Novel Ferrocenyl The Only Iron Hydrogenase Active Center Mimics The Design, Synthesis, And Nature Study

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. The synthesis, structures and redox properties have been systematically studies as described in the thesis. The main result are as follows:1. A total of 18 new iron-sulfur complexes were successfully synthesized. The structures for all these new compounds were fully characterized by elemental analysis, IR, ¹HNMR spectroscopies, as well as for some compounds containing phosphorus by ³¹P. In addition, the structure of one representative was determined by single-crystal X-ray diffraction methods.2. New complex anion (μ-ferrocenylS)(μ-S^-)Fe₂(CO)₆ was prepared. this new complex anion reacted with electrophilic reagents RX to produce four new single butterfly-shaped clusters (μ-ferrocenylS)(μ-SR)Fe₂(CO)₆, which contain a ferrocene. These complexes have been fully characterized by elemental analysis, IR, ¹HNMR spectroscopies, as well as for one representative by X-ray diffraction analysis.3 . The complexes obtained above reacted with triphenylphophane to give three new substituted iron-sulfur clusters. Similarly, reacted with ferrocene-1,1'-bis(diphenylphosphine) to give two new substituted iron-sulfur clusters, and the reaction condition was optimized. 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.4. New complex anion (μ-ferrocenylS₂)[Fe₂(CO)₆]₂(μ-S^-)₂ was prepared. this new complex anion reacted with electrophilic reagents RX to produce four new double butterfly-shaped clusters (μ-ferrocenylS₂)[Fe₂(CO)₆]₂(μ-SCH₃)₂, which contain a ferrocene. These complexes have been fully characterized by elemental analysis, IR, ¹HNMR spectroscopies, as well as for one representative by X-ray diffraction analysis. 5. The complexes obtained above reacted with triphenylphophane to give three new substituted iron-sulfur clusters. Similarly, reacted with ferrocene-1,1'-bis(diphenylphosphine) to give two new substituted iron-sulfur clusters6. Cyclic voltammograms of these phosphane substituted complexes and containing cysteinyl ligands comlexes were studied to evaluated their redox properties.