Por favor, use este identificador para citar o enlazar a este item:
http://hdl.handle.net/10261/261224
COMPARTIR / EXPORTAR:
SHARE CORE BASE | |
Visualizar otros formatos: MARC | Dublin Core | RDF | ORE | MODS | METS | DIDL | DATACITE | |
Título: | Metal–ligand cooperative proton transfer as an efficient trigger for rhodium-NHC-pyridonato catalyzed gem-specific alkyne dimerization |
Autor: | Galiana-Cameo, María CSIC ORCID; Urriolabeitia, Asier; Barrenas, Eduardo CSIC; Passarelli, Vincenzo CSIC ORCID; Pérez-Torrente, Jesús J. CSIC ORCID; Giuseppe, Andrea di CSIC ORCID CVN; Polo, Víctor CSIC ORCID; Castarlenas, Ricardo CSIC ORCID | Palabras clave: | Metal−ligand cooperation Hemilability Ligand assisted proton shuttle DFT calculations Alkyne dimerization N-heterocyclic carbene |
Fecha de publicación: | 2021 | Editor: | American Chemical Society | Citación: | ACS Catalysis 11(12): 7553-7567 (2021) | Resumen: | The mononuclear square-planar Rh{κ2-X,N-(Xpy)}(η2-coe)(IPr) (X = O, NH, NMe, S) complexes have been synthesized from the dinuclear precursor [Rh(μ-Cl)(IPr)(η2-coe)]2 and the corresponding 2-heteroatom-pyridinate salts. The Rh-NHC-pyridinato derivatives are highly efficient catalysts for gem-specific alkyne dimerization. Particularly, the chelating N,O-pyridonato complex displays turnover frequency levels of up 17 000 h–1 at room temperature. Mechanistic investigations and density functional theory calculations suggest a pyridonato-based metal–ligand cooperative proton transfer as responsible for the enhancement of catalytic activity. The initial deprotonation of a Rh-π-alkyne complex by the oxo-functionality of a κ1-N-pyridonato moiety has been established to be the rate-limiting step, whereas the preferential protonation of the terminal position of a π-coordinated alkyne accounts for the exclusive observation of head-to-tail enynes. The catalytic cycle is closed by a very fast alkenyl–alkynyl reductive elimination. | Versión del editor: | https://doi.org/10.1021/acscatal.1c00602 | URI: | http://hdl.handle.net/10261/261224 | DOI: | 10.1021/acscatal.1c00602 | E-ISSN: | 2155-5435 |
Aparece en las colecciones: | (ISQCH) Artículos |
Ficheros en este ítem:
Fichero | Descripción | Tamaño | Formato | |
---|---|---|---|---|
metaldimeriza.pdf | 4,06 MB | Adobe PDF | Visualizar/Abrir |
CORE Recommender
WEB OF SCIENCETM
Citations
12
checked on 27-feb-2024
Page view(s)
29
checked on 23-abr-2024
Download(s)
134
checked on 23-abr-2024
Google ScholarTM
Check
Altmetric
Altmetric
Este item está licenciado bajo una Licencia Creative Commons