合成與鑑定具水溶性之二鐵二硫化合物

Abstract

本論文主要是藉由化學合成的方式來模擬[鐵鐵]-氫化酵素活性中心，並合成一系列二鐵二硫化合物[{μ-3-OR-6-OR'-bdt}Fe2(CO)6] (bdt = 1,2-benzenedithiolate， R = R' = －CH2OC2H4OCH3 (3) ，R = H、R' = －CH2OC2H4OCH3 (4) ，R = R' = －C2H4N(CH3)2 (5) ，R = H、R' = －C2H4N(CH3)2 (6))及[{μ-3-OR-6-OR'-bdt}Fe2(CO)6]n (R = R' = C3H6SO3，n = -2 (2) ，R = R' = －C2H4N(CH3)3，n = +2 (7))。 在接上具親水性的官能基後，化合物3、4、5、6仍不溶於水，四個化合物在電化學表現上仍相近於無任何官能基取代的[(µ-bdt)Fe2(CO)6] 及作為合成起始物的[(µ-1,4-diol-bdt)Fe2(CO)6]，結果顯示若置換苯環上的官能基並不會影響二鐵二硫化合物在電化學上的產氫的機制。 帶有磺酸鹽類官能基的化合物2及帶有四級銨鹽官能基的化合物7則是能溶於水。以水為溶劑的循環伏安法量測實驗，化合物7在0.82 V處有一組相較化合物2在0.92 V處更正的可逆還原訊號。兩者在水相催化醋酸產生氫氣的催化效果也相較類似衍生物在有機相更佳。A series of diiron disulfur complexes [{μ-3-OR-6-OR'-bdt}Fe2(CO)6] (bdt = 1,2-benzenedithiolate, R = R' = －CH2OC2H4OCH3 (3), R = H、R' = －C H2OC2H4OCH3 (4), R = R' = －C2H4N(CH3)2 (5), R = H、R' = －C2H4N(CH3)2 (6))及[{μ-3-OR-6-OR'-bdt}Fe2(CO)6]n (R = R' = C3H6SO3, n = -2 (2) ，R = R' = －C2H4N(CH3)3, n = +2 (7)) were synthesized and characterized by FT-IR, NMR UV-vis spectroscopy, MS, X-ray single crystallography and elementalanalyses. When the dithiolate linker is functionalized by the ether or tertiary amine group, complex 3, 4, 5 and 6 are not water-soluble. Their performance in electrochemistry is similar to those of [(µ-bdt)Fe2(CO)6] and [(µ-1,4-diol-bdt)Fe2(CO)6]. As the sulfonate or the quaternary ammonium ligand is attached to the dithiolate linker, complexes 2 and 7 are soluble in aqueous solution. Both of the complexes show higher catalytic performance on reducing proton than other diiron disulfur derivatives performed in organic solvent.