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    請使用永久網址來引用或連結此文件: http://ir.lib.ncu.edu.tw/handle/987654321/85854


    題名: 雙同碳膦烷碳烯的鈀金屬鉗型錯合物之合成及其在?頭偶合反應之應用;Synthesis of Bis(carbophosphinocarbene) Palladium Pincer Complex and its application to Sonogashira Coupling Reaction
    作者: 蔡欣言;Tsai, Hsin-Yen
    貢獻者: 化學學系
    關鍵詞: 卡本;carbone
    日期: 2021-09-15
    上傳時間: 2021-12-07 11:34:16 (UTC+8)
    出版者: 國立中央大學
    摘要: 卡本的中心碳具有兩對孤對電子對,相比碳烯是一種強的電子予體,擁有良好的親核力能與金屬配位。三種子分類中的同碳雙膦烷(carbodiphosphorane, CDP) 以及同碳雙碳烯 (carbodicarbene, CDC) 作為配位基或是生成之金屬錯合物,於催化反應中已有相當程度的發展;至於同碳膦烷碳烯(carbophosphinocarbene, CPC) 雖在文獻中已被報導,相較兩者卻缺乏相關的研究。在本論文中我們以2,6-雙二苯基膦?啶為骨架連接兩個同碳膦烷碳烯,形成之鉗型配位基具有C-N-C三牙基,與雙?啶二氯化鈀反應可以成功得到鉗型鈀金屬錯合物。此設計利用σ供電子能力的同碳膦烷碳烯作為鉗型配體兩側,用以提升整體結構穩定性,進而預期能有好的催化活性。後續發現此鈀催化劑能夠進行無銅?頭偶合催化反應,即使置換不同的烷基或芳基溴與末端炔反應,也能成功生成碳碳鍵的偶聯產物。藉由此研究可以得知雙同碳膦烷碳烯的鈀錯合物具有不錯的催化能力,未來具有應用於其他催化反應之潛力。;The central carbon of carbones (CL2) bears two lone electron pairs. Due to the two lone pairs on the central carbon, carbones have been regarded as ligand with both  and -donation. This property enables carbones acting as an electron-rich ligand for metallic complexes. In the past few year, the carbodiphosphoranes (CDPs) and carbodicarbenes (CDCs) have been developed to ligate metallic complexes for catalytic application. Carbophosphinocarbenes (CPCs) has been reported recently, but there is still lack of relevant research pertaining coordination chemistry and applications in catalysis. This thesis uses the skeleton of 2,6-bis(diphenylphosphino)pyridine to connect two carbone units which form pincer-type ligand with C-N-C tridentate coordination site. We successfully obtain pincer bis(carbone) palladium complex by reacting free pincer bis(carbone) ligand with bis(pyridine)palladium(II) chloride. This design utilizes CPCs at the two sides of the pincer-type ligand to improve the overall structural stability, and hence catalytic activity. It was later discovered that this palladium complex can be applied to copper-free Sonogashira coupling reaction. With different alkyl or aryl bromides and terminal alkynes, it can form carbon-carbon bond coupling product. This research demonstrates a new bis-CPC palladium complex with moderate catalytic ability and its potential for other catalytic applications.
    顯示於類別:[化學研究所] 博碩士論文

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