@article{10272/23522,
year = {2023},
url = {https://hdl.handle.net/10272/23522},
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},
organization = {The authors thank Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21, PID2020-112825RB-I00, and CEX2019-000925-S also funded by FEDER “Una manera de hacer Europa”. They also thank Junta de Andalucía (P20-00348) and Universidad de Huelva (P.O.Feder UHU-202016). A.M.R thanks Ministerio de Universidades for FPU fellowships (FPU17/02738). CERCA Programme/Generalitat de Catalunya is also acknowledged. S.L.-R. thanks Generalitat de Catalunya for the FI–Agaur predoctoral contract (2019FI_B 01002)},
publisher = {American Chemical Society},
title = {Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction},
doi = {10.1021/acscatal.2c05069},
author = {Ramírez Rodríguez, Manuel and Moreno Rodríguez, Anabel and López Resano, Sara and Pericàs, Miquel A. and Díaz Requejo, María Mar and Maseras, Feliu and Pérez Romero, Pedro José},
}