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Characterization and Reactivity Studies of a Terminal Copper–Nitrene Species
Author(s) -
Corona Teresa,
Ribas Lídia,
Rovira Mireia,
Farquhar Erik R.,
Ribas Xavi,
Ray Kallol,
Company Anna
Publication year - 2016
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.201607238
Subject(s) - nitrene , chemistry , reactivity (psychology) , azide , adduct , copper , moiety , ligand (biochemistry) , amination , reactive intermediate , photochemistry , polymer chemistry , medicinal chemistry , stereochemistry , combinatorial chemistry , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
High‐valent terminal copper–nitrene species have been postulated as key intermediates in copper‐catalyzed aziridination and amination reactions. The high reactivity of these intermediates has prevented their characterization for decades, thereby making the mechanisms ambiguous. Very recently, the Lewis acid adduct of a copper–nitrene intermediate was trapped at −90 °C and shown to be active in various oxidation reactions. Herein, we describe for the first time the synthesis and spectroscopic characterization of a terminal copper(II)–nitrene radical species that is stable at room temperature in the absence of any Lewis acid. The azide derivative of a triazamacrocyclic ligand that had previously been utilized in the stabilization of aryl–Cu III intermediates was employed as an ancillary ligand in the study. The terminal copper(II)–nitrene radical species is able to transfer a nitrene moiety to phosphines and abstract a hydrogen atom from weak C−H bonds, leading to the formation of oxidized products in modest yields.