簡易檢索 / 詳目顯示

研究生: 陳稚愷
Chen, Jhin-Kai
論文名稱: 含銅蛋白質活性中心之擬態化合物研究— 含氮硫三牙基之一價錯合物之合成、結構及反應性探討
Synthesis, Structure, and Reactivity of Tridentate N/S Ligand of Copper(I) Complexes—Mimics for the Active Site of Copper Containing Proteins
指導教授: 李位仁
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2009
畢業學年度: 97
語文別: 中文
論文頁數: 94
中文關鍵詞: 含銅蛋白擬態化合物
論文種類: 學術論文
相關次數: 點閱:121下載:0
分享至:
查詢本校圖書館目錄 查詢臺灣博碩士論文知識加值系統 勘誤回報
  • 為了模擬藍銅蛋白以及胜肽甘胺酸-羥化氧化酶(Peptidylglycine -hydroxylating monooxygenase,簡稱PHM)的活性中心,我們合成出兩個含氮硫之三牙配位基(BMIMS)與(MITMB),並成功地合成出兩個具有BMIMS與MITMB的一價銅錯合物:[Cu2(BMIMS)2](CF3SO3)2 (1)和[Cu2(MITMB)2](CF3SO3)2 (4)。將錯合物1與硫醇鹽[SC6H4COO]2-、[SC6F5]-以及[SC6H4Si(CH3)3]-反應,其產物由核磁共振氫譜推測,有[Cu(BMIMS)SC6H4COO-]、[Cu(BMIMS)SC6F5]以及[Cu(BMIMS)SC6H4Si(CH3)3]的生成。將雙核結構的錯合物1和錯合物4與PPh3、CNC(CH3)3、CO等小分子反應則可形成一系列的單核錯合物:[Cu(BMIMS)PPh3](CF3SO3) (2)、[Cu(BMIMS)CNC(CH3)3](CF3SO3) (3)以及[Cu(MITMB)PPh3](CF3SO3) (5),而[Cu(BMIMS)(CO)](CF3SO3)與[Cu(MITMB)(CO)](CF3SO3)分子的生成由IR光譜鑑定,顯示錯合物1與4都具有良好的反應性。並且藉由核磁共振光譜與IR光譜,得知配子BMIMS的供給電子能力是略強於MITMB。若將氧氣與錯合物1在甲醇/乙腈溶液下反應,以紫外-可見光光譜偵測該溶液可發現在兩組電荷轉移吸收峰在304 nm 、352 nm類似於Cu(II)-OOH錯合物的吸收光譜。

    In order to mimic the active site of blue copper protein and peptidylglycine hydroxylating monooxygenase (PHM), we have synthesized two N2S(thioether) ligands, bis(4-methylimidazol-5-yl- methyl) sulfide (BMIMS) and 2-(4-Methylimidazol-5-ylmethyl)- thiomethyl-1-methylbenzoimidazole (MITMB). Two Cu(I) complexes of BMIMS and MITMB, [Cu2(BMIMS)2](OTf)2 (1) and [Cu2(MITMB)2]- (OTf)2 (4) have been successfully synthesized and fully characterized. We aimed to model the active site of the reduced form of blue copper protein by reacting complex 1 with thiosalicylic acid, pentafluoro- thiophenol and 2-(trimethylsilyl)benzenethiol, respectively. 1H-NMR spectra of the isolate products suggested the formation of [Cu(BMIMS)- SC6H4COO-], [Cu(BMIMS)SC6F5] and [Cu(BMIMS)SC6H4Si(CH3)3]. The dinuclear complexes 1 and 4 exhibit excellent reactivities toward small molecules, such as PPh3, CNC(CH3)3, and CO. Mononuclear Cu(I) complexes, [Cu(BMIMS)PPh3](OTf) (2), [Cu(BMIMS)CNC(CH3)3](OTf) (3) and [Cu(MITMB)PPh3](OTf) (5), were formed and structurally characterized, and [Cu(BMIMS)(CO)](OTf), [Cu(MITMB)(CO)](OTf) were characterized by IR. NMR and IR spectra illustrate that BMIMS is a stronger electron-donating ligand compared to MITMB. The reaction of dioxygen with complex 1 in a methanol/acetonitrile mixed solution monitored by UV-vis spectroscopy exhibited two charge transfer absorption bands at 304 nm and 352 nm . The UV-vis spectrum of the resulting species is similar to that of copper(II) hydroperoxide complexes.

