Rhodium(I)‐NHC complexes bearing bidentate bis‐heteroatomic acidato ligands as gem‐selective catalysts for alkyne dimerization
| العنوان: | Rhodium(I)‐NHC complexes bearing bidentate bis‐heteroatomic acidato ligands as gem‐selective catalysts for alkyne dimerization |
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| المؤلفون: | Luis A. Oro, Fernando J. Lahoz, Jesús J. Pérez-Torrente, Vincenzo Passarelli, Marina Borraz, Ricardo Castarlenas, Andrea Di Giuseppe, María Galiana-Cameo, Yaroslava Zelenkova |
| المساهمون: | Ministerio de Economía y Competitividad (España), Consejo Superior de Investigaciones Científicas (España), Diputación General de Aragón |
| المصدر: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| بيانات النشر: | Wiley-VCH, 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Denticity, Alkyne, chemistry.chemical_element, amidato, alkyne dimerization, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, Rhodium, chemistry.chemical_compound, Pyridine, N-heterocyclic carbenes, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Ligand, Aryl, Organic Chemistry, General Chemistry, 0104 chemical sciences, carboxylato, rhodium, Selectivity |
| الوصف: | A series of Rh(κ2‐BHetA)(η2‐coe)(IPr) complexes bearing 1,3‐bis‐hetereoatomic acidato ligands (BHetA) including carboxylato (O,O), thioacetato (O,S), amidato (O,N), thioamidato (N,S), and amidinato (N,N), have been prepared by reaction of the dinuclear precursor [Rh(μ‐Cl)(IPr)(η2‐coe)]2 with the corresponding anionic BHetA species. The RhI‐NHC‐BHetA compounds catalyze the dimerization of aryl alkynes, showing excellent selectivity for the head‐to‐tail enynes. Among them, the acetanilidato‐based catalyst has shown an outstanding catalytic performance reaching unprecedented TOF levels of 2500 h−1 with complete selectivity for the gem‐isomer. Investigation of the reaction mechanism supports a non‐oxidative pathway in which the BHetA ligand behaves as proton shuttle through intermediate κ1‐HBHetA species. However, in the presence of pyridine as additive, the identification of the common RhIIIH(C≡CPh)2(IPr)(py)2 intermediate gives support for an alternative oxidative route. Financial support from the Spanish Ministerio de Economía y Competitividad (MINECO/FEDER) under the Project CTQ2016‐75884‐P, the CSIC under the Project Proyectos Intramurales Especiales (201680I011), and the Diputación General de Aragón (DGA/FSE‐E42‐17R) are gratefully acknowledged. A.D.G. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for the postdoctoral grant Juan de la Cierva–Incorporación 2015 (IJCI‐2015‐27029). |
| اللغة: | English |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::e8fe2f6ba8c4cd6f03d31104216af6c4 http://hdl.handle.net/10261/239039 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....e8fe2f6ba8c4cd6f03d31104216af6c4 |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |