Development of multicompont systems of metal complexes/molecular oxygen/electron Transfer that function oxygenale-like catalytic activity

在非血红素铁配合物/分子氧/电子转移多组分体系中新的类单加氧酶和类双加氧酶催化反应的开发项目中，我们成功地开发了由Fe（III）、Fe（II）和Mn（II）配合物催化的芳烃、烷烃和烯烃的氧化新反应。在单加氧酶功能模型体系中，我们开发了一种以儿茶酚铁（III）配合物为铁中心，对苯二酚为电子和质子给体的新体系。这在烷烃、烯烃和芳烃的单氧合中给出了特征性的结果。在α-酮类酸依赖性双加氧酶的功能模型反应中，环烯和降冰片烯等烯烃的选择性环氧化反应，adamantane和环己烷等烷烃的羟基化或羰基化反应发展了新的氧合反应。铁（III）配合物对儿茶酚的选择性氧化作用已被广泛研究。除了Fe（III）选择性的醇内氧化反应外，我们还开发了Mn（II）配合物的新反应。这是锰依赖性儿茶酚双加氧酶的第一个模型系统。作为中间体，我们分离出一种新型配合物Mn(II)-半醌酸配合物。通过x -射线晶体分析、ESI-Mass、ESR、IR、UV-VIS光谱对配合物的结构进行了澄清。最有趣的是，配合物保持了Mn(II)-半醌酸盐构型的电子结构。这对研究儿茶酚双加氧酶的作用机制具有重要意义。

In the project for development of new monooxygnase- and dioxygenase-like catalytic reactions in the multicomponent system of nonheme iron complexes/molecular oxyen/electron transfer, we were successful to develop new reactions in the oxygenation of aromatics, alkanes, and alkenes catalyzed by Fe(III), Fe(II) and Mn(II) complexes. In the monooxygenase functional model systems, we have developed a new system using catecholateiron(III) comlex as the iron center and hydroquinones as the electron and proton donors. This gave characteristic results in the monooxygenation of alkanes, alkenes, and aromatics. In the functional model reactions for α-keto acid-dependent dioxygenases, new oxygenations were developed in the selective epoxidation of alkenes such as cyclooctene and norbornene, hydroxylation or carbonylation of alkanes such as adamantane and cyclohexane. Selective oxygenations of catechols by iron(III) complexes has been extensively studied. Besides the selective intradiol oxygenation by Fe(III), we have developed a new reaction by Mn(II) complex. This is the first model system for the manganese-dependent catechol dioxygenases. As an intermediate, we have isolated a Mn(II)-semiquinonate complex as a new type of complex. The structure of the complex was clarified by X-ray crystallographif analysis, ESI-Mass, ESR, IR, UV-VIS spectra. What is the most interesting is that the complex maitains the electronic structure of Mn(II)-semiquinonate configuration. This is a very important information for the mechanism of catechol dioxygenases.