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研究生： 陳昱璇
Chen, Yu-Shiuan
論文名稱： 同碳雙碳烯之鎳金屬錯合物的合成、結構鑑定以及催化應用性
Synthesis, Characterization and Catalytic Application of Nickel–Carbodicarbene Complexes
指導教授： 王朝諺
Ong, Tiow-Gan
吳學亮
Wu, Hsyueh-Liang
學位類別： 碩士
Master
系所名稱： 化學系
Department of Chemistry
論文出版年： 2019
畢業學年度： 108
語文別： 中文
論文頁數： 118
中文關鍵詞： 同碳雙碳烯 、鎳金屬錯合物 、烯烴異構化反應
英文關鍵詞： carbodicarbene, Nickel metal complex, alkene isomerization reaction
DOI URL： http://doi.org/10.6345/NTNU201901183
論文種類： 學術論文
相關次數： 點閱：150  下載：0 
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    • 同碳雙碳烯是一種彎曲型重烯，其具有獨特的碳零價中心，由兩個含氮雜環碳烯支持穩定。在有機金屬與催化化學領域中，配位基的設計對於穩定金屬錯合物與增加其反應性，扮演著至關重要的角色。
    由於同碳雙碳烯擁有良好的給予電子特性，在應用中可作為預定義配位基。本論文以 SN2 雙分子親核取代反應合成出兩側取代基相異之非對稱同碳雙碳烯與兩側取代基相同之對稱同碳雙碳烯，再分別搭配三級膦之衍生配子合成一系列鎳一價金屬錯合物。藉由 X 光單晶繞射儀解析其晶體結構，並以電子順磁共振光譜儀圖譜分析輔佐。
    我們將合成的同碳雙碳烯鎳一價金屬錯合物應用在烯烴異構化反應，證明鎳一價錯合物確實具有催化反應性；添加劑六氟銻 (V) 酸鈉能使產率提升，可能有助於催化循環的進行。
    同碳雙碳烯鎳一價金屬錯合物展現了令人期待的反應結果，進一步充分瞭解它們的反應性與特質則有其研究的必要性，這將會是一個深入探討的議題。

    The Carbodicarbene (CDC) is a bent allene with a unique divalent carbon (0) center, supported by two N-heterocyclic carbenes (NHC). Ligand design plays a crucial rule in the organometallic and catalytic chemistry for stablising metal complexes and / or enhance their reactivity.
    Due to its excellent donor property, it is a prederfinated ligand for these applications. In this thesis, we report the preparation of unsymmetrical and symmetrical carbodicarbene via SN2 reaction. We also have prepared a series of Nickel(I)-carbodicarbene complexes bearing different phosphine derivatives. The X-ray single-crystal diffraction structural analysis and EPR spectroscopic studies have been used to characterize the Ni(I) complexes.
    Furthermore, we have also investigated the catalytic properties of the Nickel(I)-carbodicarbene complexes in the isomerization reaction of alkene. The experimental data shows promising results of the catalytic activity of Ni(I) complexes in this reaction. Additionally, additive (NaSbF6) might play an auxiliary role in promoting the reactivity.
    The Nickel(I)-carbodicarbene complexes shows promising results. However, further investigation of Nickel(I)-carbodicarbene complexes are necessary to fully understand the reactivity and properties, these issues are interesting research topics.

    摘要 i ABSTRACT ii 誌謝 iii 目錄 v 表目錄 viii 圖目錄 ix 式目錄 xii 附表目錄 xiv 附圖目錄 xv 簡稱說明 xvii 第一章 緒論 1 1-1 前言 1 1-2 膦化物 6 1-3 碳烯 10 1-4 含氮雜環碳烯 13 1-5 彎曲型重烯—同碳雙碳烯 18 1-6 鎳金屬錯合物 25 1-7 鎳一價金屬錯合物 26 1-8 過渡金屬催化 (Transition-Metal Catalysis) 33 1-9 鎳金屬催化 (Nickel-promoted Catalysis) 35 1-10 烯烴異構化反應 (Alkene Isomerization) 38 1-11 研究動機 42 第二章 結果與討論 44 2-1 同碳雙碳烯化合物之合成及探討 44 2-2 同碳雙碳烯之鎳一價金屬錯合物的合成及探討 47 2-2-1 同碳雙碳烯之鎳一價金屬錯合物的晶體結構鑑定 52 2-2-2 同碳雙碳烯之鎳一價金屬錯合物的結構與圖譜分析 60 2-3 鎳一價金屬錯合物應用於烯烴異構化反應 66 2-3-1 烯烴異構化反應最佳化條件之探討 66 第三章 結論 74 第四章 實驗方法 76 4-1 實驗儀器 76 4-1-1 核磁共振儀 76 4-1-2 高解析度磁場式質譜儀 77 4-1-3 X-ray 單晶繞射解析 77 4-1-4 元素分析儀 78 4-1-5 電子順磁共振光譜儀 78 4-2 藥品與溶劑 78 4-3 實驗步驟 79 4-3-1 合成步驟 79 4-3-2 烯烴異構化反應 91 參考文獻 93 附錄一 X-ray 晶體與數據 100 附錄二 核磁共振光譜圖 110 附錄三 電子順磁共振光譜圖 115

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