本論文主要為藉由化學合成的方法，模擬[鐵鐵]氫化酵素活性中心結構，並合成出一系列的二鐵二硫化合物[(μ,κ2-bdt)(μ-PPh2)Fe2(CO)5(S-R)]（R = CH2COOMe (1), R = CH2CH2COOMe (2), R = CH2CH2COOH (3), bdt = 1,2-benzenedithiolate, Me = methyl）以及[{μ,κ2-3,6-(OC2H4R)2-bdt}Fe2(CO)5(μ-PPh2){S-(CH2)4COOMe}]n （R = NMe2, n = 0 (4), R = NMe3, n = + 2 (5), Me = methyl）。化合物1-5皆利用紅外線光譜儀（FTIR）、紫外線-可見光光譜儀（UV-vis）、質譜分析（MS）及核磁共振光譜儀（NMR）鑑定其結構，另外化合物1、2、3及化合物4也透過元素分析（EA）進行鑑定，且化合物1、2及化合物3亦透過X-ray單晶繞射儀進行鑑定。
為改善二鐵二硫化合物之疏水性，化合物3以具親水性的羧基官能基加以修飾，而化合物5以具親水性的四級銨鹽基團加以修飾，進而以不同修飾方法增加水溶性，並比較化合物之電催化表現差異。在乙腈（acetonitrile，CH3CN）溶液中以三氟乙酸（trifluoroacetic acid，TFA）作為酸源，並於過電位（overpotential）約等於1 V的條件下進行勻相加酸催化，結果顯示相較於化合物2，化合物3含有較高之產氫催化轉化率（turnover frequency，TOF），不過因化合物中皆含有diphenylphosphide的強疏水性基團，因此兩者水溶性程度皆不佳；然而化合物5將含氮官能基甲基化後，其化合物本身呈帶電的離子態，因此在水溶液中擁有良好的溶解度，並利用循環伏安法測量其於不同pH值之緩衝溶液中的電化學表現。結果顯示於pH = 7之水相的電化學表現，其在- 0.98 V （vs. SHE）有一個不可逆的還原訊號；當水溶液環境之pH值大於11時，其無催化效果，且可看到化合物之部分可逆（quasi-reversible）氧化還原訊號；當水溶液環境之pH值小於3時，其有較顯著之還原電流。

In this thesis, a series of diiron disulfide complexes [(μ,κ2-bdt)(μ-PPh2)Fe2(CO)5(S-R)] （R = CH2COOMe (1), R = CH2CH2COOMe (2), R = CH2CH2COOH (3), bdt = 1,2-benzenedithiolate, Me = methyl） and [{μ,κ2-3,6-(OC2H4R)2-bdt}Fe2(CO)5(μ-PPh2){S-(CH2)4COOMe}]n （R = NMe2, n = 0 (4), R = NMe3, n = + 2 (5), Me = methyl） were synthesized. All of them were characterized by Fourier transform infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV- vis), mass spectrometry (MS) and nuclear magnetic resonance spectroscopy (NMR), and complexes 1, 2, 3 and 4 were analyzed by elemental analysis (EA), and complexes 1, 2 and 3 were also analyzed by X-ray single crystal crystallography.
In order to improve the water solubility of diiron disulfide complexes, complex 3 was modified with a hydrophilic carboxyl functional group and complex 5 was modified with a hydrophilic quaternary ammonium salt group. Different modification of functional groups were used to increase the water solubility. Comparison of electrocatalytic performance of complexes was also discussed. In acetonitrile solution, trifluoroacetic acid was used as proton source, and under the condition of overpotential about 1 V, homogeneous hydrogen evolution reactions showed that complex 3 has a higher turnover frequency than complex 2. Unfortunately, both of complexes 2 and 3 have a poor water solubility due to hydrophobicity of the diphenylphosphide ligand. On the other hand, complex 5 bearing quaternary ammonium cation groups has a high solubility in aqueous solution. Electrocatalytic performance was investigated in aqueous solution under various pH conditions by cyclic voltammetry. An irreversible redox potential at - 0.98 V (vs. SHE) was observed at pH=7 whereas a quasi-reversible redox peak which infers limiting catalytic effect was recorded when pH is higher than 11. In addition, the higher reduction current was observed when pH is lower than 3.

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