| Hydrogenase can reversibly catalyze the reduction of H2 or the oxidation of H+.In recent years, due to the great research value of the hydrogenases in the development and utilization of hydrogen energy, the scientists pay much attention on it. For organometallic chemists, the goal of modeling the active site of the hydrogenase is to get cheap organometallic catalysts to replace Pt to make hydrogen.In this dissertation, we designed and synthesized a series of new mimics of the active site of [Fe]-hydrogenase.First, we’ve synthesized a series of mimics 3-1, 3-2, 3-3and 3-4, whose structures are very close to the active site of [Fe]-hydrogenase. Models 3-1, 3-4 are both hexa-coordinated compounds. In model 3-1, the iron is coordinated with three CO,an iodine atom and a bidentate acylmethylpyridinol ligand. Model 3-4containing 2-hydroxypyridine unit was obtained after the removal of tert-butoxy in mimic 3-1. Models 3-2, 3-3 are five coordinated compounds. There are two cis-CO and a sulfur atom coordinating with the iron in Models 3-2 and 3-3. The structures of models 3-2 and 3-3 are much closer to the [Fe]-hydrogenase active site.This is very useful to explore the role of the various ligands coordinated with the iron.Furthermore we observed and verified the exchange of model 3-1 between tricarbonyl and dicarbonyl structures. Meanwhile, we synthesized the ligand 4-1 and its ruthenium complex 4-2. Unexpectedly, 4-2 is a diruthenium complex.It is possible to catalyze the reduction of H2 or the oxidation of H+ for[Fe]-hydrogenase due to the cooperative interaction between the metal and the ligand. Many organometallic catalysts with such interaction are efficient catalysts in hydrogenation or hydrogen transferring reaction. Based on the two points, we synthesized a new ligand 5-3 with 2-hydroxypyridine unit. Then we’ve got tridentate complex 5-4, and its catalytic activies in hydrogen transferring reactions are waiting to be explored. |
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