臺灣博碩士論文加值系統

合成及鑑定具二茂鐵單取代二級氧化磷配位基前驅物
(η5-C5H5)(η5-C5H4-P(=O)(tBu)(H))Fe (5a)、
(η5-C5H5)(η5-C5H4-P(=O)(Cy)(H))Fe (5b)、
(η5-C5H5)(η5-C5H4-P(=O)(Ph)(H))Fe (5c)，
並利用X-ray單晶繞射法確認5a之結構。藉由其互變異構化的特性，將二級磷酸接上鈀金屬，變成具提供電子能力之配位基。而此二級氧化磷(5a)在溶液中與其異構物--較不穩定的二級磷酸(secondary phosphonic acid)(5a’)存在著互變異構(Tautomerism)反應的性質。5a和鈀金屬反應，形成錯合物6及7。化合物6及7均利用X-ray單晶繞射法確認其結構。因二級氧化磷基不怕水氣之特性，使其保存容易，並將之運用在Suzuki偶合反應上。結果顯示以二茂鐵二級氧化磷基配位之鈀錯合物在硼酸與含推電子基芳香溴化物之耦合上有不錯的效果。

Ferrocenyl secondary phosphine oxides
(η5-C5H5)(η5-C5H4-P(=O)(tBu)(H))Fe (5a)、
(η5-C5H5)(η5-C5H4-P(=O)(Cy)(H))Fe (5b)、
(η5-C5H5)(η5-C5H4-P(=O)(Ph)(H))Fe (5c)were prepared. The molecular structures of 5a and 6、7 were determined by single-crystal X-ray diffraction methods. Palladium-catalyzed Suzuki reactions employing 5a as ligands gave satisfactory results. Judging from these results, a tautomeric equilibrium between 5a and its isomeric form ((

第一章 序 論
第一節 利用鈀金屬進行偶合之簡介-----------------------------------------2
第二節 Suzuki-Miyaura偶合反應---------------------------------------------6
第三節 二級磷氧化物(dialkyl phosphonates)的簡介---------------------9
第四節 現階段以磷化物為配位基所遇到的問題及嘗試解決的方法---------------------------------------------------------------------------12
第五節 有機及過渡金屬配位基---------------------------------------------15
第六節 二茂鐵(Ferrocene)的衍生物----------------------------------------19
第七節 研究方向---------------------------------------------------------------21

第二章 結果與討論
第一節 含二茂鐵單牙氧化磷基 5a、5b、5c、6、7 的製備---------------24
第二節 含二茂鐵單牙氧化磷基 5a及錯合物6、7的結構探討---------------28
第三節 含二茂鐵雙牙氧化磷基5a、6、7的Suzuki偶合反應機制探討----------------------------------------------------------------------33
第四節 含二茂鐵雙牙氧化磷基5a、5b、5c在Suzuki偶合反應上的應用-------------------------------------------------------------------------35

第三章 結論
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第四章 實驗部份
第一節 儀器與藥品------------------------------------------------------------48
第二節 操作技巧---------------------------------------------------------------52
第三節 合成與鑑定------------------------------------------------------------53
第四節 Suzuki催化反應步驟------------------------------------------------59
第五節 偶合產物光譜數據---------------------------------------------------61

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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