RT Journal Article
T1 Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction
A1 Ramírez Rodríguez, Manuel
A1 Moreno Rodríguez, Anabel
A1 López Resano, Sara
A1 Pericàs, Miquel A.
A1 Díaz Requejo, María Mar
A1 Maseras, Feliu
A1 Pérez Romero, Pedro José
AB In the context of copper-catalyzed nitrene transferto olefins, many systems operate upon mixing a CuX salt (X =halide, OTf) and a polydentate N-based ligand, assuming that theX ligand is displaced from the coordination sphere toward acounterion position. Herein, we demonstrated that such generalassumption should be in doubt since studies carried out with thewell-defined copper(I) complexes (TTM)CuCl and [(TTM)Cu-(NCMe)]PF6 (TTM = tris(triazolyl)methane ligand) demonstratea dual behavior from a catalytic and mechanistic point of view thatexclusively depends on the presence or absence of the chlorideligand bonded to the metal center. When coordinated, theturnover-limiting step corresponds to the formation of thecarbon−nitrene bond, whereas in its absence, the highest barriercorresponds to the formation of the copper−nitrene intermediate
PB American Chemical Society
SN 2155-5435 (electrónico)
YR 2023
FD 2023
LK https://hdl.handle.net/10272/23522
UL https://hdl.handle.net/10272/23522
LA eng
NO Rodríguez, M. R., M Rodríguez, A., López-Resano, S., Pericàs, M. A., Díaz-Requejo, M. M., Maseras, F., & Pérez, P. J. (2022). Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction. In ACS Catalysis (Vol. 13, Issue 1, pp. 706–713). American Chemical Society (ACS). https://doi.org/10.1021/acscatal.2c05069
NO 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)
DS Repositorio Institucional de la Universidad de Huelva
RD 15 jun 2026