Deeper Mechanistic Insight into Ru ...
Type de document :
Article dans une revue scientifique
DOI :
URL permanente :
Titre :
Deeper Mechanistic Insight into Ru Pincer-Mediated Acceptorless Dehydrogenative Coupling of Alcohols: Exchanges, Intermediates, and Deactivation Species
Auteur(s) :
Nguyen, Duc Hanh [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Trivelli, Xavier [Auteur]
Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 [UGSF]
Capet, Frederic [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Swesi, Youssef [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Favre-Réguillon, Alain [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Vanoye, Laurent [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Dumeignil, Franck [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Gauvin, Regis [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Trivelli, Xavier [Auteur]
Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 [UGSF]
Capet, Frederic [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Swesi, Youssef [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Favre-Réguillon, Alain [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Vanoye, Laurent [Auteur]
Laboratoire de Génie des Procédés Catalytiques [LGPC]
Dumeignil, Franck [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Gauvin, Regis [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Titre de la revue :
ACS Catalysis
Numéro :
8
Pagination :
4719-4734
Date de publication :
2018
Mot(s)-clé(s) en anglais :
Alcohols
Organic compounds
Aldehydes
Ethyl groups
Ethanol
Organic compounds
Aldehydes
Ethyl groups
Ethanol
Discipline(s) HAL :
Chimie/Catalyse
Résumé en anglais : [en]
The mechanism of acceptorless dehydrogenative coupling reaction (ADC) of alcohols to esters catalyzed by aliphatic pincer PHNP ruthenium complexes was experimentally studied. Relevant intermediate species involved in the ...
Lire la suite >The mechanism of acceptorless dehydrogenative coupling reaction (ADC) of alcohols to esters catalyzed by aliphatic pincer PHNP ruthenium complexes was experimentally studied. Relevant intermediate species involved in the catalytic cycle were isolated and structurally characterized by single-crystal X-ray diffraction studies, and their reactivity (including toward substrates related to the catalytic process) was probed. VT NMR studies unveiled several chemical exchanges connecting the Ru amido hydride, the Ru alkoxide, and the alcohol substrate. Under catalytic conditions, in situ IR spectroscopy monitoring demonstrated the production of ester via aldehyde as intermediate. A Tishchenko-like pathway is proposed as the main path for the production of ester from aldehyde, involving alkoxide and hemiacetaloxide Ru species (the latter being identified in the reaction mixture by NMR). Catalytic system deactivation under base-free conditions was found to be related to water traces in the reaction medium (either as impurity or derived from aldol reactions) that lead to the formation of catalytically inactive acetato Ru complexes. These react with alkali metal alkoxides to afford catalytically active Ru species. In line with this observation, running the ADC reaction in the presence of water scavengers or alkoxides allows maintaining sustained catalytic activity.Lire moins >
Lire la suite >The mechanism of acceptorless dehydrogenative coupling reaction (ADC) of alcohols to esters catalyzed by aliphatic pincer PHNP ruthenium complexes was experimentally studied. Relevant intermediate species involved in the catalytic cycle were isolated and structurally characterized by single-crystal X-ray diffraction studies, and their reactivity (including toward substrates related to the catalytic process) was probed. VT NMR studies unveiled several chemical exchanges connecting the Ru amido hydride, the Ru alkoxide, and the alcohol substrate. Under catalytic conditions, in situ IR spectroscopy monitoring demonstrated the production of ester via aldehyde as intermediate. A Tishchenko-like pathway is proposed as the main path for the production of ester from aldehyde, involving alkoxide and hemiacetaloxide Ru species (the latter being identified in the reaction mixture by NMR). Catalytic system deactivation under base-free conditions was found to be related to water traces in the reaction medium (either as impurity or derived from aldol reactions) that lead to the formation of catalytically inactive acetato Ru complexes. These react with alkali metal alkoxides to afford catalytically active Ru species. In line with this observation, running the ADC reaction in the presence of water scavengers or alkoxides allows maintaining sustained catalytic activity.Lire moins >
Langue :
Anglais
Audience :
Internationale
Vulgarisation :
Non
Établissement(s) :
ENSCL
CNRS
Centrale Lille
Univ. Artois
Université de Lille
CNRS
Centrale Lille
Univ. Artois
Université de Lille
Collections :
Équipe(s) de recherche :
Catalyse et synthèse éco-compatible (CASECO)
Valorisation des alcanes et de la biomasse (VAALBIO)
Valorisation des alcanes et de la biomasse (VAALBIO)
Date de dépôt :
2019-09-25T14:37:53Z
2020-02-11T11:43:12Z
2020-09-25T10:35:03Z
2020-02-11T11:43:12Z
2020-09-25T10:35:03Z
Fichiers
- RuMgCe_HMF-FDCA.pdf
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