臺灣博碩士論文加值系統

Tris[3-(2-pyridyl)pyrazolyl]hydroborate 配位基在活化小分子的金屬催化&;#37238;的例子中是非常重要的。但是KTp(py)在文獻中，並沒有KTp(py)以鐵二價為中心的模型化合物的例子。這是很令人好奇的因為在自然界中常常看到，以鐵為活性中心活化小分子的例子。因此本文採用鐵為中心的化合物[Tp(py)FeCl]。利用外懸臂模擬金屬催化&;#37238;的氨基酸殘基或是形成氫鍵以穩定化合物的存在。本文進一步的去測試Tp(py)FeCl的反應性，並去模擬金屬催化&;#37238;的模型化合物，如Nitrite Reductase的亞硝酸鹽金屬螯合物，與模擬Methane monooxygenase系統中的中間產物Tp(py)FeOH，或是模擬 Cytochrome P450與Catechol Dioxygenases的高價金屬氧化態的前驅物[Tp(py)FeN3](1) 的晶體結構以及IR光譜。在其它反應性方面也成功的得到[Tp(py)FeCN](2)的IR光譜,以及NMR的光譜圖譜。

Trispyrazolylborate (Tp&;#8722;) type compound is a very important ligand set for small molecules activation the metalloenzyme mimicking system. Tris[3-(2-pyridyl)pyrazolyl]-hydroborate (Tp(py)&;#8722;) is a new type of Tp- ligand set which provides additional pyridine coordination site in 3-postion to explore some new coordination behavior for metal complexes. It is worth mentioning that there are no example of iron complexes containing Tp(py)&;#8722; ligand. Therefore, we focus on the synthesis and reactivity study of Tp(py)FeCl compound for the outer pyridine arm may mimic the amino acid residue around metalloenzyme active center. The Tp(py)FeCl complex represents as the first example of iron complex containing Tp(py)&;#8722; ligand and the dangling pyridine arm can be used to mimic the second sphere coordination environment of the iron containing enzyme active site. The coordinated chloride ligand were replaced by N3&;#8722; and CN&;#8722; in DMF solution to give Tp(py)FeN3 (1) and Tp(py)FeCN (2) respectively. The structure of complex 1 was characterized by X-ray crystallography showing a five-coordination Fe(II) center similar to that of Tp(py)FeCl. Complexes 1 and 2 were all examined by UV-vis and Infrared spectroscopies. Complex 2 also can be characterized by NMR spectroscopy to confirm the low spin electron configuration and diamagnetism.

摘要 VIII
Abstract IX
第壹章、前言 1
1-1、氮循環: 1
1-2、Nitrite Reductase: 6
1-3、Cytochrome P450: 8
1-4、Methane monooxygenase: 10
1-5、Catechol Dioxygenases 13
1-6、高價氧化態鐵化合物: 16
1-7、Tris[3-(2-pyridyl)pyrazolyl]hydroborate Iron chloride: 19
1-8、外源性生物配位基(Exogenous Biological Ligands): 23
1-9、研究目的 25
第貳章、結果與討論 26
2-1、化合物Tp(py)FeN3(1)的合成 26
2-2、化合物Tp(py)FeCN(2)的合成 33
2-3、化合物Tp(py)FeN3(1)的探討 38
2-4、化合物Tp(py)FeCN(2)的探討 46
2-5、 Tp(py)FeCl化合物的其它反應與合成探討 49
第&;#21442;章、結論 51
第肆章、實驗部分 52
4.1試藥來源及前處理 52
4.2儀器部分 54
4.3實驗步驟 56
參考文獻 60

(1)Maia, L. B.; Moura, J. J. G. Chemical Reviews 2014, 114, 5273.
(2)Meyer, F.; Tolman, W. B. Inorganic Chemistry 2015, 54, 5039.
(3)Coyne, M. S.; Arunakumari, A.; Averill, B. A.; Tiedje, J. M. Applied and -Environmental Microbiology 1989, 55, 2924.
(4)Williams, P. A.; Fulop, V.; Garman, E. F.; Saunders, N. F.; Ferguson, S. J.; Hajdu, -J. Nature 1997, 389, 406.
