Investigation Into The Synthesis And Electron Transfer Mechanism Of The[FeFe]-Hydrongenase

In this thesis, we simulated the active site of [FeFe]-hydrogenase and its surroundings for catalyzing rezction by chemical synthesization.In the first section, three diiron complexes (1-Ph,2-OH, and3-OCOFc) as the mimics of the diiron subunit of [FeFe]-hydrogenase were electrochemically investigated in0.1mol·L-1[NBut4]BF4/acetonitrile (MeCN) under CO and Ar atmosphere, respectively. Complex3-OCOFc was prepared from the reaction of complex2-OH with ferrocenylacyl chloride (FcOCCl). The complex was fully characterised using a variety of spectroscopic techniques. Its structure was established using X-ray single crystal diffraction analysis. In addition to the well-established ECE (E for electrochemical and C for chemical) mechanism, it was revealed that a further reversible reduction at a potential more negative by ca.600mV was observed. It was further proposed based on the analysis of electrochemical and infrared spectroscopic data that the second redox was due to a process of supposedly a tetrairon cluster which was formed in-situ from the reaction between the dianion generated from the ECE process and its parent complex (1-Ph,2-OH, and3-OCOFc) and which is supposedly of a core "Fe4(Ⅱ)". This reaction involved CO-binding since the presence of CO enhanced greatly the formation of the product. An overall mechanism to describe the electron transfer and coupled chemical reactions was proposed.In the second section, following the one-to-one principle for click chemistry, we co-polymerized complex A, B, C, D with different proportion. Finally we got a series of polymers functionalized with base moietie of different proportion and containing carboxyl. Combining the data of infrared spectroscopy, Mossbauer spectroscopy, thermal gravimetric analysis, scanning electron microscopy, transmission electron microscopy for them with the research of electrochemistry ability, we research into the influence of base moietie and carboxyl on these series of polymers. It is propitious to research its surroundings of [FeFe]-hydrogenase active center for catalyzing reaction...