簡易檢索 / 詳目顯示

研究生: 李鴻章
Lee, Hong-Chang
論文名稱: 多核釕金屬超分子的合成與鑑定
The synthesis and determination of polyruthenium supramolecular
指導教授: 許拱北
Shiu, Kom-Bei
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2002
畢業學年度: 90
語文別: 中文
論文頁數: 59
中文關鍵詞: 雙羧酸超分子四核八核六核
外文關鍵詞: ruthenium, dicarboxylic acid, supramolecular
相關次數: 點閱:143下載:1
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
  • [Ru3(CO)12] 與草酸 (HO2CCO2H) 和PR3 (R = Me, Ph, p-tol ) 反應,可獲得八核 [{Ru2(CO)4(PMe3)2}{μ4,η4–O2CCO2}]4 (1),四核 [{Ru2(CO)4(PMe3)2}{μ4,η4–O2CCH2CO2}]2 (2) ,和六核金屬釕化合物 [{Ru2(CO)4(PR3)2}{μ4,η4–O2CX CO2}]3 ( X = C6H4 (3), C6H4C6H4 (4))。化合物1-4的單晶構造已經確定為:1為方形體的構造 (見ORTEP圖1),2為環狀的構造 (見ORTEP圖2),3和4為三角柱狀的構造(見ORTEP圖3 , 4),其中1為全世界第一個含 [Ru2(CO)4(PR3)2] 單位的八核金屬錯化物。

    The reaction of [Ru3(CO)12] with oxalic acid (HO2CCO2H) and PR3 (R = Me, Ph, p-tol ) gives octaruthenium complex [{Ru2(CO)4(PMe3)2}{μ4,η4–O2CCO2}]4 (1),tetraruthenium complex [{Ru2(CO)4(PMe3)2}{μ4,η4–O2CCH2CO2}]2 (2) and hexaruthenium complexes [{Ru2(CO)4(PR3)2}{μ4,η4–O2CX CO2}]3 ( X = C6H4 (3), C6H4C6H4 (4))。The single crystal structure of complexes 1- 4 have been determined ;1 is a square box,2 is a molecular loop,3 and 4 are molecular triangles,1 is the first octanuclear complex containing [Ru2(CO)4(PR3)2] unit in the world.

    目 錄 中文摘要 Ⅰ 英文摘要 Ⅱ 致謝 Ⅲ 目錄 Ⅳ 圖目錄 Ⅵ 表目錄 Ⅶ 光譜圖目錄 Ⅷ 第一章 緒論 1 1.多金屬核幾何錯化物 1 1-1. 雙金屬核(M-M , M = Mo, W, Re, Rh, )與雙羧酸的反應 2 1-1-1. 合成方法的簡介 2 1-1-2. 化合物的結構及形狀 5 1-1-2-1. 四金屬核化合物(ㄇ字型、雙十型及環狀分子) 5 1-1-2-2. 六金屬核化合物(三角柱及螺旋槳狀) 10 1-1-2-3. 八金屬核化合物(方形體) 13 1-1-2-4. 十二金屬核籠狀化合物 15 1-2. Ru3(CO)12與雙羧酸的反應 16 2.研究動機及構想 18 第二章 實驗部分 19 2-1.儀器、藥品及實驗裝置 19 2-2.錯合物的合成與鑑定 22 第三章 結果與討論 25 3-1. 多核釕錯化物的合成及其構造 25 3-1-1. 八核釕錯化物的合成及構造 ( [{Ru2(CO)4(PMe3)2} {μ4,η4–O2CCO2}]4 (1) ) 25 3-1-2. 四核釕錯化物的合成及構造 ( [{Ru2(CO)4(PMe3)2} {μ4,η4–O2CCH2 CO2}]2 (2) ) 26 3-2. 多核釕錯化物的晶體討論 29 3-2-1.錯化物鍵長的比較 35 3-2-2.錯化物鍵角的比較 37 3-3.不同雙羧酸對多核釕錯化物結構的影響 38 第四章 結論 40 參考文獻 41 附錄一:Ru3(CO)12與其他雙羧酸的反應(HO2CXCO2H, X= C6H4 , C6H4C6H4 , C10H6) 43 附錄二:IR, 1H-NMR, 和31P-NMR光譜圖 49 附錄三:各晶體之數據、鍵角和鍵長 72

