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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/5944

    Title: 利用聯?啶系列進行有機鐵化合物的金屬移;除反應之研究 Demetallation of organoiron complexes
    Authors: 林美齡;Lin-May Ling
    Contributors: 化學研究所
    Keywords: 金屬移除;Demetallation
    Date: 2003-07-10
    Issue Date: 2009-09-22 10:10:52 (UTC+8)
    Publisher: 國立中央大學圖書館
    Abstract: 摘 要 傳統上有機鐵化合物進行金屬移除反應(Demetallation)都是利用酸或強氧化劑將鐵金屬中心氧化後移除的。我們發現有機鐵化合物,鐵金屬中心氧化態由正二價到零價,都會和聯?啶系列的有機配子直接產生穩定的聯?啶鐵化合物並不需酸或氧化劑的協助。因而引起了我們的興趣,進行了一系列的研究與討論。近年來含氮雜環配位基特別是多聯?啶已被廣泛地研究,已知2,2、-聯比啶可配位至金屬離子生成錯合物。但極少有人利用這種配位化學的知識來達成有機金屬化合物的金屬移除反應。我們試著了解?啶在其中的角色,除了是很好的配位基之外,很有可能是微量?啶的還原性質引發了金屬移除反應,有機金屬化合物利用 17e-19e自由基的機制行配位子取代反應,最後生成三聯?啶鐵錯合物。 有機鐵化合物 [(η5-C5H5)Fe(CO)2I]、[(η5-C5H5)Fe(CO)2PPh3]+、[(η5-C5H5)Fe(CO)2]2、[{(η5-C5H5)Fe(CO)2}2(μ-PPh2)]+、[(η4-C5H5Me)Fe(CO)2PPh3]分別在氮氣下和聯?啶在乙醚的溶液中混合攪拌,可產生鮮紅色三聯?啶鐵陽離子的沉澱。我們利用紅外線光譜儀(IR)來追蹤有機鐵化合物中羰基(νCO)的吸收峰變化,以觀測有機鐵化合物殘存程度。用核磁共振氫譜(1HNMR)和電子吸收光譜(UV-Vis),以確認紅色的沉澱是三聯?啶鐵化合物。對不同價數鐵的 有機鐵化合物,我們也分析了[(η5-C5H5)Fe(CO)2I]和[(η4-C5H5Me)Fe(CO)2PPh3]的競爭反應。兩價的有機鐵化合物比零價的反應性好:在紅外線光譜中兩價鐵化合物羰基(νCO)的吸收峰消失時,零價鐵化合物的並未完全消失。 ?啶配位基擴展至啡?衍生物時,也會進行有機鐵化合物的金屬移除反應,生成三啡?鐵陽離子錯合物。我們利用電子吸收光譜及循環伏安儀來分析在不同電子效應下的啡?配位基對金屬鐵中心的影響。藉由旋轉伏安儀的技術,研究有機金屬鐵化合物和2,2、-聯?啶反應時,其電子轉移的變化情形。我們也利用封管方式的核磁共振氫譜實驗,持續追蹤?啶和有機鐵化合物的金屬移除反應,並推論反應機制。 Abstract : The demetallation of organoiron complexes is usually achieved under strong oxidizing reaction conditions. We found that the organoiron complexs , that oxidation state from +2 to 0, all react with bpy and get stable Fe(bpy)32+ complex,and don’t need strong acid or oxidation reagent. Therefore, we have design a series of experiment to investigate and discuss. Recently , polydentate ligands containing N-donor heterocyclic rings have played an important role in the development of coordination chemistry and continued to be widespread interest , particularly centered upon complexes of diimine-type ligands, 2,2’-bipyridine(bpy), 1,10-phenanthroline (phen) . But most of these complexes, were synthesized from metal ion, seldom people use this kind of concept to synthesize the Fe(bpy)32+. We try to understand the role of bpy, not only for a good coordination ligand, but also the possibility of the redutivity for bpy induced the demetallation of orgnoiron complex. We used the FT-IR、1HNMR、UV-Vis、CV to investigate the chemistry. From these data, we have confirm the demetallation product is Fe(bpy)32+. And we also use 1HNMR、UV-vis、RDE to monitor the change of reaction try to understand the mechanism with 17e-19e mechanism. We also extended our interests to other phen type ligand, and synthesized the Fe2+ complexes with phen type ligand. Use UV-vis and CV to investigate the difference.
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