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研究生: 任少緯
Jen, Shao-Wei
論文名稱: 四價鎳、錳錯合物之合成及鑑定與其質子還原反應之探討
Synthesis, Characterization of Nickel(IV) and Manganese(IV) Complexes and Studies of Their Proton Reduction Performance
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: 2015
畢業學年度: 103
語文別: 中文
論文頁數: 79
中文關鍵詞: 四價鎳錯合物四價錳錯合物質子還原反應
英文關鍵詞: Nickel(IV) complexes, Manganese(IV) complexes, Proton reduction
論文種類: 學術論文
相關次數: 點閱:137下載:0
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  • 此研究延續先前本實驗室許育禎學姊之論文,以兩分子H2PS2三牙配位基製備出Ni(PS2)2 (1),空氣穩定之四價鎳錯合物,並且藉由取代基的修飾以及錳金屬置換,進而合成出一系列鎳及錳四價錯合物,Ni(PS2TMS)2 (2)、Ni(PDMAS2)2 (3)、Mn(PS2)2 (4)、Mn(PS2TMS)2 (5)及Mn(PDMAS2)2 (6)。六個錯合物依據不同電子組態,分別進行NMR及EPR的鑑定,同時,利用紫外光/可見光光譜及X光吸收光譜進行光譜的分析。電化學方面利用循環伏安法鑑定錯合物之氧化還原性質以及探討其應用於質子還原反應性的可能性。

    To extend the research of our previously developed six-coordinated Ni(IV) complex supported by two R-PS22- ligand, Ni(PS2)2 (1). The Ni(IV) complex was modified with trimethylsilane and dimethylamino as substituent group. Besides, Mn(IV) complex was also synthesized with the same ligands. Here we present a series of nickel(IV) and manganese(IV) complexes (Ni(PS2TMS)2 (2), Ni(PDMAS2)2 (3), Mn(PS2)2 (4), Mn(PS2TMS)2 (5) and Mn(PDMAS2)2 (6). These complexes was characterized by X-ray crystallography, NMR, EPR, UV-vis spectra, X-ray absorption spectroscopy, and cyclic voltammetry. Cyclic voltammogram revealed two redox waves, which could provide the possibility of two electron reduction to Ni(II) or Mn(II) species. To examine these complexes as potential electrocatalysts for proton reduction, TFA was added to each complex solution and the system was examined by cyclic voltammetry.

    第一章 緒論 1 前言 1 第一節 氫化酵素之擬態錯合物 2 第二節 PS配位基錯合物系列研究 5 第三節 質子還原反應 7 第四節 研究方向 10 第二章 實驗部分 11 第一節 實驗儀器、藥品及條件 11 第二節 配位基之合成與鑑定 18 第三節 錯合物之合成與鑑定 23 第四節 電化學實驗 29 第五節 X-ray吸收光譜 32 第三章 結果與討論 35 第一節 配位基合成探討 35 第二節 鎳錯合物之合成及光譜探討 37 第三節 錳錯合物之合成及光譜探討 45 第四節 錯合物之X光吸收光譜 55 第五節 電化學性質與質子還原反應性之探討 60 第四章 結論與展望 75 參考文獻 77

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