論文使用權限 Thesis access permission:自定論文開放時間 user define
開放時間 Available:
校內 Campus: 已公開 available
校外 Off-campus: 已公開 available
論文名稱 Title |
開環富勒烯與三釕羰基金屬簇之反應性研究 Reactions of Open-Cage Fullerene with Triruthenium Carbonyl Cluster |
||
系所名稱 Department |
|||
畢業學年期 Year, semester |
語文別 Language |
||
學位類別 Degree |
頁數 Number of pages |
91 |
|
研究生 Author |
|||
指導教授 Advisor |
|||
召集委員 Convenor |
|||
口試委員 Advisory Committee |
|||
口試日期 Date of Exam |
2013-07-25 |
繳交日期 Date of Submission |
2013-07-30 |
關鍵字 Keywords |
三釕羰基金屬簇、碳六十、開環富勒烯 Fullerene, Open-Cage Fullerene, Triruthenium Carbonyl Cluster |
||
統計 Statistics |
本論文已被瀏覽 5664 次,被下載 331 次 The thesis/dissertation has been browsed 5664 times, has been downloaded 331 times. |
中文摘要 |
本論文主要是研究碳六十開環化合物與三釕羰基金屬簇之反應研究。利用具有十二圓環開環富勒烯 C80H14N2O2 (2) 與 Ru3(CO)12 於氯苯 (Chlorobenzene) 下反應得到一個具有八圓環的開環富勒烯錯合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3),接著利用化合物 3 進行熱裂反應得到一個具有十一圓環開環富勒烯雙釕錯合物 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4),最後藉由 X-Ray、IR、MASS、1H及13C NMR、UV-Vis、電化學來對其作一系列的鑑定與探討。 |
Abstract |
Reaction of C80H14N2O2 (2) and Ru3(CO)12 in refluxing chlorobenzene affords Ru3(CO)8(μ2, η7-(C63NO2Ph2Py)) (3). Compound 3 apparentily arises from C-C bond activation of 2 to generate an diol ligand bridging motif. In contrast, compound 4 is produced by C-H / C-O activation insertion of one ruthenium atom into a pentagonal ring of 3, together with the Ru3 cluster fragmentation. Complexes 3 and 4 have been characterized by IR, NMR, UV-Vis, CV, Mass spectroscopies, and single-crystal X-ray diffraction study. |
目次 Table of Contents |
摘要 (中): ..........................................................................................................................i Abstract ................................................................................................................... ii 謝誌 ......................................................................................................................... iii 目錄 ..........................................................................................................................iv 圖目錄 .......................................................................................................................vi 表目錄 .......................................................................................................................viii 第壹章 緒論 ............................................................................................................... 1 1.1 碳六十介紹 ...........................................................................................................1 1.2 碳六十與金屬的反應 ............................................................................................. 3 1.3 開環富勒烯介紹 ................................................................................................... 4 1.4 開環富勒烯與金屬的反應動機 ................................................................................ 9 第貳章 結果與討論 ......................................................................................................10 2.1 合成化合物 C80H14N2O2 (2)................................................................................. 10 2.2 化合物 C80H14N2O2 (2)與Ru3(CO)12反應 ............................................................. 12 2.3 化合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3)之鑑定 ................................................13 2.4 化合物 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 之熱裂反應 ........................................ 