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

开发具有类氧化催化活性的金属配合物/分子氧/电子转移多组分系统

基本信息

批准号：
09555270
负责人：
FUNABIKI Takuzo
金额：
$ 7.87万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1999
项目状态：
已结题

项目摘要

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.

在非血红素铁配合物/分子氧/电子转移多组分体系中开发新的单加氧酶和双加氧酶样催化反应的项目中，我们成功地开发了由Fe（III），Fe（II）和Mn（II）配合物催化的芳烃，烷烃和烯烃氧化的新反应。在单加氧酶功能模型体系中，我们开发了一个新的体系，该体系以邻苯二酚铁（III）配合物为铁中心，对苯二酚为电子和质子供体。这给出了烷烃、烯烃和芳烃的单氧化的特征结果。在α-酮酸双加氧酶的功能模型反应中，新的含氧反应在环辛烯和异辛烯等烯烃的选择性环氧化反应，金刚烷和环己烷等烷烃的羟基化或羰基化反应中得到了发展。铁（III）配合物对邻苯二酚的选择性氧化作用已被广泛研究。除了Fe（III）的选择性二醇内氧化外，我们还开发了Mn（II）配合物的新反应。这是第一个模型系统的锰依赖性儿茶酚双加氧酶。作为中间体，我们已经分离出Mn（II）-semiquinonate配合物作为一种新型的配合物。通过X射线单晶衍射、ESI-Mass、ESR、IR、UV-VIS等光谱表征了配合物的结构。最有趣的是配合物保持了Mn（II）-semiquinonate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。