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.
1. Wessel, J.; Crabtree, R. H., Nonradical tetrabutylammonium
monopersulfate oxidation of hydrocarbons catalyzed by
[Mn(3)O(4)bipy(4)(H2O)(2)](ClO4)(4). J. Mol. Catal. A-Chem. 1996, 113
(1-2), 13-22.
2. do Nascimento, E.; Silva, G. D.; Caetano, F. A.; Fernandez, M. A. M.;
da Silva, D. C.; de Carvalho, M.; Pernaut, J. M.; Reboucas, J. S.; Idemori, Y. M., Partially and fully beta-brominated Mn-porphyrins in P450 biomimetic
systems: Effects of the degree of bromination on electrochemical and
catalytic properties. J. Inorg. Biochem. 2005, 99 (5), 1193-1204.
3. Smith, J. R. L.; Iamamoto, Y.; Vinhado, F. S., Oxidation of alkanes by
iodosylbenzene (PhIO) catalysed by supported Mn(III) porphyrins: Activity
and mechanism. J. Mol. Catal. A-Chem. 2006, 252 (1-2), 23-30.
4. Rose, E.; Andrioletti, B.; Zrig, S.; Quelquejeu-Ehteve, M.,
Enantioselective epoxidation of olefins with chiral metalloporphyrin
catalysts. Chem. Soc. Rev. 2005, 34 (7), 573-583.
5. Cavallo, L.; Jacobsen, H., Radical intermediates in the Jacobsen-Katsuki epoxidation. Angew. Chem.-Int. Edit. 2000, 39 (3), 589-592.
6. Dismukes, G. C., Manganese enzymes with binuclear active sites. Chem. Rev. 1996, 96 (7), 2909-2926.
7. He, J.; Hertweck, C., Iteration as programmed event during polyketide
assembly; molecular analysis of the aureothin biosynthesis gene cluster.
Chem. Biol. 2003, 10 (12), 1225-1232.
8. He, J.; Hertweck, C., Biosynthetic origin of the rare nitroaryl moiety of
the polyketide antibiotic aureothin: Involvement of an unprecedented
N-oxygenase. J. Am. Chem. Soc. 2004, 126 (12), 3694-3695.
9. Winkler, R.; Hertweck, C., Sequential enzymatic oxidation of
aminoarenes to nitroarenes via hydroxylamines. Angew. Chem.-Int. Edit.
2005, 44 (26), 4083-4087.
10. Jacob S. Kanady, A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II. Science. 2011, vol 333.
11. Georgiy B. Shul’pine, Mild oxidative functionalization of alkanes and alcohols catalyzed by new mono- and dicopper(II) aminopolyalcoholates, Journal of Molecular Catalysis A: Chemical, 2011, 350
12. Lowell D. Kispert., Generation of superoxide anion and most likely singlet oxygen in irradiated TiO2 nanoparticles modified by carotenoids, Journal of Photochemistry and Photobiology A: Chemistry, 2004 , 162.