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，我们将调查的光氧化还原活性铜配合物作为催化剂在可见光介导的过程中的特殊功能的基础上，电子转移以外的内球机制参与，而不是广泛应用的钌和铱基催化剂的假设。我们将开发单核铜（I）和铜（II）的配合物，这将允许光催化生成的自由基或碳负离子稳定的有机铜（II）和有机铜（III）的中间体。这些中间体将在有机铜化学中开辟新的途径，目前有机铜（I）化合物占主导地位。该项目的中心目标是开发具有延长的激发寿命和强还原或氧化电位的新的铜（I）和铜（II）络合物，并推导出它们在光诱导ATRA型过程中的作用模式的机制。有机和金属有机合成与配位化学的综合方法（奥利弗雷泽，或），光谱学和理论（Julia Risbein，JR）将紧随其后，这将进一步补充在ps-TRIR领域的合作（帕特里克Nürnberger，物理化学，里根斯堡大学），在低至1.5 K的可变温度下的吸附和发射光谱（Rafal Czerwieniec，物理化学，里根斯堡大学）和XAS光谱学（Michael Rübhausen，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).