李位仁Lee, Way-Zen林威呈Lin, Wei-Cheng2020-10-192025-07-012020-10-192020http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22G060742060S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/111159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.超氧化鐵錯合物催化反應反應速率Iron superoxoCatalytic reactionRate of reaction