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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
Author(s) -
Basumatary Biju,
Hashiguchi Ikuho,
Mori Shigeki,
Shimizu Soji,
Ishida Masatoshi,
Furuta Hiroyuki
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202005167
Subject(s) - copper , singlet state , metalation , chemistry , delocalized electron , linkage (software) , ligand (biochemistry) , corrole , ground state , stereochemistry , oxidation state , crystallography , catalysis , photochemistry , atomic physics , physics , receptor , organic chemistry , biochemistry , gene , excited state
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 3 d x 2 - y 2orbital energy, thereby making such compounds invaluable for copper‐based catalytic applications.