Copper-catalyzed and organocopper-involved reactions are of great significance in organic synthesis. To have a deep understanding of the reaction mechanisms, the structural characterizations of organocopper intermediates become indispensable. Meanwhile, the structure-function relationship of organocopper compounds could advance the rational design and development of new Cu-based reactions and organocopper reagents. Compared to the mono-carbonic ligand, the C,N- and C,C-bidentate ligands better stabilize unstable organocopper compounds. Bidentate ligands can chelate to the same copper atom via η²-mode, forming a mono-cupra-cyclic compounds with at least one acute C-Cu-C angle. When the bidentate ligands bind to two copper atoms via η¹-mode at each coordinating site, the bimetallic macrocyclic compounds will form nearly linear C-Cu-C angles. The anionic coordinating sites of the bidentate ligand can also bridge two metals via μ₂-mode, forming organocopper aggregates with Cu-Cu interactions and organocuprates with contact ion pair structures. The reaction chemistry of some selected organocopper compounds is highlighted, showing their unique structure–reactivity relationships.

中文翻译：

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C,C- 和 C,N-螯合有机铜化合物

铜催化和有机铜参与的反应在有机合成中具有重要意义。为了深入了解反应机理，有机铜中间体的结构表征变得不可或缺。同时，有机铜化合物的结构-功能关系可以促进新的铜基反应和有机铜试剂的合理设计和开发。与单碳配体相比，C,N-和 C,C-二齿配体更好地稳定不稳定的有机铜化合物。双齿配体可以通过η ^{2 -}模式螯合到同一铜原子上，形成具有至少一个锐角 C-Cu-C 的单铜环化合物。当双齿配体通过η ¹与两个铜原子结合时-mode 在每个配位点，双金属大环化合物将形成几乎线性的 C-Cu-C 角。双齿配体的阴离子配位位点还可以通过μ ₂模式桥接两种金属，形成具有 Cu-Cu 相互作用的有机铜聚集体和具有接触离子对结构的有机铜酸盐。突出显示了一些选定有机铜化合物的反应化学，显示了它们独特的结构-反应关系。