Soc. 2007, 129, 14160.
35.Arikawa, Y.; Matsumoto, N.; Asayama, T.; Umakoshi, K.; Onishi, M. Dalton Trans. 2011, 40, 2148.
36.Xu, N.; Campbell, A. L. O.; Powell, D. R.; Khandogin, J.; Richter-Addo, G. B. J. Am. Chem. Soc. 2009, 131, 2460.
37.Berto, T. C.; Xu, N.; Lee, S. R.; McNeil, A. J.; Alp, E. E.; Zhao, J. Y.; Richter-Addo, G. B.; Lehnert, N. Inorg. Chem. 2014, 53, 6398.
38.Wright, A. M.; Wu, G.; Hayton, T. W. J. Am. Chem. Soc. 2012, 134, 9930.
39.Wijeratne, G. B.; Hematian, S.; Siegler, M. A.; Karlin, K. D. J. Am. Chem. Soc. 2017, 139, 13276.
40.Kundu, S.; Phu, P. N.; Ghosh, P.; Kozimor, S. A.; Bertke, J. A.; Stieber, S. C. E.; Warren, T. H. J. Am. Chem. Soc. 2019, 141, 1415.
41.Ferretti, E.; Dechert, S.; Demeshko, S.; Holthausen, M. C.; Meyer, F. Angew. Chem. Int. Ed. Engl. 2019, 58, 1705.
42.Bau, R.; Sabherwa, I. H.; Burg, A. B. J. Am. Chem. Soc. 1971, 93, 4926.
43.Lu, T.-T.; Tsou, C.-C.; Huang, H.-W.; Hsu, I.-J.; Chen, J.-M.; Kuo, T.-S.; Wang, Y.; Liaw, W.-F. Inorg. Chem. 2008, 47, 6040-6050.
44.Tsai, F.-T.; Chen, P.-L.; Liaw, W.-F. J. Am. Chem. Soc. 2010, 132, 5290.