    中文摘要..................................................Ι英文摘要..................................................Ⅱ 圖索引....................................................Ⅲ 表索引....................................................Ⅷ 附錄索引..................................................Ⅸ 第一章 緒論 第一節 研究動機與目的………………………..….………………..1 第二節 研究背景...........................................3 第三節 相關文獻探討......................................11 第四節 一價銅的配位幾何構形介紹……………………………....23 第二章 實驗部分 第一節 實驗儀器、藥品及條件…………..…………...………..25 第二節 配位基的合成與鑑定……………..……………………….33 第三節 一價銅錯合物的合成……………………...………………39 第四節 一價銅錯合物與硫醇鹽類的反應…………………...……44 第三章 結果與討論 第一節 配子的合成與討論…………………………………....……51 第二節 配子BMIMS的一價銅錯合物合成、結構之探討......…….57 第三節 配子MITMB的一價銅錯合物合成、結構之探討...........72 第四節 含氮硫三牙基BMIMS與硫醇鹽類反應之探討…….........84 第四章 結論與展望……………………………………………..……92 參考文獻………………………………..………………………………94 附錄

    1. Edward I. Solomon, Angew. Chem. Int. Ed. 2001, 40, 4570 - 4590
    2. Nar, H.; Messerschmidt, A.; Huber, R.; van de Kamp, M.; Canters, G. W. J. Mol. Biol. 1991, 221, 765.
    3. Kitajima, N.; Fujisawa, K.; Tanaka, M. Adv. Inorg. Chem. 1992, 39, 1.
    4. Ramshaw, J. A. M. Nature. 1978, 272, 319.
    5. Richard H. Holm, Edward I. Solomon, Chem. Rev. 1996, 96, 2239 - 2314.
    6. Lippard, S. J. Principle Of Bioinorganic chemisrtry; University Science Books:Mill
    Vally, 1994, p 86 and p 237-242
    7. Edward I. Solomon, Chem. Rev. 2004, 104, 419 - 458
    8. L. Mario Amzel, Science, 1997, 278, 1300 - 1305
    9. L. M. Amzela, Cell. Mol. Life Sci. 2000, 57, 1236 – 1259
    10. L. Mario Amzel, Science, 2004, 304, 864 – 867
    11. Kenneth D. Karlin, Inorg. Chem. 2006, 45, 10098 - 10107
    12. Kazunari Yoshizawa, Inorg. Chem. 2006, 45, 3034 - 3041
    13. http://en.wikipedia.org/wiki/Dopamine
    14. Ibers, J. A. Proc. Natl. Acad. Sci. USA 1977, 74, 3114 - 3118
    15. Marks, T. J.; Ibers, J. A. J. Am. Chem. Soc. 1979, 101, 4180 - 4192
    16. Kitajima, N; Moro-oka, Y.; Fujisawa, K. J. Am. Chem. Soc. 1990, 112, 3210 - 3212
    17. Kitajima, N.; Fujisawa, K.; Tanaka, M. J. Am. Chem. Soc, 1992, 114, 9232.- 9233
    18. Nobumasa Kitajima, Thomas G, Spiro. J. Am. Chem. Soc. 1994, 116, 2585 – 2590
    19. Patrick L. Holland, William B. Tolman. J. Am. Chem. Soc. 1999, 121, 7270 - 7271
    20. Patrick L. Holland, William B. Tolman. J. Am. Chem. Soc. 2000, 122, 6331 - 6332
    21. Jorg Sundermeyer, Siegfried Schindler, Angew. Chem. Int. Ed. 2004, 43, 4360 - 4363
    22. Edward I. Solomon, Proc. Natl. Acad. Sci. 2004, 101, 13105 - 13110
    23. Jorg Sundermeyer, Siegfried Schindler, Angew. Chem. Int. Ed. 2006, 45, 3867 – 3869
    24. Kenneth D. Karlin, J. Am. Chem. Soc. 2007, 129, 264 - 265
    25. Kenneth D. Karlin, Angew. Chem. Int. Ed. 2008, 47, 82 – 85
    26. Vicent Moliner, J. Am. Chem. Soc. 2007, 129, 11700 - 11707
    27. Judith P. Klinman, J. Biol. Chem. 2006, 281, 3013–3016.
