The Only Iron Hydrogenase Active Center Chemistry Simulation

Sulfur-iron clusters are important in both theoretical and practical fields and the studies of sulfur-iron clusters can be traced back more than half a century. The recent growing up of chemistry of hydrogenases, especially the Fe-only hydrogenase have renewed interest in classical organometallic diiron dithiolate complexes. Chemical mimic of the Fe-only hydrogenase active site is mainly discussed in this thesis.In this dissertation, eight new sulfur-iron complexes, six new phosphine ligand substituted sulfur-iron complexes, and five containing L-cysteine mimic of the Fe-only hydrogenase active site were fully synthesized. The structures for all these new compounds were fully characterized by ¹H NMR, IR spectroscopies and elemental analysis, as well as for some compounds containing phosphorus by ³¹P NMR and for containing L-cysteine complexes by MS, and for three representatives by single-crystal X-ray diffraction methods.The lively anions {[(μ-CO)Fe₂(CO)₆](μ-SR)}' [Et₃NH]⁺ were prepared through reaction of methyl mercaptoacetate or ethyl 3-mercaptopropionate with Fe³(CO)₁₂ in the presence of Et₃N. This new type of anions reacted with electrophilic reagents such as aromatic acyl chloride to produce eight new butterfly-shaped clusters. One representative was characterized by single-crystal X-ray diffraction methods.Then, the complexes obtained above reacted with triphenylphophane to give six new substituted sulfur-iron clusters. All these new compounds were fully characterized. The change of properties can be found according to compared the data of various spectroscopies of this complexes, and it is useful to sulfur-iron clusters reactive chemistry. One representative was characterized by single-crystal X-ray diffraction methods.