Metal–ligand cooperative proton transfer as an efficient trigger for rhodium-NHC-pyridonato catalyzed gem-specific alkyne dimerization
| العنوان: | Metal–ligand cooperative proton transfer as an efficient trigger for rhodium-NHC-pyridonato catalyzed gem-specific alkyne dimerization |
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| المؤلفون: | Asier Urriolabeitia, Victor Polo, Andrea Di Giuseppe, Eduardo Barrenas, Ricardo Castarlenas, María Galiana-Cameo, Vincenzo Passarelli, Jesús J. Pérez-Torrente |
| المساهمون: | Ministerio de Ciencia, Innovación y Universidades (España), Agencia Estatal de Investigación (España), Diputación General de Aragón, European Commission, Ministerio de Economía y Competitividad (España), Ministerio de Educación, Cultura y Deporte (España) |
| المصدر: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| بيانات النشر: | American Chemical Society, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | chemistry.chemical_classification, Ligand assisted proton shuttle, Proton, Ligand, Alkyne dimerization, chemistry.chemical_element, Alkyne, General Chemistry, Hemilability, Metal−ligand cooperation, DFT calculations, Combinatorial chemistry, Catalysis, Rhodium, Metal, metal−ligand cooperation ligand assisted proton shuttle alkyne dimerization N-heterocyclic carbene DFT calculations hemilability, chemistry, visual_art, visual_art.visual_art_medium, N-heterocyclic carbene |
| الوصف: | 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. Financial support from the Spanish Ministerio de Ciencia e Innovación (MICINN/FEDER) under the Projects PID2019-103965GB-I00 and PGC2018-099383-B-I00, and the Diputación General de Aragón (FEDER 2014-2020 “Building Europe from Aragón”, group E42_20R) 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). A.U. thankfully acknowledges the Spanish MECD for a FPU fellowship (FPU 2017/05417). The authors would like to acknowledge the use of Servicio General de Apoyo a la Investigación-SAI, Universidad de Zaragoza and the computational resources provided by the Institute for Biocomputation and the Physics of Complex Systems (BIFI)–Universidad de Zaragoza. |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::552b399b8f202df4d18be595c25245bf http://hdl.handle.net/10261/261224 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....552b399b8f202df4d18be595c25245bf |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |