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

铜（I）和铜（II）配合物的光控反应性：通过内球机制进行光氧化还原催化的独特机会

• 批准号: 433136929
• 负责人: Professorin Dr. Julia Rehbein
• 金额: --
• 依托单位: Institut für Organische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/433136929?language=en
• 关键词: Light; controlled; reactivity; copper; II

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).

在这个项目中，我们将研究光氧化还原活性铜络合物作为可见光催化过程中的特殊特性，假设涉及电子转移以外的内球机制，而不是广泛应用的Ru和Ir基催化剂。我们将开发单核铜(I)和铜(II)配合物，使其能够光催化生成稳定为有机铜(II)和有机铜(III)中间体的自由基或碳负离子。这些中间体将为目前由有机铜(I)化合物主导的有机铜化学开辟新的途径。该项目的中心目标是开发新的具有更长的激发寿命和较强的还原或氧化电位的铜(I)和铜(II)配合物，并推断它们在光诱导ATRA类过程中的作用机制。将遵循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，并将在PS-TRIR(帕特里克·纽伯格，雷根斯堡大学物理化学)、吸附和发射光谱(低至1.5K的Rafal Czerwieniec，雷根斯堡大学物理化学)和XAS光谱学(Michael Rübhausen，CFEL，汉堡)等领域的合作进一步补充。