(5)Nurizzo, D.; Cutruzzol&;#224;, F.; Arese, M.; Bourgeois, D.; Brunori, M.; Cambillau, -C.; Tegoni, M. Biochemistry 1998, 37, 13987.
(6)Marques, N.; Sella, A.; Takats, J. Chemical Reviews 2002, 102, 2137.
(7)Lorkovi&;#263;, I.; Ford, P. C. Journal of the American Chemical Society 2000, 122, -6516.
(8)Nasri, H.; Haller, K. J.; Wang, Y.; Huynh Boi, H.; Scheidt, W. R. Inorganic -Chemistry 1992, 31, 3459.
(9)Patterson, J. C.; Lorkovi&;#263;, I. M.; Ford, P. C. Inorganic Chemistry 2003, 42, 4902.
(10)Nasri, H.; Ellison, M. K.; Krebs, C.; Huynh, B. H.; Scheidt, W. R. Journal of the American Chemical Society 2000, 122, 10795.
(11)Wang, J.; Schopfer, M. P.; Sarjeant, A. A. N.; Karlin, K. D. Journal of the -American Chemical Society 2009, 131, 450.
(12)Arulsamy, N.; Bohle, D. S.; Hansert, B.; Powell, A. K.; Thomson, A. J.; Wocaldo, -S. Inorganic Chemistry 1998, 37, 746.
(13)Sono, M.; Roach, M. P.; Coulter, E. D.; Dawson, J. H. Chemical Reviews 1996, 96, 2841.
(14)Sirajuddin, S.; Rosenzweig, A. C. Biochemistry 2015, 54, 2283.
(15)Citek, C.; Gary, J. B.; Wasinger, E. C.; Stack, T. D. P. Journal of the American -Chemical Society 2015.
(16)Chidambarampadmavathy, K.; Obulisamy P, K.; Heimann, K. Engineering in -Life Sciences 2015, 15, 387.
(17)Sigdel, S.; Hui, G.; Smith, T. J.; Murrell, J. C.; Lee, J.K. Bioorganic &; -Medicinal Chemistry Letters 2015, 25, 1611.
(18)Costas, M.; Mehn, M. P.; Jensen, M. P.; Que, L. Chemical Reviews 2004, 104, 939.
(19)Que, L.; Ho, R. Y. N. Chemical Reviews 1996, 96, 2607.
(20)Bennett, B. K.; Lovell, S.; Mayer, J. M. Journal of the American Chemical -Society 2001, 123, 4336.
(21)Slep, L. D.; Mijovilovich, A.; Meyer-Klaucke, W.; Weyherm&;#252;ller, T.; Bill, E.; -Bothe, E.; Neese, F.; Wieghardt, K. Journal of the American Chemical Society 2003, 125, 15554.
(22)Rohde, J.-U.; Torelli, S.; Shan, X.; Lim, M. H.; Klinker, E. J.; Kaizer, J.; Chen, -K.; Nam, W.; Que, L. Journal of the American Chemical Society 2004, 126, 16750.
(23)Lim, M. H.; Rohde, J.U.; Stubna, A.; Bukowski, M. R.; Costas, M.; Ho, R. Y. N.; M&;#252;nck, E.; Nam, W.; Que, L. Proceedings of the National Academy of Sciences 2003, 100, 3665.
(24)Rohde, J.-U.; In, J.-H.; Lim, M. H.; Brennessel, W. W.; Bukowski, M. R.; Stubna, A.; M&;#252;nck, E.; Nam, W.; Que, L. Science 2003, 299, 1037.
(25)Zheng, H.; Yoo, S. J.; M&;#252;nck, E.; Que, L. Journal of the American Chemical -Society 2000, 122, 3789.
(26)Costas, M.; Rohde, J.-U.; Stubna, A.; Ho, R. Y. N.; Quaroni, L.; M&;#252;nck, E.; Que, -L. Journal of the American Chemical Society 2001, 123, 12931.
(27)Crevier, T. J.; Bennett, B. K.; Soper, J. D.; Bowman, J. A.; Dehestani, A.; Hrovat, -D. A.; Lovell, S.; Kaminsky, W.; Mayer, J. M. Journal of the American Chemical -Society 2001, 123, 1059.
