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.

在新的单氧化氢酶和二氧酶的新项目中，在非血红素铁复合物/分子氧/电子转移的多组分系统中，我们成功地在芳香族，烷烃，烷烃，烷烃和烯烃催化的Fe（III）和MN（III）和MN（III）和MN（III）和MN（III）和MN（III）和MN（III）和MN（III）和MN（III）和MN（II）和MN（II）和MN（III），MN（III）和MN（II）和MN（III）和MN（III）和MN（II）和MN（III），MN（III）和MN（II），MN（III）和MN（II）和MN（III）和MN。在单加氧化酶函数模型系统中，我们使用儿茶分析（III）Comlex作为铁中心和羟基酮作为电子和质子供体开发了一个新系统。这给出了烷烃，烷烃和芳香族的单氧化的特征结果。在烯烃酸依赖性双加氧酶的功能模型反应中，在烯类烷烃的选择性环氧化（例如环烯烯和Norbormbornen）的选择性环氧化中，羟那烷（如adamantane和Cyclohexane）开发了新的氧化。铁（III）配合物对儿茶酚的选择性充氧已广泛研究。除了Fe（III）的选择性内二醇氧合外，我们还通过Mn（II）复合物发展了一种新反应。这是第一个用于锰依赖性儿茶酚二氧酶的模型系统。作为一个中级，我们已经将Mn（II） - 氯喹酸盐复合物分离为一种新型的复合物。通过X射线晶体学分析，ESI-MAS，ESR，IR，UV-VIS光谱来阐明复合物的结构。最有趣的是，复杂的Maitains的电子结构（ii） - 氯喹啉酸盐构型。这是儿茶酚二氧酶机制的非常重要的信息。