    28. Csoregh, I.; Kierkegaard, P.; Norrestam, R. Acta Crystallogr. 1975, B31, 314.
    29. Lewin, A. H.; Michl, R. J. Chem. Commun. 1971, 1400 - 1401
    30. Sorrell, T. N.; Jameson, D. L. J. Am. Chem. Soc. 1983, 105, 6013 - 6018
    31. Sanyal, I.; Karlin, K. D.; Strange, R. W.; Blackburn, N. J. J. Am. Chem. Soc. 1993, 115, 11259 - 11270
    32. Sorrell, T. N.; Malachowski, M. R. Inorg. Chem. 1983, 22, 1883 - 1887
    33. Aboelella, N. W.; Reynold, A. M.; Holland, P. L.; Tolman, W. B. J. Am. Chem. Soc. 2002, 124, 2108 - 2109
    34. Clainche, L. L.; Giorgi, M.; Reinaud, O. Eur. J. Inorg. Chem. 2000, 1931 - 1933
    35. Schilstra, M. J.; Birker, P. J. M. W. L.; Verschoor, G. C.; Reedijk, J. Inorg. Chem. 1982, 21, 2637 - 2644
    36. Gagne, R. R.; Allison, J. L.; Gall, R. S.; Koval, C. A. J. Am. Chem. Soc. 1977, 99, 7170 - 7178
    37. W. L. Driessen, Synthetic Commu., 1988, 18, 1581 - 1588
    38. Casella, L.; Gullotti, M.; Suardi, E., Dalton Trans. 1990, 2843 - 2851
    39. Casella, L.; Gullotti, M.; Pintar, A.; Pinciroli, F.; Viganò, R., Dalton Trans. 1989, 1161 - 1169
    40. Milner, E. S.; jun.; Snyder, S.; Joullié, M. M. J. Chem. Soc. 1964, 4151 - 4153
    41. 周櫻旻,國立台灣師範大學化學研究所碩士論文,2003
    42. Eric Block, J. Am. Chem. Soc. 1989, 111, 658 - 665
    43. Toso, R; Sega, A; Mihalic, M; Kajfez F. Chim Ital. 1979, 109, 529
    44. Dagdigian, J. V.; McKee, V.; Reed, C. A. Inorg. Chem. 1982, 21, 1332 - 1342
    45. Gagné, R. R.; Allison, J. L.; Gall, R. S.; Koval, C. A. J. Am. Chem. Soc. 1977, 22,
    7170.
    46. Kenneth M. Nicholas, Inorg. Chem. 2007, 46, 2316 - 2321
    47. Kenneth D. Karlin, Inorg. Chem. 2006, 45, 3004 - 3013
    48. Steven H. Strauss, J. Am. Chem. Soc. 1994,116, 10003 - 10014
    49. Christopher J. Cramer and Shinobu Itoh, Inorg. Chem. 2008, 47, 8222 - 8232
    50. (a) Karlin, K. D. J. Am. Chem. Soc. 2003, 125, 634 - 635. (b) Neuhold, Y.-M.; Karlin, K. D.; Zuberbűhler, A. D. Inorg. Chem. 2003, 42, 1807 - 1824.
    51. Dagdigian, J. V.; Reed, C. A. Inorg. Chem. 1979, 18, 2623 - 2626
    52. Bosnich, B.; Downes, J. M.; Whelan, J. Inorg. Chem. 1981, 20, 1081 - 1086
    53. Willem L. Driessen, Dalton Trans. 1990, 3175 -3182
    54. Vivian Wing-Wah Yam, Inorg. Chem. 2001, 40, 3435 - 3442
    55. Dance, I. G. Polyhedron 1986, 2, 1031.
    56. Healy, P. C.; Bott, R. C.; Sagatys, D. S. Chem. Commun. 1998, 2403 - 2404
    57. Ian G. Dance, Inorg. Chem. 1983, 22, 2883 - 2887
    58. Nakamura, A.; Okamura, T.; Ueyama, N.; Ainscough, E. W.; Brodie, A. M.; Waters, J.M. J. Chem. Soc. Chem. Commun., 1993, 1658 - 1660
    59. Vittal, J. J.; Lai, G. X.; Deivaraj, T. C. Inorg. Chem, 2000, 39, 1028 - 1034
    60. Gunnoe, T. B.; Delp, S. A.; Munro-Leighton, C.; Goj, L. A. ; Ramírez, M. A.; Petersen, J. L.; Boyle, P. Inorg. Chem. 2007, 46, 2365 - 2367

    無法下載圖示 本全文未授權公開
    QR CODE