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研究生: 林耘瑄
Yun-Hsuan Lin
論文名稱: 二席夫鹼雙亞硝基鐵錯合物之鑑定及其反應性
Characterization and Reactivities of Dinitrosyliron Complexes with Bis-Schiff Bases
指導教授: 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: 2013
畢業學年度: 101
語文別: 中文
論文頁數: 84
中文關鍵詞: 雙亞硝基鐵錯合物過氧化亞硝酸根陰離子一氧化氮
英文關鍵詞: DNICs, peroxynitrite, nitric oxide
論文種類: 學術論文
相關次數: 點閱:125下載:3
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  • 一氧化氮具有多種生理上的功能,可以調節免疫系統、使平滑肌細胞放鬆。雙亞硝基鐵錯合物在生物系統中被視為負責儲存和傳遞一氧化氮。利用[L1 = N,N’-(2,6-diisopropylphenyl)-2,3-dimethyl- 1,4-diaza-1,3-butadiene]配位基,可合成錯合物L1Fe(NO)2 (1)並確認結構。經由遠紅外線光譜儀偵測可得νNO = 1674, 1714 cm-1兩支吸收峰。錯合物1為深紫色,是因為Fe-NO電荷轉移(λmax = 550, 924 nm)所致。類似物L2Fe(NO)2 (2) [L2 = N,N’-(2,6-diisopropylphenyl)bis(imino)- acenaphthene]也被合成出來。由於錯合物2共軛骨架的影響造成遠紅外線吸收峰在1690, 1723 cm-1以及紫外/可見光吸收峰位移到λmax = 582, 1037 nm。錯合物1和2皆為空氣敏感物質,在−80 oC有氧氣的條件下,錯合物1及2的特徵吸收峰會逐漸減小,過程中沒有捕捉到含過氧化亞硝酸根的中間產物。因此,針對配位基進行修飾,選用2-吡啶甲醛以降低配位基的立體障礙、並增加配位基的電子密度。各種不同提供能力的配位基之雙亞硝基鐵錯合物[L3Fe(NO)2] (3), [L4Fe(NO)2] (4), [L5Fe(NO)2] (5) [L3 = 2,6-Diisopropyl-N-((pyridine-2-yl)methylene)benzenamine, L4 = N,N-dimethyl-N-(pyridine-2-ylmethylene)benzene-1,4-diamine, L5 = N-(2-pyridylmethylene)-4-fluorophenylamine]被一一合成。在氧氣存在的環境,錯合物3的紫外/可見光吸收峰的強度在−80 oC下逐漸減弱。我們推測在雙亞硝基鐵錯合物中,若配位基上的氮屬於sp2混成時,電子供給能力比配位基含sp3混成還弱,因此,在所合成的雙亞硝基鐵錯合物與氧氣的反應中,無法觀察到過氧化亞硝酸根中間體的生成。

    Nitric oxide (NO) has versatile physiological functions including immune system regulation, and smooth muscle relaxation. It has been suggested that dinitrosyliron complexes (DNICs) is responsible for storage and transport of NO in biological systems. Dinitrosyliron complex, L1Fe(NO)2 (1) (L1 = N,N’-(2,6-diisopropylphenyl)-2,3-dimethyl-1,4- diaza-1,3-butadiene), was synthesized and structurally characterized. Two characteristic IR absorption bands (νNO = 1674, 1714 cm-1) were observed in the THF solution of 1. Complex 1 has intensive purple color due to the absorption of Fe-NO charge transfer transition (λmax = 550, 924 nm). An analogous, L2Fe(NO)2 (2) (L2 = N,N’-(2,6-diisopropylphenyl)bis(imino)-
    acenaphthene), was also synthesized. Infrared (1690, 1723 cm-1) and UV/vis absorptions (λmax = 582, 1037 nm) of 2 indicate the electronic influence of L2 from its conjugated backbone. Both 1 and 2 are air-sensitive. In the presence of O2, UV-vis absorption bands of 1 and 2 gradually diminish even below −80 oC. In the process, catch peroxynitrite intermediate was not observed. Hence, we manage to modify ligands which employing 2-pyridinecarboxaldehyde for reducing the steric hindrance and strengthening electron density of ligands. The L3Fe(NO)2 (3), L4Fe(NO)2 (4), and L5Fe(NO)2 (5) (L3 = 2,6-diisopropyl-N- ((pyridine-2-yl)methylene)benzenamine, L4 = N,N-dimethyl-N-(pyridine- 2-ylmethylene)benzene-1,4-diamine, L5 = N-(2-pyridylmethylene)-4- fluorophenylamine) containing differential electron donating ligands was synthesized. In the presence of O2, UV-vis absorption bands of 3 also diminish below −80 oC. We speculate that the prepared DNICs containing sp2 nitrogen donor ligands which possess less electron-donating ability than that of sp3 nitrogen donor ligands. Therefore, no peroxynitrite intermediate were observed in the reactions of the prepared DNICs and O2.

    目錄 I 圖引索 III 表引索 VI 謝誌 VII 中文摘要 VIII Abstract X 第一章 緒論 1 1-1 一氧化氮在生物體之重要性 1 1-2 一氧化氮在生物體內的儲存及運輸方式 2 1-3含氮之DNICs 10 1-4過氧化亞硝酸根陰離子(peroxynitrite, ONOO−) 14 第二章 實驗部分 16 2-1實驗儀器及條件 16 2-3 鐵錯合物之合成與鑑定 22 2-4 雙亞硝基鐵錯合物之合成與鑑定 24 2-5錯合物之氧化反應性 28 第三章 結果與討論 31 3-1配位基之設計概念 31 3-2不對稱配位基之設計概念 49 3-2-2金屬錯合物3、4與5之紅外線吸收光譜比較 53 3-2-3金屬錯合物之電化學性質探討 53 3-2-4錯合物3與氧氣之反應 56 3-2-5錯合物3與氧化劑之反應 57 第四章 結論 61 參考文獻 62 附錄 64

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