Untersuchungen zu einkernigen Kupfer- und Eisenkomplexen mit biomimetischer Relevanz zur Reaktionsweise von Radikalen in biologischen Prozessen

近年来，自由基在生物过程的讨论中越来越受到重视。本课题的目的是合成含铜酶半乳糖氧化酶和铜胺氧化酶以及含铁酶内切儿茶酚双加氧酶的活性位点的仿生配合物，并研究这些配合物的结构和电子性质以及反应活性。所有这些酶的自由基已知或被认为参与了反应机制。因此，将合成新的铜（II）苯氧基配合物，作为半乳糖氧化酶活性位点反应性的功能模型配合物。铜胺氧化酶反应活性的再现，特别是铜离子与活性部位的4-氨基间苯二甲酸辅因子之间发生的分子内氧化还原反应的模拟，是铜配合物研究的目标，其中2-羟基1,4-醌单元或其衍生物直接配位于铜离子或仅放置在铜离子附近。本建议的最后一部分集中在功能模型复合物上，它解决了分子氧与铁（III）儿茶酚酸盐物种的反应发生在醇内裂解儿茶酚双加氧酶催化转化过程中的原因。

In recent years radicals have gained more and more importance in the discussion of biological processes. Objectives of this proposal are the synthesis of biomimetic complexes for the active sites in the copper-containing enzymes galactose oxidase and copper amine oxidase and in the iron-containing enzyme intradiol-cleaving catechol dioxygenase - all enzymes for which radicals are either known or believed to be involved in the reaction mechanisms - and the investigation of the structural and electronic properties as well as of the reactivity of these complexes. Thus, novel copper(II) phenoxyl radical complexes will be synthesized to serve as functional model complexes for the reactivity of the active site in galactose oxidase. The reproduction of the reactivity of copper amine oxidase and especially the modelling of the intramolecular redox reaction occurring between the copper ion and the 4-aminoresorcine cofactor in the active site are the objectives of a study focusing on copper complexes in which a 2-hydroxy-1,4-quinone unit or derivatives thereof are either directly coordinated to the copper ion or only placed in the proximity of the copper ion. The last part of this proposal concentrates on functional model complexes which address the reasons why the reaction of molecular oxygen with an iron(III) catecholate species occurs during catalytic turnovers of intradiol-cleaving catechol dioxygenases.