Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction.
ACS Catal
; 13(1): 706-713, 2023 Jan 06.
Article
em En
| MEDLINE
| ID: mdl-37808365
ABSTRACT
In the context of copper-catalyzed nitrene transfer to olefins, many systems operate upon mixing a CuX salt (X = halide, OTf) and a polydentate N-based ligand, assuming that the X ligand is displaced from the coordination sphere toward a counterion position. Herein, we demonstrated that such general assumption should be in doubt since studies carried out with the well-defined copper(I) complexes (TTM)CuCl and [(TTM)Cu(NCMe)]PF6 (TTM = tris(triazolyl)methane ligand) demonstrate a dual behavior from a catalytic and mechanistic point of view that exclusively depends on the presence or absence of the chloride ligand bonded to the metal center. When coordinated, the turnover-limiting step corresponds to the formation of the carbon-nitrene bond, whereas in its absence, the highest barrier corresponds to the formation of the copper-nitrene intermediate.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
ACS Catal
Ano de publicação:
2023
Tipo de documento:
Article
País de afiliação:
Espanha