由於在生物體內發現的鐵鐵氫化酶在自然界中能夠可逆地催化氫氣的氧化和質子的還原反應,而其金屬活性中心的結構和功能模擬近年來引起生物無機學家們的興趣。因此本論文計畫透過置換配位基來合成類似鐵鐵氫化酶活性中心的雙亞硝基鐵化合物(DNICs),並且以含氮異環碳烯N-Heterocyclic Carbenes(NHC)配位基來穩定結構。同時分別以2-aminothiophenol (L1)、2-(dimethylamino)benzenethiol (L2)做為pentdant base合成化合物iMes-Fe(NO)2SPhNH2(1)與iMes-Fe(NO)2SPhNMe2 (2),在紅外光光譜與循環伏安法的比較其二對鐵中心的影響,在此系統中發現2-(dimethylamino)benzenethiol有較佳的σ-donating能力。 本論文也透過置換中心金屬合成含有與上述所提之相同配位基的雙亞硝基鈷化合物,然而在紅外光光譜中理論上含有σ-donating能力較好的2-(dimethylamino)benzenethiol的化合物3比化合物4往高波數位移,此結果是與鐵為金屬中心的結果相反的,同時我們將化合物1、2、3、4與對甲苯磺酸反應得到portonation後的產物,比較後發現化合物1、3在紅外光光譜分別在1793cm-1、1837cm-1處有一小包峰值,透過1H NMR光譜鑑定後推測可能為metal hydride的形成,往後也將利用養晶來確認我們的推測是否為正確。
The [Fe-Fe] hydrogenase found in organism can catalyze the oxidation of hydrogen and the reduction of protons reversibly in nature, and the structure and function simulation of its metal active center has attracted the interest of bioinorganic scientists in recent years. Therefore, in this thesis, we plan to synthesize dinitrosyl iron complex (DNICs) similar to [Fe-Fe] hydrogenase active centers by replacing ligands, and stabilize the structures with N-Heterocyclic Carbenes (NHC) ligands. At the same time, 2-aminothiophenol and 2- (dimethylamino) benzenethiol were used as pentdant bases respectively, and the effect on iron centers was compared in the infrared spectrum and cyclic voltammetry. This thesis also synthesizes dinitrosyl cobalt complex containing the same ligands as mentioned above by replacing the central metal, but theoretically compound 8 contains 2- (dimethylamino) benzenethiol with better σ-donating ability was shifted to a higher wave number than compound 7 in the infrared spectrum. This result is the opposite of the result of iron as the metal center. When we tried to figure out the phenomenon using the crystal structure of the two compounds after protonation, we also found that it was unexpectedly discovered that there may be the formation of meatl hydride.In the future, crystal growth will also be used to confirm whether our guess is correct.
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