    1. M. Fujita, Chem. Soc. Rev. 1998, 27, 417. and reference therein
    2. S. Leininger, P. J. Stang, B. Olenyuk, Chem. Rev. 2000, 100, 853.
    3. B. J. Holliday, C. A. Mirkin, Angew. Chem. Int. Ed. 2001, 40, 2022.
    4. J. M. Lehn, Angew. Chem. Int. Ed. Engl. 1988, 27, 90.
    5. J. M. Lehn, Angew. Chem. Int. Ed. Engl. 1990, 29, 1304.
    6. D. S. Lawrence, T. Jiang, M. Levett. Chem. Rev. 1995, 95, 2229.
    7. D. Philp and J. F. Stoddart. Angew. Chem. Int. Ed. Engl. 1996, 35, 1154.
    8. H. M. Colquhoun, J. F. Stoddart, D. J. Williams, Angew. Chem. Int. Ed. Engl. 1986, 25, 487.
    9. M. Fujita, Chem. Soc. Rev. 1998, 27, 417.
    10. P. J. Stang, B. Olenyuk, Acc. Chem. Res. 1997, 30, 502.
    11. J. M. Lehn. Supramolecular chemistry :concepts and perspectives : a personal account built upon the George Fisher Baker non-resident lectureship in chemistry at Cornell University and the Lezione Lincee, New York , 1995
    12. G. M. Whitesides, J. P. Mathias, C. T. Seto, Science, 1991, 254, 1312.
    13. M. Fujita, D. Oguro, K. Ogura, Nature, 1995, 378, 30.
    14. F. A. Cotton, C. Lin, C. A. Murillo, Acc. Chem. Res. 2001, 34, 759.
    15. R. H. Cayton, M. H. Chisholm, J. C. Huffman, E. B. Lokovsky, J. Am. Chem. Soc. 1991, 113, 8709.
    16. F. A. Cotton, C. Lin, C. A. Murillo, J. Chem. Soc. Dalton. Trans. 1998, 3151.
    17. F. A. Cotton, J. P. Donahue, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 1234.
    18. J. K. Bera, P. Angaridis, F. A. Cotton, M. A. Petrukhina, P. E. Fanwick, R. A. Walton, J. Am. Chem. Soc. 2001, 123, 1515.
    19. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 472.
    20. F. A. Cotton, C. Lin, C. A. Murillo, J. Chem. Soc. Dalton. Trans. 2001, 499.
    21. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 575.
    22. F. A. Cotton, L.M. Daniels, C. A. Murillo, J. Am. Chem. Soc. 1999, 121, 4538.
    23. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. Commun. 2001, 4, 130.
    24. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 478.
    25. F. A. Cotton, L. M. Daniels, C. Lin, C. A. Murillo, J. Chem. Soc. Dalton. Trans. 2001, 502.
    26. R. P. Bonar-Law, T. D. McGrath, N. Singh, J. F. Bickley, A. Steiner, Chem. Commun. 1999, 2457.
    27. J. F. Bickley, R. P. Bonar-Law, C. Femoni, E. J. MacLean, A. Steiner, S. J. Teat, J. Chem. Soc. Dalton. Trans. 2000, 4025.
    28. F. A. Cotton, L. M. Daniels, C. Lin, C. A. Murillo, Chem. Commun. 1999, 841.
    29. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 6413.
    30. F. A. Cotton, C. Lin, C. A. Murillo, Chem. Commun. 2001, 11.
    31. F. A. Cotton, C. Lin, C. A. Murillo, Inorg. Chem. 2001, 40, 5886.
    32. G. R. Crooks, B. F. G. Johnson, J. Lewis, I. G. Williams, G. Gamlen, J. Chem. Soc. 1969, 2761.
    33. M. Bianchi, P. Frediani, U. Matteoli, G. Menchi, F. Piacenti, G. Petrucci, J. Organomet. Chem. 1983, 259, 207.
    34. G. Suss-Fink, J.-L. Wolfender, F. Neumann, H. Stoeckli-Evans, Angew. Chem. Int. Ed. Engl. 1990, 29, 429.
    35. G. M. Sheldrick, “SHELX-76”. Program for Crystal Structure Determination, Universitat Gottingen 1986
    36. E. Whelan, M. Devereux, M. McCann, V. McKee, Chem. Commun. 1997, 427.
    37. J. L. Derissen, P. H. Smit, Acta. Cryst. 1974, 2240.
    38. J. A. Goedkoop, G. H. MacGillavry , Acta. Cryst. 1957, 10, 125.
    39. M. Bailey, C. J. Brown, Acta. Cryst. 1967, 22, 387.

    下載圖示 校內:立即公開
    校外:2002-06-14公開
    QR CODE