Preparation and Spectroscopic Characterization of Unstable Active Oxygen Species

1.利用受阻的吡唑类化合物合成了新型的N_2和N_3配体。对于这些配体，我们还讨论了电子和空间位阻对得到的络合物的影响。2.为了得到单核铜氧络合物，我们探索了最受阻碍的配体体系。通过这些配体，我们得到了超氧基铜(II)配合物，并对它们进行了表征。3.我们观察到了铜-S和铜-氧键性质的一些差异。4.制备了单核铁(II)α-酮和羧基配合物作为非血红素铁加氧酶活性中心的模型。α-酮酸络合物的氧化速率常数比羧酸络合物快2个数量级。因此，我们得出结论：α-酮官能团在这些酶的氧活化中起着关键作用。5.我们观察了烷基过氧基铁(III)络合物的详细电子结构，这些结果表明这些酶中存在O-O键的溶血裂解。6.我们发现了利用锰(II)离子的新型烯烃聚合催化剂。7.我们讨论了通过“自由基控制”的中间体进行苯酚聚合反应的反应机理。8.我们合成了新型的铜(I)-双氮烯配合物，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.