Ramírez Rodríguez, ManuelMoreno Rodríguez, AnabelLópez Resano, SaraPericàs, Miquel A.Díaz Requejo, María MarMaseras, FeliuPérez Romero, Pedro José2024-04-182024-04-182023Rodríguez, 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.2c050692155-5435 (electrónico)https://hdl.handle.net/10272/23522In 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 intermediateengAtribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/Olefin aziridinationNitrene transferNoninnocent ligandsMechanistic studiesCopper catalysisjournal article10.1021/acscatal.2c05069open access23 Química