24 2.5 化合物 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 之鑑定 ........................................ 25 2.6 化合物 (5) 之鑑定 ................................................................................................. 35 2.7 化合物 (6) 之鑑定 ................................................................................................. 35 2.8 化合物 3 及化合物 4 的結構探討 ............................................................................ 36 2.9 化合物 1-4 的紫外光-可見光光譜的探討 ............................................................. 37 2.10 化合物 1-4 的電化學探討 .................................................................................. 39 2.11 結論 ................................................................................................................. 40 第參章 實驗部分 .........................................................................................................41 3.1 使用儀器 ............................................................................................................. 41 3.2 試藥來源及前處理 ................................................................................................ 42 3.3 C80H14N2 (1) 的合成 ........................................................................................... 43 3.4 C80H14N2O2 (2) 的合成 ....................................................................................... 43 3.5 C80H14N2O2 (2) 與Ru3(CO)12的反應 .................................................................... 44 3.5.1 C80H14N2O2 (2) 空白反應: ................................................................................ 45 3.5.2 Ru3(CO)12 空白反應: ........................................................................................ 45 3.6 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的熱裂反應 .................................................. 46 3.6.1 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的固態熱裂反應: ....................................... 46 3.6.2 Ru3(CO)8(μ2, η5-(C63NO2Ph2Py)) (3) 的液態熱裂反應: ....................................... 47 3.7 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 固態熱裂反應: ....................................... 47 3.8 HRu2(CO)3(μ2, η7-(C63N(C6H4)PhPy)) (4) 液態熱裂反應: ....................................... 47 3.9 循環伏安法的測定 ................................................................................................ 48 參考文獻 .................................................................................................................. 49 附錄一 ...................................................................................................................... A-1 附錄二 .................................................................................................................... A-14 附錄三 .................................................................................................................... A-26 附錄四 .................................................................................................................... A-27 |
參考文獻 References |
[1] Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Nature, 1985, 318, 162-163. [2] Prato, M. J. Mater. Chem. 1997, 7, 1097-1109. [3] Cross, R. J.; Jime´nez-Va´zquez, H. A.; Lu, Q.; Saunders, M.; Schuster, D. I.; Wilson, S. R.; Zhao, H. J. Am. Chem. Soc. 1996, 118, 11454-11459. [4] Balch, A. L.; Olmstead, M. M. Chem. Rev. 1998, 98, 2123-2165. [5] Hirsch, A. Nature Materials, 2010, 9, 868-871. [6] Kratschmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. Nature, 1990, 347, 354-358. [7] (a) Xie, Q.; Ptrez-Cordero, E.; Echegoyen, L. J. Am. Chem. Soc. 1992, 114, 3978-3980. (b) Zhou, F.; Jehoulet, C.; Bard, A. J. J. Am. Chem. Soc. 1992, 114, 11004-11006. [8] (a) Nalwa, H. S. Adv. Mater. 1993, 5, 341-358. (b) Tutt, L. W.; Kost, A. Nature 1992, 356, 226-228. (c) Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F. Science 1992, 258, 1474-1476. [9] (a) Jensen, A. W.; Wilson, S. R.; Schuster, D. I. Bioorg. Med. Chem. 1996, 4, 767-779. (b) Nakamura, E.; Tokuyama, H.; Yamago, S.; Shiraki, T.; Sugiura, Y. Bull. Chem. Soc. Jpn. 1996, 69, 2143-2159. (c) Friedman, S. H.; Decamp, D. L.; Sijbesma, R. P.; Srdanov, G.; Wudl, F.; Kenyon, G. L. J. Am. Chem. Soc. 1993, 115, 6506-6509. [10] Fagan, P. J.; Calabrese, J. C.; Malone, B. Science, 1991, 252, 1160-1161. [11] Hsu, H. F.; Shapley, J. R. J. Am. Chem. Soc. 1996, 118, 9192-9193. [12] Song, H.; Lee, K.; Park, J. T.; Choi, M. G. Organometallics, 1998, 17, 4477-4483. [13] Park, J. T.; Song, H.; Cho, J. J.; Chung, M. K.; Lee, J. H.; Suh, I. H. Organometallics, 1998, 17, 227-236. [14] Lee, K.; Song, H.; Park, J. T. Acc. Chem. Res. 2003, 36, 78-86. [15] Murata, M.; Murata, Y.; Komatsu, K. Chem. Commun. 2008, 6083-6094. [16] (a) Diederich, F.; Kessinger, R. Acc. Chem. Res. 1999, 32, 537-545. (b) Hirsch, A. Angew. Chem. Int. Ed. 2001, 40, 1195-1196. [17] Hummelen, J. C.; Prato, M.; Wudl, F. J. Am. Chem. Soc. 1995, 117, 7003-7004. [18] Arce, M. J.; Viado, A. L.; An, Y. Z.; Khan, S. I.; Rubin, Y. J. Am. Chem. Soc. 1996, 118, 3775-3776. [19] Rubin, Y. Chem. Eur. J. 1997. 3. 1009-1017. [20] Kurotobi, K.; Murata, Y. Science, 2011, 333,612-616. [21] Schick, G.; Jarrosson, T.; Rubin, Y. Angew. Chem. Int. Ed. 1999, 38, 2360-2363. [22] Rubin, Y.; Jarrosson, T.; Wang, G. W.; Bartberger, M. D.; Houk, K. N.; Schick, G.; Saunders, M.; Cross, R. J. Angew. Chem. Int. Ed. 2001, 40, 1543-1546. [23] Schick, G.; Jarrosson, T.; Rubin, Y. Angew. Chem. Int. Ed. 1999, 38, 2360-2363. [24] Vougioukalakis, G. C.; Prassides, K.; Orfanopoulos, M. Org. Lett. 2004, 6, 1245-1247. [25] Vougioukalakis, G. C.; Roubelakisb, M. M.; Orfanopoulos, M. Chem. Soc. Rev. 2010, 39, 817-844. [26] Roubelakis, M. M.; Vougioukalakis, G. C.; Orfanopoulos, M. J. Org. Chem. 2007, 72,6526-6533. [27] Murata, Y.; Murata, M.; Komatsu, K. Chem. Eur. J. 2003, 9, 1600-1609. [28] Inoue, H.; Yamaguchi, H.; Suzuki, T.; Akasaka, T.; Murata, S. Synlett, 2000, 1178-1180. [29] Inoue, H.; Yamaguchi, H.; Iwamatsu, S. I.; Uozaki, T.; Suzuki, T.; Akasaka, T.; Nagase, S.; Murata, S. Tetrahedron Lett. 2001, 42, 895-950. [30] Murata, Y.; Murata, M., Komatsu, K. J. Org. Chem. 2001, 66, 8187-8197. [31] Li, Y.; Lei, X.; Lawler, R. G.; Murata, Y.; Komatsu, K.; Turro, N. J. Org. Lett. 2012, 14, 3822-3825. [32] Sawa, H.; Wakabayashi, Y.; Murata, Y.; Murata, M.; Komatsu, K. Angew. Chem. Int. Ed. 2005, 44, 1981-1983. [33] Chuang, S. C.; Murata, Y.; Murata, M.; Mori, S.; Maeda, S.; Tanabe, F.; Komatsu, K. Chem. Commun. 