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Copper 1,19‐Diaza‐21,24‐dicarbacorrole: A Corrole Analogue with an N−N Linkage Stabilizes a Ground‐State Singlet Organocopper Species

Biju Basumatary, Ikuho Hashiguchi, Shigeki Mori, Soji Shimizu, Masatoshi Ishida, Hiroyuki Furuta

2020Angewandte Chemie International Edition24 citationsDOIOpen Access PDF

Abstract

Abstract A copper complex of a heterocorrole analogue with an N–N linkage, 1,19‐diaza‐21,24‐dicarbadibenzocorrole ( Cu‐5 ), was successfully synthesized via oxidative metalation–cyclization of a tetrapyrrolic precursor. The N–N linkage in the skeleton of Cu‐5 , which serves as a mediator of π‐electron delocalization, features an 18π aromatic system. The electronic structure of Cu‐5 is best described as a ground‐state singlet species stabilized by the distinct NNCC coordination core. This finding shows how the ligand's design can be used to modulate the Cu orbital energy, thereby making such compounds invaluable for copper‐based catalytic applications.

Topics & Concepts

CopperSinglet stateMetalationChemistryDelocalized electronLinkage (software)Ligand (biochemistry)CorroleGround stateStereochemistryOxidation stateCrystallographyCatalysisPhotochemistryAtomic physicsPhysicsReceptorOrganic chemistryExcited stateGeneBiochemistryPorphyrin and Phthalocyanine ChemistryMetal-Catalyzed Oxygenation MechanismsSurface Chemistry and Catalysis
Copper 1,19‐Diaza‐21,24‐dicarbacorrole: A Corrole Analogue with an N−N Linkage Stabilizes a Ground‐State Singlet Organocopper Species | Litcius