研究生: |
張茲儀 Zi-Yi Zhang |
---|---|
論文名稱: |
含甲氧基取代之二鐵二硫化合物之合成、鑑定及電化學探討 Synthesis and Electrochemical Studies of [2Fe2S] Complexes Containing Methoxy Group |
指導教授: |
林昇佃
Shawn D. Lin 江明錫 Ming-Hsi Chiang |
口試委員: |
何郡軒
Jinn-Hsuan Ho 林昇佃 Shawn D. Lin |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2020 |
畢業學年度: | 108 |
語文別: | 中文 |
論文頁數: | 160 |
中文關鍵詞: | [鐵鐵]-氫化酵素 、氫氣 |
外文關鍵詞: | [FeFe]-hydrogenase, hydrogen |
相關次數: | 點閱:249 下載:0 |
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本論文的主軸為利用化學合成方法模擬[鐵鐵]氫化酵素活化中心的結構,並合成出一系列二鐵二硫化合物。
[(μ,κ2-3,6-(OCH3)2-bdt)(μ-PPh2)Fe2(CO)5](tS-R)(R= CH3,3;R= CH2CH2N(CH3)2,5)的合成、化學反應及電催化產氫機制探討,當化合物3與鹽酸反應,成功合成出來一次質子化的產物,{[(μ,κ2-3,6-(OCH3)2-bdt)(μ-H)(μ-PPh2)Fe2(CO)5](tS-CH3)}(BArF24)(4),證實其質子化的位置於雙鐵之間(bridge hydride);化合物5與鹽酸反應後可以進行三次質子化反應,分別得到:四級銨鹽(化合物6)、bridge hydride(化合物7)和S-protonated(化合物8;—SH)的產物,推測化合物7在質子化的過程,會使S—C鍵斷鍵與質子鍵結,形成化合物8。
利用1H和31P{1H}核磁共振(NMR)、紅外線光譜(FTIR)、質譜(MS)以及元素分析(EA)對所有化合物進行鑑定,由1H和31P{1H} NMR可以證實化合物3在溶液中會有兩種結構異構物,並透過X-ray繞射分析加以證實其固態結構。
化合物3和4分別利用循環伏安法觀察氧化還原行為,可以得知化合物4經過還原反應後會脫去橋接於雙鐵之間質子,回到化合物3;分別使用醋酸(HOAc)、三氟乙酸(TFA)和三氟甲磺酸(HOTf),三種不同強度的酸作為質子的來源,進行電催化產生氫氣,同時提出其電催化質子還原的作用機制。
A series of diiron dithiolate complexes were synthesized for [FeFe]-hydrogenase modeling study. Herein, I report the syntheses, electrochemistry and electrocatalytic activity of [(μ,κ2-3,6-(OCH3)2-bdt)(μ-PPh2)Fe2(CO)5](tS-R) (R=CH3, 3; R=CH2CH2N (CH3)2, 5) and protonated species of 5 (complexes 4, 6, 7 and 8).
All complexes are characterized by 1H and 31P{1H} NMR spectroscopies, fourier transform infrared spectroscopy (FTIR), mass spectrometry (MS) and elemental analysis (EA). According to 1H and 31P{1H} NMR results of complex 3, two types of isomers are present in the solution. Molecular structure of complex 3 is confirmed by X-ray crystallography. Furthermore, electrocatalytic proton reduction by the complexes have been studied in the presence of acetic acid, CF3COOH and CF3SO3H.
Molecular structure of complex 4, generated from the protonationindicates that of 3, protonation occurs onto the Fe—Fe vector to form the Fe bridging hydride species. The catalytic mechanism of hydrogen formation by complexes 3 and 4 is investigated.
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