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变得越来越重要。这项建议的目标是合成含铜酶半乳糖氧化酶和铜胺氧化酶以及含铁酶裂解邻苯二酚双加氧酶中活性部位的仿生络合物-所有这些酶的自由基都已知或被认为参与了反应机理-并研究了这些络合物的结构和电子性质以及反应活性。因此，我们将合成新型的铜(II)-苯氧基自由基络合物，作为半乳糖氧化酶活性中心的功能模型络合物。铜胺氧化酶反应性的再现，特别是铜离子与活性中心4-氨基间苯二酚辅因子之间分子内氧化还原反应的模拟，是重点研究2-羟基-1，4-苯二酮单元或其衍生物直接与铜离子配位或仅放置在铜离子附近的铜配合物的研究目标。这项建议的最后部分集中在功能模型络合物上，这些络合物解决了为什么分子氧与铁(III)的儿茶酚物种在催化裂解传统的儿茶酚双加氧酶过程中发生反应的原因。

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.