(28)Crevier, T. J.; Lovell, S.; Mayer, J. M.; Rheingold, A. L.; Guzei, I. A. Journal of -the American Chemical Society 1998, 120, 6607.
(29)Betley, T. A.; Peters, J. C. Journal of the American Chemical Society 2004, 126, 6252.
(30)Wagner, W. D.; Nakamoto, K. Journal of the American Chemical Society 1988, 110, 4044.
(31)Meyer, K.; Bill, E.; Mienert, B.; Weyherm&;#252;ller, T.; Wieghardt, K. Journal of the -American Chemical Society 1999, 121, 4859.
(32)Crevier, T. J.; Mayer, J. M. Angewandte Chemie International Edition 1998, 37, 1891.
(33)Gu, S.-Y.; Sheu, J.-H.; Su, M.-D. Inorganic Chemistry 2007, 46, 2028.
(34)Singh, U. P.; Aggarwal, V.; Kashyap, S. Journal of Coordination Chemistry 2009, 62, 3157.
(35)Amoroso, A. J.; Thompson, A. M. C.; Jeffery, J. C.; Jones, P. L.; McCleverty, J. -A.; Ward, M. D. Journal of the Chemical Society, Chemical Communications 1994, 2751.
(36)Kitajima, N.; Tolman, W. B. In Progress in Inorganic Chemistry; John Wiley &; -Sons, Inc.: 2007, p 419.
(37)Davies, G. M.; Adams, H.; Ward, M. D. Acta Crystallographica Section C 2005, 61, m221.
(38)Kealey, S.; White, A. J. P.; Gee, A. D.; Long, N. J. European Journal of -Inorganic Chemistry 2014, 2014, 1896.
(39)Amoroso, A. J.; Jeffery, J. C.; Jones, P. L.; McCleverty, J. A.; Ward, M. D. -Polyhedron 1996, 15, 2023.
(40)Bardwell, D. A.; Jeffery, J. C.; Jones, P. L.; McCleverty, J. A.; Ward, M. D. -Journal of the Chemical Society, Dalton Transactions 1995, 2921.
(41)Davies, G. M.; Aarons, R. J.; Motson, G. R.; Jeffery, J. C.; Adams, H.; Faulkner, -S.; Ward, M. D. Dalton Transactions 2004, 1136.
(42)Holm, R. H.; Kennepohl, P.; Solomon, E. I. Chemical Reviews 1996, 96, 2239.
(43)Vincent, K. A. Triggered infrared spectroscopy for investigating metalloprotein -chemistry, 2010; Vol. 368.
(44)Han, J.; Blackburn, N. J.; Loehr, T. M. Inorganic Chemistry 1992, 31, 3223.
(45)Callan, B.; Manning, A. R.; Stephens, F. S. Journal of Organometallic Chemistry 1987, 331, 357.
(46)Scepaniak, J. J.; Bontchev, R. P.; Johnson, D. L.; Smith, J. M. Angewandte -Chemie International Edition 2011, 50, 6630.
(47)Fukui, H.; Ito, M.; Morooka, Y.; Kitajima, N. Inorganic Chemistry 1990, 29, 2868.
(48)Malvolti, F.; Trujillo, A.; Cador, O.; Gendron, F.; Costuas, K.; Halet, J.-F.; -Bondon, A.; Toupet, L.; Molard, Y.; Cordier, S.; Paul, F. Inorganica Chimica Acta 2011, 374, 288.
(49)Scepaniak, J. J.; Young, J. A.; Bontchev, R. P.; Smith, J. M. Angewandte Chemie -International Edition 2009, 48, 3158.
(50)Scepaniak, J. J.; Fulton, M. D.; Bontchev, R. P.; Duesler, E. N.; Kirk, M. L.; -Smith, J. M. Journal of the American Chemical Society 2008, 130, 10515.
(51)Kim, J.; Han, S.; Cho, I.-K.; Choi, K. Y.; Heu, M.; Yoon, S.; Suh, B. J. -Polyhedron 2004, 23, 1333.
(52)Li, D.; Parkin, S.; Wang, G.; Yee, G. T.; Holmes, S. M. Inorganic Chemistry 2006, 45, 1951.
(53)Nihei, M.; Ui, M.; Hoshino, N.; Oshio, H. Inorganic Chemistry 2008, 47, 6106.