臺灣博碩士論文加值系統

合成並鑑定含二茂鐵之單邊取代二級氧化磷基
(η5-C5H5)(η5-C5H4-P(=O)(Ph)(H))Fe (S1)及雙邊取代二級氧化磷基(η5-C5H4-P(=O)(Ph)(H))2Fe (S2)，並利用X-ray單晶繞射法鑑定其結構。我們利用其互變異構化的特性，將二級磷酸接上鈀金屬，成為具提供電子能力之配位基。因其不怕水氣之特性，我們嘗試使用水做為反應溶劑以符合綠色化學的理想，並將之運用在Suzuki耦合反應上。結果顯示含二茂鐵之二級氧化磷基在硼酸與含推電子基芳香溴化物之耦合上有不錯的效果。

New Ferrocenyl secondary phosphine oxides (η5-C5H4-P(=O)(Ph)(H))(η5-C5H5)Fe S1 and (η5-C5H4-P(=O)(Ph)(H))2Fe S2 were prepared. The molecular structures of S1 and S2 were determined by single-crystal X-ray diffraction methods.
Palladium-catalyzed Suzuki reactions employing S1 and S2 as ligands gave satisfactory results. Judging from these results, a tautomeric equilibrium between S2 and its isomeric form (η5-C5H4-P(OH)(Ph))2Fe S2’ indeed takes place. It is also true for the S1 and its isomeric form (η5-C5H4-P(OH)(Ph))(η5-C5H5)Fe S1’. Furthermore, Suzuki cross-coupling reactions employed S2 as phosphine source and water as solvent were carried out for less reactive aryl bromides and phenyl boronic acid. Fair to good efficiencies were observed.

一、 序論
（一） 耦合反應的簡介---------------------------------------------------2
（二） Suzuki耦合反應---------------------------------------------------3
（三） 有機及過渡金屬配位基------------------------------------------5
（四） 二級氧化磷基的簡介--------------------------------------------7
（五） 二茂鐵（Ferrocene）的衍生物-----------------------------------9
（六） 研究方向----------------------------------------------------------10

二、 結果與討論
（一） 含二茂鐵單雙牙氧化磷基 S1、S2 的製備-----------------12
（二） 含二茂鐵單雙牙氧化磷基 S1、S2 的結構探討-----------15
（三） 含二茂鐵雙牙氧化磷基S2的Suzuki耦合反應機制探--20
（四） 含二茂鐵雙牙氧化磷基S2在Suzuki耦合反應上的應--23

三、 結論
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四、 實驗部份
（一） 儀器與藥品-------------------------------------------------------34
（二） 操作技巧----------------------------------------------------------37
（三） 合成與鑑定-------------------------------------------------------38
（四） Suzuki催化反應步驟-------------------------------------------42
（五） 耦合產物光譜數據----------------------------------------------43

參考文獻
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附錄
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光譜數據
晶體數據

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