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研究生: 曾宜秀
論文名稱: 碳-氫鍵活化合成錸金屬環錯合物及其分子辨識研究
Preparation of Rhenium-Based Metallacycles via C-H Bond Activation and Their Molecular Recognition Capabilities
指導教授: 許貫中
Hsu, Kung-Chung
呂光烈
Lu, Kuang-Lieh
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2008
畢業學年度: 96
語文別: 中文
論文頁數: 160
中文關鍵詞: 金屬環錯合物晶體結構分子辨識碳-氫鍵活化
英文關鍵詞: metallacycle, rhenium, crystal structure, molecular recognition
論文種類: 學術論文
相關次數: 點閱:181下載:2
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  • 本論文的研究是利用Re2(CO)10與2-(2-pyridyl)-benzimidazole (HBim-C6H4N)
    及1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1)、
    α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2) 、
    1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3) 、
    1,2-bis(4-pyridyl)ethane (bpea, L4)或1,3-bis(4-pyridyl)propane (bppa, L5)等有機配
    子在水熱條件下自組裝合成,分別得到[{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1)、
    [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3)、
    [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4)、[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)等錸
    金屬錯合物。錯合物15經由UV-vis、IR、NMR、FAB-MS等方法鑑定,其結構
    也以單晶X光繞射法解析。化合物1為一雙核非環狀錯合物,具發光特性,可藉
    由可見-紫外光光譜上的差異來辨識Hg+、Cu2+及Ag+等三種金屬離子。化合物25
    的結構為雙核金屬環化物,除了其光物理性質之外,該系列分子的特色是錸金屬
    將有機配子2-(2-pyridyl)benzimidazole中3號位置(C3)的碳-氫鍵活化而形成雙核
    環化物。

    Compounds [{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1),
    [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2), [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3),
    [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4), and [{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)
    were successfully synthesized by treatment of Re2(CO)10 with
    2-(2-pyridyl)-benzimidazole (HBim-C6H4N) and
    1,4-bis(benzimidazole-1-ylmethyl)-2,3,5,6-tetramethylbenzene (p-TXyBim, L1),
    α,α′-bis(benzimidazol-1-yl)-o-xylene (o-XyBim, L2),
    1,3-bis(benzimidazole-1-ylmethyl)-2,4,6-trismethylbenzene (m-TXyBim, L3),
    1,2-bis(4-pyridyl)ethane (bpea, L4), or 1,3-bis(4-pyridyl)propane (bppa, L5)
    respectively, under solvothermal conditions. The series of rhenium-based complexes
    15 was characterized using IR, UV-vis, and NMR spectroscopic techniques. The
    structures were further confirmed by X-ray single-crystal diffraction analysis.
    Compound 1 is a dimetallic complex with an acyclic conformation. Compound 1
    exhibited luminescent properties. In addition, it recognized Hg+,Cu2+ and Ag+ ions
    by means of discrimination on UV-vis spectra. Crystal structures showed that
    compounds 25 possess dimetallic cyclic conformations. It is noteworthy that C-H
    activation on 2-(2-pyridyl)benzimidazole occurred during preparation of these
    metallacyclic compounds.

    中文摘要I 英文摘要II 目錄III 圖目錄V 表目錄VII 第一章序論1 第一節金屬環化錯合物(Metallacycle) 1 第二節感測器(Sensor) 11 第三節研究動機16 第二章實驗部份20 第一節儀器設備及實驗藥品20 第二節水熱合成法23 第三節有機配子介紹25 第四節錸金屬錯合物之合成步驟27 第三章結果與討論37 有機配子的合成及鑑定37 錸金屬錯合物之合成及鑑定 Application of rhenium complex in sensor Preparation of metallacyclophanes of via C–H activation 第四章結論 參考文獻 37 42 54 70 71 附錄77 附錄一化合物15 之FTIR 圖譜79 附錄二有機配子L, L1, L2, L3,化合物25 之NMR 圖譜84 附錄三有機配子L,化合物25 之COSY 圖譜92 附錄四化合物[{Re(CO)3(μ-Bim-C6H4N)}2(μ-L1)] (1)的原子參數、熱參 數、鍵長鍵角與平移參數 97 附錄五化合物[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L2)] (2)的原子參數、熱參107 IV 數、鍵長鍵角與平移參數 附錄六化合物[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L3)] (3)的原子參數、熱參 數、鍵長鍵角與平移參數 117 附錄七化合物[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L4)] (4)的原子參數、熱參 數、鍵長鍵角與平移參數 130 附錄八化合物[{Re(CO)3}2(μ-Bim-C6H3N)(μ-L5)] (5)的原子參數、熱參 數、鍵長鍵角與平移參數 138

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