结构明确的苯基二价铜的化学反应性质及规律研究

有机铜化学是金属有机化学的组成部分，有机一价铜化合物是重要的有机合成试剂，高价有机铜中间体也被认为普遍存在于铜催化或促进的有机反应中，然而除了得以大量研究的一价有机铜化合物和近年来引起人们关注的芳基三价铜化合物外，有机二价铜化合物极为罕见，它们的反应性能人们更是知之甚少。最近，通过氮杂杯[1]芳烃[3]吡啶与高氯酸铜反应，我们获得了第一例结构明确的苯基二价铜。本项目拟以我们自己建立和发展的结构明确地苯基二价铜为平台分子，系统研究其与多类亲电试剂、亲核试剂、金属有机试剂、自由基物种的反应，考察其氧化还原反应和水解/质子解反应，全面认识苯基二价铜的电子态结构，揭示和阐明苯基二价铜的反应机理，为理解铜促进和催化的芳基碳-氢键活化和交叉偶联反应本质提供新的理论和实验依据，填补有机二价铜研究空白，丰富和发展有机铜化学。

Organocopper chemistry is an indispensable part of organometallics chemistry. Organocopper(I) compounds are important organometallic reagents in synthesis. High valent organocopper intermediates have been thought of being involved in copper-mediated or catalyzed C-H bond activation and cross-coupling reactions. In contrast to well documented organocopper(I) compounds and recently emerged organocopper (III) compounds, organocopper(II) compounds are extremely rare and their reactivity remains almost unknown. By means of the reaction of azacalix[1]arene[3]pyridines with Cu(ClO4)2, we obtained the first examples of structurally well-defined phenylcopper(II) compounds. Utilizing substituted phenylcopper(II) compounds as a molecular platform, we aim to conduct a systematic and in-depth study of the reactions of phenylcopper(II) compounds with various nucleophiles, electrophiles and radical species. We will also investigate the redox property, hydrolysis and protonation of phenylcopper(II) compounds. On the basis of theoretical calculations and EPR measurements, we hope to reveal the electronic structure of phenylcopper(II). The ultimate goal of this proposed project is to provide a deeper insight into to mechanistic aspects of copper-mediated or catalyzed C-H bond activation and cross-coupling reactions, broadening our understanding and comprehension of organocopper chemistry.