2007, 1278-1280. [34] Murata, Y.; Murata, M.; Komatsu, K. J. Am. Chem. Soc. 2003, 125, 7152-7153. [35] Murata, M.; Murata, Y.; Komatsu, K. J. Am. Chem. Soc. 2006, 128, 8024-8033. [36] Frunzi, M.; Lei, X.; Murata, Y.; Komatsu, K.; Iwamatsu, S. I.; Murata, S.; Lawler, R. G. Nicholas J. Turro J. Phys. Chem. Lett. 2010, 1, 1420-1422. [37] Carravetta, M.; Danquigny, A.; Mamone, S.; Cuda, F.; Johannessen, O. G.; Heinmaa, I.; Panesar, K.; Stern, R.; Grossel, M. C.; Horsewill, A. J.; Samoson, A.; Murata, M.; Murata, Y.; Komatsud, K.; Levitt, M. H. Phys. Chem. Chem. Phys. 2007, 9, 4879-4894. [38] Komatsu, K.; Murata, M.; Murata, Y. Science, 2005, 307, 238-240. [39] Turro, N. J.; Chen, J. Y. C.; Sartori, E.; Ruzzi, M.; Marti, A.; Lawler, R.; Jockusch, S.; Gejo, J. P.; Komatsu, K.; Murata, Y. Acc. Chem. Res. 2010, 43, 335-345. [40] Carravetta, M.; Murata, Y.; Murata, M.; Heinmaa, I.; Stern, R.; Tontcheva, A.; Samoson, A.; Rubin, Y.; Komatsu, K.; Levitt, M. H. J. Am. Chem. Soc. 2004, 126, 4092-4093. [41] Murata, Y.; Maeda, S.; Murata, M.; Komatsu, K. J. Am. Chem. Soc. 2008, 130, 6702-6703. [42] Iwamatsu, S. I.; Stanisky, C. M.; Cross, R. J.; Saunders, M.; Mizorogi, N.; Nagase, S.; Murata, S. Angew. Chem. Int. Ed. 2006, 45, 5337-5340. [43] Whitener, K. E.; Frunzi, M.; Iwamatsu, S. I.; Murata, S.; Cross, R. J.; Saunders, M. J. Am. Chem. Soc. 2008, 130, 13996-13999. [44] Whitener, K. E.; Cross, R. J.; Saunders, M.; Iwamatsu, S. I.; Murata, S.; Mizorogi, N.; Nagase, S. J. Am. Chem. Soc. 2009, 131, 6338-6339. [45] Frunzi, M.; Baldwin, A. M.; Shibata, N.; Iwamatsu, S. I.; Lawler, R. G.; Turro, N. J. J. Phys. Chem. A, 2011, 115, 735-740. [46] Iwamatsu, S. I.; Murata, S. Synlett, 2005, 2117-2129. [47] Iwamatsu, S. I.; Murata, S.; Andoh, Y.; Minoura, M.; Kobayashi, K.; Mizorogi, N.; Nagase, S. J. Org. Chem. 2005, 70, 4820-4825. [48] Stanisky, C. M.; Cross, R. J.; Saunders, M. J. Am. Chem. Soc. 2009, 131, 3392-3395. [49] Xiao, Z.; Ye, G.; Liu, Y.; Chen, S.; Peng, Q.; Zuo, Q.; Ding, L. Angew. Chem. Int. Ed. 2012, 51, 9038-9041. [50] Iwamatsua, S. I.; Murata, S. Tetrahedron Letters, 2004, 45, 6391-6394. [51] Liu, S.; Zhang, Q.; Yu, Y.; Gan, L. Org. Lett. 2012, 14, 4002-4005. [52] Yu, Y.; Shi, L.; Yang, D.; Gan, L. Chem. Sci. 2013, 4, 814-818. [53] Yu, Y.; Xie, X.; Zhang, T.; Liu, S.; Shao, Y.; Gan, L.; Li, Y. J. Org. Chem. 2011, 76, 10148-10153. [54] Xin, N.; Yang, X.; Zhou, Z.; Zhang, J.; Zhang, S.; Gan, L. J. Org. Chem. 2013, 78, 1157-1162. [55] Xiao, Z.; Yao, J.; Yang, D.; Wang, F.; Huang, S.; Gan, L.; Jia, Z.; Jiang, Z.; Yang, X.; Zheng, B.; Yuan, G.; Zhang, S.; Wang, Z. J. Am. Chem. Soc. 2007, 129, 16149-16162. [56] Arce, M. J.; Viado, A. L.; An, Y. Z.; Khan, S. I.; Rubin, Y. J. Am. Chem. Soc. 1996, 118, 3775-3776. [57] Lien, S. T.; Yeh, W. Y. J. Organomet. Chem. 2012, 715, 69-72. [58] Murata, Y.; Kato, N.; Komatsu, K. J. Org. Chem. 2001, 66, 7235-7239 . [59] Darensbourg, D. J.; Fonta1, J. B.; Chojnacki, S. S.; Klausmeyer, K. K.; Reibenspies, J. H. Inorg. Chem. 1994, 33, 3526-3532. [60] Vandoorn, J. A.; Vanleeuwen, P. W. N. M. J. Organomet. Chem. 1981, 222, 299-309. [61] Refosco, F.; Bandoli, G.; Mazzi, U.; Tisato, F.; Dolmella, A.; Nicolinit, M. Inorg. Chem. 1990, 29, 2179-2180. [62] Echegoyen, L.; Echegoyen, L. E. Acc. Chem. Res. 1998, 31, 593-601. [63] Keshavarz-K, M.; Knight, B.; Srdanov, G.; Wudl, F. J. Am. Chem. Soc. 1995, 117, 11371-11372. [64] Johnson, B. F. G.; Lewis, J.; Nelson, W. J. H.; Nicholls, J. N.; Puga, J.; Raithby, P. R.; Rosales, M. J.; Schröder, M.; Vargas, M. D. J. Chem. Soc., Dalton Trans. 1983, 2447-2457. |
電子全文 Fulltext |
本電子全文僅授權使用者為學術研究之目的,進行個人非營利性質之檢索、閱讀、列印。請遵守中華民國著作權法之相關規定,切勿任意重製、散佈、改作、轉貼、播送,以免觸法。 論文使用權限 Thesis access permission:自定論文開放時間 user define 開放時間 Available: 校內 Campus: 已公開 available 校外 Off-campus: 已公開 available |
紙本論文 Printed copies |
紙本論文的公開資訊在102學年度以後相對較為完整。如果需要查詢101學年度以前的紙本論文公開資訊,請聯繫圖資處紙本論文服務櫃台。如有不便之處敬請見諒。 開放時間 available 已公開 available |
QR Code |