Abstract

• Organocopper(III) are key intermediates in a variety of copper-catalyzed cross-coupling reactions. • Four types of well-defined organocopper(III) complexes were summarized. • Development of organocopper(III) complexes will boost the new reaction discovery. Organocopper(III) species were generally considered as the key intermediates in a variety of copper-catalyzed cross-coupling reactions, aerobic oxidations, as well as enzyme-catalyzed oxidation reactions. The preparation and characterization of thermal stable organocopper(III) complexes, as well as investigation of their elementary bond-forming reductive elimination is missing in the chemistry map for a longtime, and is urgently needed, since these studies would deepen our understanding about the fundamentals of the copper catalysis and boost the new reaction discovery. In this review, the preparation and characterization of four types of well-defined copper(III) complexes including copper(III) complexes without copper-carbon bond, organocopper(III) complexes with rigid macrocyclic ligands, organocopper(III) complexes with fluoroalkylated ligands and other organocopper(III) complexes were summarized. In addition, the reactivities as well as bond-forming reductive elimination elementary reactions of a few organocopper(III) complexes were also discussed.

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