Modelling The Metal Center Of Hydrogenases

Scientists and governments put a great emphasis on hydrogen, a renewable, high energy/mass ratio, environment-friendly clean energy, to solve the energy crisis and environmental degradation. This dissertation focuses on the hydrogenase model compounds, comprise mainly the following aspects:1. A simple hydrogenase mimic was synthesized from Fe3(CO)12and a ready-made ligand,2,2'-((pyridin-2-ylmethyl)azanediyl)diethanethiol. The reaction mixture and product were charactered carefully and a possible mechanism for the C-S/N bonds formation/cleavage in the formation of the complex is proposed.2. A phenylethene containing [FeFe]-hydrogenase mimic complex [Fe2(μ-S2)CHCPh(CO)6](FCC) was designed and synthesized. The complex FCC was characterized with spectra and single X-ray crystal diffraction. Complex FCC was a typical hexa-carbonyl compound which had the relevant characters from the IR spectrum and the crystal structure. The electrochemical reversibility of complex FCC was poorer than benzenedithiol diiron complex for the benzene ring which is connected to the [2Fe2S] center by a vinyl group.3. A benzenedithiol containing [FeFe]-hydrogenase mimic complex [Fe2(μ-S2)C6H2(OH)(OOCCH2N3)(CO)6] designed and synthesized. The complex was fully characterized and we had collected its single X-ray diffraction data. The mimic complex is linked to the alkyne modified polyethyleneimine (PEI) via "Click" reaction, have polymer PEI-2Fe2S. The electrochemistry investigation of polymer PEI-2Fe2S shows that the steric hindrance of the frame work of polyethyleneimine block the intro molecule rotate via two electron ECE reduction process. The reversible redox of polymer is one electron process and the other process is the reduction of decomposer form the previsional reduction. The catalytic performance of the polymer at high acid concentration is better than the mimic complex [Fe2(μ-S2)C6H2(OH)(OOCCH2N3)(CO)6].4. A new multi-dental, N-containing ligand L was synthesized by "Click" reaction. This ligand was fully characterized. Two complexes CuClL·EtOH and Fe(NCS)2L-MeCN were synthesized by reacting the ligand L and copper(II) and iron(Ⅱ) salts, respectively. We had characterized these two complexes by single crystal X-ray diffraction.