Preparation and Spectroscopic Characterization of Unstable Active Oxygen Species

1.利用受阻吡唑衍生物，我们合成了新型的N2和N3配体。我们还讨论了电子和空间位阻对配合物的影响。2.为了获得单核铜-二氧配合物，我们探索了最受阻的配体体系。3.观察到Cu-S键和Cu-O键特征的一些差异。4.制备了α-酮基和羧酸基Mono铁（II）配合物作为非血红素铁加氧酶活性中心的模型。α-酮酸配合物的氧化速率常数比羧酸配合物快2个数量级。因此，我们认为，5.对烷基过氧铁（III）配合物的电子结构进行了详细的研究，结果表明这些酶具有O-O键的溶血断裂作用; 6.利用锰（II）离子发现了新的烯烃聚合催化剂; 7.通过“自由基控制”的方法探讨了苯酚聚合反应的机理。8.我们还制备了新型的Cu（I）-二氮烯配合物并对其进行了表征。

1.With hindered pyrazole derivatives, we synthesized novel N2 and N3 ligands. With these ligands, we also discussed the electronic and steric influences on the obtained complexes.2.To obtain mononuclear copper-dioxygen complexes, we explored the most hindered ligand systems. With these ligands, we obtained the superoxo copper(II) complexes and characterized them well3.We observed some differences between Cu-S and Cu-O bond characters.4.Mononuclear iron(II) α-keto and carboxylato complexes were prepared as models for the active sites non-heme iron oxygenases. The oxygenation rate constants of the α-keto acid complexes are faster by 2 orders than those of carboxylato complexes. Therefore, we concluded the key role of the α-keto functionality in oxygen activation by these enzymes.5.We observed the detailed electronic structures of alkylperoxo iron(III) complexes.These results indicate O-O bond hemolytic cleavage in these enzymes.6.We found new olefin polymerization catalysts by use manganese(II) ion.7.We discussed the reaction mechanism of phenol polymerization reaction through"radical controlled"intermediates.8.We also prepared novel Cu(I)-diazene complexes and characterized them well.