含氮多牙基之金屬錯合物合成、結構及其對於3-羥基黃酮氧化斷裂之催化反應的研究

Synthesis and Structure of Metal Complexes with a N-Containing Polydentate Ligand and Their Catalysis towards Oxidative Cleavage of 3-Hydroxyflavone

簡秀萍(Chien Hsiu Ping)

指導教授 ： 李位仁 老師

國立臺灣師範大學/理學院/化學系在職進修碩士班/碩士(2009年)

摘要

中文摘要
為了模擬可催化黃酮醇類(flavonols)氧化斷裂反應之槲黃素氧化酶(quercetin 2,3-dioxygenase)的活化中心，本研究製備一個含雙苯咪唑的多牙基配子bis(1-methylbenzimidazole-2-ylmethyl)-N-p-toluenesulfonylamine (L)，用以合成二價鎳、銅、鋅和錳等錯合物，並利用元素分析、紫外線/可見光光譜、電灑質譜、紅外線光譜及X-光單晶繞射解析法完成錯合物的鑑定。所合成的錯合物在1 mol%、5 mol%和10 mol%的比例下，分別與3-羥基黃酮(3-hydroxyflavone)和氧氣一起反應，並利用紫外光/可見光光譜儀追蹤反應的過程，我們發現二價鎳錯合物[LNi(DMF)3](ClO4)2 (3)及LNiCl2 (4)會催化3-羥基黃酮的氧化斷裂反應，在文獻中這是第一個例子。以10 mol%的錯合物3或4進行催化反應時，其受質的消耗速率分別比進行空白實驗時受質的消耗速率快6.0或5.8倍。但是銅錯合物[LCu-(DMF)3](ClO4)2 (1)、LCuCl2•0.5CH3OH (2)、錳錯合物[LMn(H2O)-(DMF)(CH3CN)](ClO4)2 (6)及並沒有顯現催化的能力，可能是錯合物1、2和6的配子從中心金屬解離了；而鋅錯合物[LZn(H2O)(CH3CN)](ClO4)2 (5)也沒有顯現催化的效果，其受質的消耗速率比空白實驗慢，可能是錯合物5與受質反應時，不會再進一步與氧氣進行氧化斷裂的反應。

關鍵字

3-羥基黃酮

並列摘要

Abstract
In order to mimic the active site of quercetin 2,3-dioxygenase, which catalyzes the oxidative cleavage of flavonals, a bis(benzimidazolyl) polydentate ligand, bis(1-methylbenzimidazole-2-ylmethyl)-N-p-toluene- sulfonylamine (L), was prepared to synthesize complexes of Ni(II), Cu(II), Zn(II), and Mn(II), which were fully characterized by elemental analysis, UV/vis, ESI-MS, IR spectroscopies, and X-ray crystallography. The synthesized complexes was employed to examine the reactions of 3-hydroxyflavone and dioxygen in the presence of 1 mol%, 5 mol%, and 10 mol% of mental complexes, and the reactions were monitored by UV/vis spectroscopy. Two complexes, [LNi(DMF)3](ClO4)2 (3) and LNiCl2 (4), were found to possess the catalytic ability towards the oxidative cleavage reaction of 3-hydroxyflavone. With 10 mol% of complexes 3 or 4, the catalytic rate of the reactions were 6.0 or 5.8 times faster than that of the control experiment. This is the first example in the literature. However, complexes, [LCu-(DMF)3](ClO4)2 (1), LCuCl2•0.5- CH3OH (2), [LMn(H2O)(DMF)-(CH3CN)](ClO4)2 (6), and [LZn(H2O)(CH3CN)](ClO4)2 (5), can not catalyze the above reaction. It is possible that L of 1, 2, and 6 was dissociated from the complexes in the reaction with 3-hydroxyflavone, or the substrate, 3-hydroxyflavone, was only coordinated to 5 and not to be catalyzed.

並列關鍵字

3-hydroxyflavone

參考文獻

A.; Kekos, D.; Macris, B. J.; Christakopoulos, P. Food Biotech. 2004,

5. Tranchimand S.; Tron T.; Gaudin C. and Iacazio G. FEMS Microbiology Letters 2005, 253, 289.

11.Lewis, E. A.; Tolman, W. B. Chem. Rev. 2004, 104, 1047.

16. Steiner, R. A.; Kalk, K. H.; Dijkstra, B. W. Proc. Natl. Acad. Sci. 2002, 99, 16625-16630.

19. Balogh-Hergovich, E.; Speier, G.; Argay, G. J. Chem. Soc., Chem. Commun., 1991, 551.