鐵(Ⅲ)錯合物具兒茶酚及半醌配位基的合成、結構和反應性研究

Synthesis, structure and reactivity of Iron(Ⅲ) complexes with catecholate and semiquinone ligands

呂建緯(Jian-Wei Lu)

指導教授 ： 魏和祥

淡江大學/理學院/化學學系碩士班/碩士(2008年)

https://doi.org/10.6846/TKU.2008.00841

摘要

本論文合成具兒茶酚及半醌配位基的鐵(Ⅲ)錯合物(1)~(4)，性質及其物性由X-ray單晶繞射儀、UV-Vis光譜、元素分析儀、電化學、電子順磁共振光譜及紅外線光譜方法來分析。
具半醌及兒茶酚配位基錯合物:
(1) [Fe(L1)(C6Cl4O2)]2•OCH3
(2) [Fe(L2)(C6Cl4O2)Cl2]
(3) [Fe(L2)(C6Cl4O2)2]
(4) [Fe(L3)(C6Cl4O2)2]CH3CN•CH3OH
L1: 2-((E)-(2-(2-aminoethylamino)ethylimino)methyl)phenol
L2:(E)-N1-(2-(dimethylamino)ethyl)-N2-((5-methyl-1H-imidazol-4-yl)methylene)
ethane-1,2-diamine
L3: N,N-diethyl-2-(2-(pyridin-2-yl)imidazolidin-1-yl)ethanamine

錯合物(1)~(4)對1,2雙加氧酶在甲醇溶液中的反應活性，由添加入四種不同的兒茶酚陰離子tetrabromocatechol(TBC), tetrachlorocatechol(TCC), catechol(HC),和3,5-di-tert-butylcatechol(3,5-DTBC)與[Fe(L1)Cl2]、[Fe(L2-3)Cl3]反應，根據吸收位置與路易士酸性的關係可發現，路易士酸性越強的錯合物[Fe(L2) 3,5-DTBC]有較佳加氧酶的催化反應性。

關鍵字

兒茶酚 ； 半醌 ； 鐵(Ⅲ)錯合物 ； X-ray結構 ； EPR光譜

並列摘要

The following complexes(1)~(4) with catecholate and semiquinone ligands
were synthesized and physical properties of complexes(1)~(4) were measured by
X-ray Single diffraction, UV-Vis spectroscopy, infrared spectra, element analyzer, and
Electronchemical analysises.
Iron(Ⅲ) complexes with catecholate and semiquinone ligands were prepared:
(1) [Fe(L1)(C6Cl4O2)]2•OCH3
(2) [Fe(L2)(C6Cl4O2)Cl2]
(3) [Fe(L2)(C6Cl4O2)2]
(4) [Fe(L3)(C6Cl4O2)2]CH3CN•CH3OH
L1: 2-((E)-(2-(2-aminoethylamino)ethylimino)methyl)phenol
L2:(E)-N1-(2-(dimethylamino)ethyl)-N2-((5-methyl-1H-imidazol-4-yl)methylene)
ethane-1,2-diamine
L3: N,N-diethyl-2-(2-(pyridin-2-yl)imidazolidin-1-yl)ethanamine

The methanol solutions of complexes(1)~(4) were titrated with catecholate anions of tetrabromocatechol(TBC), tetrachlorocatechol(TCC), catechol(HC), and 3,5-di-tert-butylcatechol(3,5-DTBC). The results show that the high lewis acidity iron(III) complexes [Fe(L2) 3,5-DTBC] exhibits the higher catechol 1,2-dioxygenase reactivity.

並列關鍵字

semiquinone ； catecholate ； Iron(III) complexes ； X-ray structure ； EPR spectrum

參考文獻

1. Gerdemann, C. ; Eicken, C. ; Krebs, B., Acc. Chem. Res. 2002, 35, 183.

3. Hayaishi, O. ; Hashimoto, Z., J. Biochem. 1950, 37, 371.

4. Hayashi, O. ; Katagin, M. ; Rothberg, S., J. Am. Chem. Soc. 1955, 77, 5450.

7. Nozaki, M., Topics in Current Chem. 1979, 78, 145.

9. Que, L. Jr. ; Ho, R. Y. N., Chem. Rev. 1996, 96, 2607.