三價鐵超氧化物催化與動力學研究之探討
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2020
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Abstract
此研究使用本實驗室先前所開發之 N3O2 五牙基 H2BDPP，經去質子化後與 FeCl2 反應生成五配位二價鐵錯合物 Fe(BDPP) (1)，並可將其與氧氣反應形成超氧化合物 Fe(BDPP)(O2•) (2)，之後與 9,10-二氫蒽(9,10-dihydroanthracene, DHA) 行催化反應。錯合物 1 使用紫外－可見光光譜儀 (UV-Vis Spectroscopy) 及氣相層析質譜儀 (GasChromatography Mass Spectroscopy) 來追蹤反應過程和鑑定產物蒽(Anthracene)。在室溫下將錯合物 1 溶入四氫呋喃 (THF)，並與氧氧在 -90 ℃ 形成錯合物 2，從紫外－可見光光譜儀可發現反應溶液在330 nm 具有特徵吸收峰。並將錯合物 2 當成催化劑進行 9,10-二氫蒽(DHA) 的催化，生成蒽 (Anthracene)，使用氣相層析質譜儀鑑定產物及產率。最後計算出此反應的速率常數 (k2) 以及米氏常數 (KM) 。另一方面，使用電子順磁共振光譜儀 (Electron aramagnetic
Resonance Spectrometer) 及紫外－可見光光譜儀來鑑定反應的中間體，並根據上述兩種儀器的鑑定結果，找出此催化反應最有可能的反應機構。
A N3O2 pentadentate ligand, H2BDPP, previously developed by our laboratory was used to react with FeCl2 after deprotonation to generate a pentacoordinated iron complex Fe(BDPP) (1), which will react with dioxygen to produce a matal-superoxo complex, Fe(BDPP)(O2•) (2). Complex 2 is capable of catalyzing 9,10-dihydroanthracene (DHA) to produce anthracene. The reaction was monitored by UV-Vis spectroscopy and was identified by Gas Chromatography Mass Spectrometry. Notably, the rate constant (k2) and Michaelis-Menten constant (KM) of this reaction was obtained from Eadie-Hofstee plot. In addition, we use Electron Paramagnetic Resonance Spectrometer and UV-Vis Spectrometer to comfirm the intermediates of the reaction, and find out the most likely reaction mechanism of this catalytic reaction based on the findings resulting from the spectroscopic study.
A N3O2 pentadentate ligand, H2BDPP, previously developed by our laboratory was used to react with FeCl2 after deprotonation to generate a pentacoordinated iron complex Fe(BDPP) (1), which will react with dioxygen to produce a matal-superoxo complex, Fe(BDPP)(O2•) (2). Complex 2 is capable of catalyzing 9,10-dihydroanthracene (DHA) to produce anthracene. The reaction was monitored by UV-Vis spectroscopy and was identified by Gas Chromatography Mass Spectrometry. Notably, the rate constant (k2) and Michaelis-Menten constant (KM) of this reaction was obtained from Eadie-Hofstee plot. In addition, we use Electron Paramagnetic Resonance Spectrometer and UV-Vis Spectrometer to comfirm the intermediates of the reaction, and find out the most likely reaction mechanism of this catalytic reaction based on the findings resulting from the spectroscopic study.
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超氧化鐵錯合物, 催化反應, 反應速率, Iron superoxo, Catalytic reaction, Rate of reaction