研究生: |
游曼彤 Yu, Man-Tung |
---|---|
論文名稱: |
鈷金屬錯合物催化碳-磷鍵偶合反應的研究 Cobalt-Catalyzed C-P Coupling Reactions |
指導教授: |
鄭建鴻
Cheng, Chien-Hong |
口試委員: | |
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: | 2010 |
畢業學年度: | 99 |
語文別: | 中文 |
論文頁數: | 230 |
中文關鍵詞: | 鈷金屬錯合物催化 、碳磷鍵 、偶合反應 、有機磷化合物 、三芳香環膦化合物 、膦氧化合物 、二苯基膦 、磷配位基 、芳香鹵化合物 、二苯基膦氧 、二芳基膦-噁唑啉配位基 |
外文關鍵詞: | Cobalt-Catalyzed, carbon-phosphorus (C – P) bond, Coupling Reactions, organophosphines, unsymmetrical triarylphosphines, triarylphosphine oxides, diphenylphosphine, Arylphosphine ligands, aryl halides, diphenylphosphine oxide, phosphinooxazoline |
相關次數: | 點閱:2 下載:0 |
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有機磷化合物(organophosphines) 在勻相金屬催化反應(homogeneous catalysis) 中扮演相當重要的角色;然而,選擇合適的含磷配位基在催化反應中更是影響反應的結果關鍵。本篇論文探討以鈷金屬催化方式進行碳-磷鍵的偶合反應,使二苯基膦或二苯基膦氧與芳香鹵化物與鈷金屬進行加成反應,以合成出一系列具有高度合成應用價值的三芳香環膦化合物以及膦氧化合物,其加成方式與催化條件在相關領域中首次被報導。
此外,本文進一步深入探討二苯基膦於此鈷金屬催化系統中可能之反應機構;有趣的是將Zn 替換為ZnI2,意即沒有還原劑將Co(II)I2還原成Co(I)I 時,反應仍然進行。而藉由實驗設計,將鋅試劑與二苯基膦進行反應測試,排除形成鋅試劑反應機構之可能性。
本論文最後嘗試將所開發出來的鈷金屬催化碳-磷鍵偶合反應,應用於合成掌性二芳基膦-噁唑啉配位基 (PHOX),但所得到的結果是含有兩個掌性配位基的鈷金屬錯合物。
Arylphosphine ligands play an extremely important role in homogeneous catalysis, and it’s also the crucial factor in determining the success of a reaction. In this thesis, we used an inexpensive cobalt-catalyzed to synthesize a species of unsymmetrical triarylphosphines and triarylphosphine oxides from diphenylphosphine or diphenylphosphine oxide with aryl halides. This is the first successful Co-catalyzed couplings of carbon-phosphorus (C – P) bond forming.
In addition, we tried to study more details in the mechanism of the presenting coupling reaction. Interestingly, the reaction could also work without the reducing agent when the additive in the reaction condition was changed from Zn to ZnI2. Since the reaction failed to formation of carbon-phosphorus bond when replacing aryl halides by the organozinc reagent, the associative mechanism mediated by the organozinc reagent had been excluded.
At the last part of this thesis, we attempted to synthesis of the phosphinooxazoline derivatves by this methodology. Finally, we got the corresponding complexes of two phosphinooxzaolines with cobalt iodides.
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