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研究生: 莊堯舜
論文名稱: 似單氧化酵素之三核錳金屬簇化物之研究
Monooxygenase-like Trinuclear Manganese complex
指導教授: 陳炳宇
Chen, Ping-Yu
李位仁
Lee, Way-Zen
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2012
畢業學年度: 100
語文別: 中文
論文頁數: 67
中文關鍵詞: 似單氧化酵素三核錳金屬簇化物催化
論文種類: 學術論文
相關次數: 點閱:88下載:1
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  • 本實驗室先前的研究中,我們發展出7-Dipy配位基成功合成出三核錳金屬簇離子化合物 [MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) ,作為高價態的錳金屬簇離子化合物的前驅物,藉由加入二當量氧化劑TBHP氧化[MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) ,可得一組16根特徵吸收之ERP光譜,在此假定得到一活性中間體[MnIIIMnIII(μ-O)2MnIV(7-Dipy)]4+ (4),在催化上,可藉由加入氧化劑TBHP可將環己烷氧化為環己醇與環己酮。
    在我的研究中,將受質嘗試使用其他環烷類與長鏈烷類,包含
    環戊烷、正戊烷、正己烷、正庚烷與正辛烷,皆能進行催化生成多碳位氧化的醇類及酮類。
    為了解三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] 催化反應,是自由基反應或是經由單氧直接嵌入的一步反應機構,我們利用DMPO對自由基物質相當靈敏的特性,將三核錳金屬簇化物加入DMPO進行實驗,由實驗的EPR光譜可以得到,我們推測三核錳金屬簇化物[MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] ,以甲醇為溶劑,加入TBHP進行催化反應立即所測知ERP光譜與DMPO=O之ERP光譜類似。

    Previous studies in our laboratory, we developed a 7-Dipy ligand base successfully synthesized of trinuclear manganese complex. This trinuclear manganese complex [MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) was synthexized as a precursor for the high-valent manganese species. Further oxidation of [MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) by treating two equivalents of TBHP (tert-butyl hydroperoxide) is able to obtain a 16-line characteristic EPR spectrum, which is postulated as a active intermediate, [MnIIIMnIII(μ-O)2MnIV(7-Dipy)]4+ (4)is able to catalyze the oxidation of C-H bonds of cyclohexane to a mixture of cyclohexanol and cyclohexanone.
    In my study, a series of substrates, other cycloalkane and long-chain alkanes, including cyclopentane, n-pentane, n-hexane, n-heptane and n-octane, are able to be oxidized.
    To further understand the trinuclear manganese complex [MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) carrying out catalytic raction are free radical reaction mechanism or via a single oxygen step reaxtion mechanism. Therefore, we designed a series of experiments using very sensitive to free radicals, DMPO to detect the trinuclear manganese complex [MnII(OAc)2MnII(μ-OAc)2MnII(7-Dipy)] (3) by adding TBHP catalytic reaction immediately by detect ERP spectra, which shows a NO. radical species and is similar to the DMPO  O of the ERP spectrum similar.

    致謝.......................................................I 中文摘要...................................................II 英文摘要..................................................III 第一章 前言.................................................1 第二章 實驗部分 2-1 藥品與儀器.......................................6 2-2 3,3’-(1,4-di azepane-1,4-diyl)bis(1- chloropropan-2-ol) (1) 之合成...................7 2-3 3,3’-(1,4-diazepane-1,4-diyl)bis(1-(bis (pyridine-2-ylmethyl)amino)propan-2-ol (2)之合成.8 2-4 三核錳金屬簇離子化合物 [MnII(OAc)2MnII(μ-OAc)2MnII(7- dipy)] (3) 之合成................................9 2-5 三核錳金屬簇離子化合物 [MnIIIMnIII(μ-O)2MnIV(7-dipy)] 4+ (4) 之合成...................................11 2-6 產物的鑑定.......................................13 化合物結構與編號.......................................14 第三章 結果與討論 3-1 三核錳金屬簇離子化合物之EPR光譜......................15 3-2 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)](3)之UV-Vis與CV光譜........................20 3-3 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3)與環己烷的催化反應.......................23 3-4 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環己烷的催化反應,改變合成三核錳金屬簇離子化合 物之NEt3當量數....................................29 3-5 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環己烷的催化反應,改變反應溶劑的使用量.....33 3-6 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環己烷的催化反應,改變氧化劑,以TBHP在 5.0~6.0 M solution in Decane 進行催化反應.........35 3-7 三核錳金屬簇離子化合物 [MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環己烷的催化反應,以C2H5OH 當作溶劑......37 3-8 三核錳金屬簇離子化合物 [MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環己烷的催化反應,以 1-Propanol 當作溶劑.39 3-9 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與環戊烷的催化反應......................42 3-10 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與正戊烷的催化反應......................44 3-11 三核錳金屬簇離子化合物 [MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與正己烷的催化反應......................46 3-12 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與正庚烷的催化反應......................48 3-13 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與正辛烷的催化反應......................51 3-14 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 與TBHP反應時中間物之EPR研究..............55 3-15 三核錳金屬簇離子化合物[MnII(OAc)2MnII(μ-OAc)2MnII(7- Dipy)] (3) 之養晶研究.............................59 第四章 結論................................................60 第五章 參考文獻.............................................61 附圖目錄 附圖 一 7-Cl (1) (1) 之 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 1H NMR H NMR H NMR H NMR H NMR 光譜 ……………………… ……………………… ……………………… 63 附圖 二 7-Cl (1) (1) 之 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 13 C NMR C NMR C NMR 光譜 …………………… …………………… …………………… 64 附圖 三 7-DipyDipyDipyDipy (2) (2) 之 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 1H NMR H NMR H NMR H NMR 光譜 …………………… …………………… …………………… 65 附圖 四 7-DipyDipyDipyDipy (2) (2) 之 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 400 MHz 13 C NMR C NMR C NMR 光譜 ………………… ………………… 66 附圖 五 7-DpiyDpiyDpiyDpiy (2) (2) 之 LCQLCQ -ESI MassESI Mass ESI Mass ESI MassESI Mass光譜 ……………………… ……………………… ……………………… 67

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