التفاصيل البيبلوغرافية
| العنوان: |
Non-innocent Role of the Halide Ligand in the Copper-Catalyzed Olefin Aziridination Reaction |
| المؤلفون: |
Manuel R. Rodríguez (9128630), Anabel M Rodríguez (14298048), Sara López-Resano (14298051), Miquel A. Pericàs (1368555), M. Mar Díaz-Requejo (1621270), Feliu Maseras (1347684), Pedro J. Pérez (1621264) |
| سنة النشر: |
2022 |
| مصطلحات موضوعية: |
Biophysics, Biochemistry, Molecular Biology, Biotechnology, Computational Biology, Chemical Sciences not elsewhere classified, ncme )] pf, limiting step corresponds, highest barrier corresponds, coordination sphere toward, catalyzed nitrene transfer, chloride ligand bonded, 6 , methane ligand, based ligand, polydentate n, metal center, mechanistic point, innocent role, general assumption, exclusively depends, dual behavior, cux salt, counterion position |
| الوصف: |
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)]PF 6 (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. |
| نوع الوثيقة: |
article in journal/newspaper |
| اللغة: |
unknown |
| Relation: |
https://figshare.com/articles/journal_contribution/Non-innocent_Role_of_the_Halide_Ligand_in_the_Copper-Catalyzed_Olefin_Aziridination_Reaction/21776706 |
| DOI: |
10.1021/acscatal.2c05069.s001 |
| الاتاحة: |
https://doi.org/10.1021/acscatal.2c05069.s001 |
| Rights: |
CC BY-NC 4.0 |
| رقم الانضمام: |
edsbas.61112975 |
| قاعدة البيانات: |
BASE |