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    Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/74019


    Title: 具四鐵四硫、二鐵二硫化合物之合成、鑑定與反應性之探討;Synthesis and Characterization of [4Fe4S] complexes、[2Fe2S] complexes and Their Application toward Hydrogen Evolution
    Authors: 賴彥霖;Lai, Yen-Lin
    Contributors: 化學學系
    Keywords: 四鐵四硫化合物;[4Fe4S] complexes
    Date: 2017-08-17
    Issue Date: 2017-10-27 12:59:29 (UTC+8)
    Publisher: 國立中央大學
    Abstract: 本論文主要是藉由化學合成的方法模擬鐵-鐵氫化酵素,並合成一系列四鐵四硫之化合物 [{μ,μ,κ2-3,6-(OSitBuMe2)2-bdt}2(μ-PPh2)2(μ-H)xFe4(CO)8][B(C6F5)4]x (bdt = 1,2-benzenedithiolate,x = 0 (3),x = 1 (4),x = 2 (5) )及雙鐵雙硫化合物 [(μ-3,6-R2-bdt)Fe2(CO)6] (R = OCO2C2H5 (7),OCH2CONH2 (8),OC3H6SO3 (9) )。
    在四鐵四硫化合物的部分,當 bdt上的H被推電子基 OSitBuMe2取代後,而得到化合物 [{μ,μ,κ2-3,6-(OSitBuMe2)2-bdt}2(μ-PPh2)2Fe4(CO)8] (3),四鐵四硫催化劑產氫催化速率kcat值從1393 M-1 s-1 增加至3308 M-1 s-1,速率增加約2.5倍。當化合物3和 [(Et3Si)2H][B(C6F5)4] 反應,成功合成出來一次質子化和二次質子化的產物4和5。
    在雙鐵雙硫化合物的部分,以水溶性的官能基修飾雙鐵雙硫化合物,合成出化合物7、8、9。紫外光-可見光光譜的結果,指出化合物7、8並不溶水,而化合物9在水中的最大溶解度為9.42 mM。化合物7、8在有機相的酸催化效率,分別為kcat = 392 M-1 s-1與kcat = 351 M-1 s-1,催化效果與無任何官能基取代的 [(μ-bdt)Fe2(CO)6] (kcat = 632 M-1 s-1) 相近。另外,在水相下對化合物9在水溶液下催化醋酸產生氫氣,其kcat值為1446 M-1 s-1,較相似衍生物在有機溶劑下之催化效果佳。
    ;A series of tetra-iron complexes [{μ,μ,κ2-3,6-(OSitBuMe2)2-bdt}2(μ-PPh2)2(μ-H)x Fe4(CO)8][B(C6F5)4]x (bdt = 1,2-benzenedithiolate,x = 0 (3),x = 1 (4),x = 2 (5) ) and di-iron complexes [(μ-3,6-R2-bdt)Fe2(CO)6] (R = OCO2C2H5 (7),OCH2CONH2 (8),OC3H6SO3 (9) ) have been synthesized and characterized.
      Electrochemical analysis of complex 3, bearing electron rich groups OSitBuMe2 on bdt site, has an apparent improvement in kcat value, from 1393 M-1 s-1 to 3308 M-1 s-1. Intermediates 4 and 5 were successfully synthesized with the reaction of 3 and [(Et3Si)2H][B(C6F5)4].
      Complexes 7-9, developed as fundamental models of the two-iron subsite in the [Fe-Fe]-hydrogenase enzyme active site show water solubility by virtue of different water-soluble functional groups in corporated into the benzenedithiolate unit that bridges two Fe(CO)3 moieties. These complexes were characterized by IR, NMR, UV-vis spectroscopy and electrochemistry. Apart from complex 9, complexes 7 and 8 are not soluble in water. The kcat value of 7 (392 M-1 s-1) and 8 (351 M-1 s-1) are similar to [(μ-bdt)Fe2(CO)6] (kcat = 632 M-1 s-1). However, the kcat value of 9 in the presence of water is 1446 M-1 s-1, shows a higher performance than other diiron dithiolate derivatives in organic solvent.
    Appears in Collections:[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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