Light controlled reactivity of copper(I) and copper(II) complexes: Unique opportunities for photoredox catalysis via inner sphere mechanisms

在这个项目中，我们将研究光氧化还原活性cu配合物作为催化剂在可见光介导过程中的特殊特征，基于一个假设，即涉及电子转移以外的内球机制，而不是广泛应用的钌和铱基催化剂。我们将开发单核铜(I)和铜（II）配合物，这些配合物将允许光催化生成自由基或碳离子，作为有机ocu （II）和有机ocu （III）中间体稳定。这些中间体将为目前以有机铜(I)化合物为主的有机铜化学开辟新的途径。该项目的中心目标是开发具有延长激发寿命和强还原或氧化电位的新型铜(I)和铜（II）配合物，并推断其在光诱导atra型过程中的作用模式的机制。有机和有机金属合成和配位化学（Oliver Reiser， OR），光谱学和理论（Julia Rehbein， JR）的综合方法将遵循，这将进一步补充ps-TRIR （Patrick n<e:1> rnberger，物理化学，雷根斯堡大学），吸附和发射光谱在1.5 K以下的变温（Rafal Czerwieniec，物理化学，雷根斯堡大学）和XAS光谱(Michael r<e:2> bhausen，CFEL汉堡)。

In this project we will investigate the special features of photoredox active Cu-complexes as catalysts in visible light mediated processes based on the hypothesis that inner sphere mechanisms beyond electron transfer are involved as opposed to widely applied ruthenium and iridium based catalysts. We will develop mononuclear copper (I) and copper(II) complexes that will allow the photocatalytic generation of radicals or carbanions stabilized as organoCu(II) and organoCu(III) intermediates. Such intermediates would open new avenues in organocopper chemistry, which is currently dominated by organocopper(I) compounds. The central aim of the project is to develop new copper(I) and copper(II) complexes with extended excited life times and strong reduction or oxidation potentials and to deduce the mechanisms of their mode of action in light induced ATRA-type processes. An integrated approach of organic and organometallic synthesis and coordination chemistry (Oliver Reiser, OR), spectroscopy and theory (Julia Rehbein, JR) will be followed, which will be further complemented by collaborations in the areas of ps-TRIR (Patrick Nürnberger, Physical Chemistry, University of Regensburg), adsorption and emission spectra a variable temperatures down to 1.5 K (Rafal Czerwieniec, Physical Chemistry, University of Regensburg) and XAS spectroscopy (Michael Rübhausen, CFEL, Hamburg).