Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction
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...
| Autores: | , , , , , , |
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| Tipo de documento: | artigo |
| Data de publicação: | 2023 |
| País: | España |
| Recursos: | Universidad de Huelva (UHU) |
| Repositório: | Arias Montano. Repositorio Institucional de la Universidad de Huelva |
| Idioma: | inglês |
| OAI Identifier: | oai:ariasmontano.uhu.es:10272/23522 |
| Acesso em linha: | https://hdl.handle.net/10272/23522 |
| Access Level: | Acceso aberto |
| Palavra-chave: | Olefin aziridination Nitrene transfer Noninnocent ligands Mechanistic studies Copper catalysis 23 Química |
| Resumo: | 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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