Deciphering the Mechanism of the ...
Type de document :
Article dans une revue scientifique
DOI :
URL permanente :
Titre :
Deciphering the Mechanism of the Nickel-Catalyzed Hydroalkoxylation Reaction: A Combined Experimental and Computational Study
Auteur(s) :
Mifleur, Alexis [Auteur]
Mérel, Delphine S. [Auteur]
Mortreux, Andre [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Suisse, Isabelle [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Capet, Frederic [Auteur]
Trivelli, Xavier [Auteur]
Unité de Glycobiologie Structurale et Fonctionnelle UMR 8576 [UGSF]
Unité de Glycobiologie Structurale et Fonctionnelle (UGSF) - UMR 8576
Sauthier, Mathieu [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Macgregor, Stuart A. [Auteur]
Mérel, Delphine S. [Auteur]
Mortreux, Andre [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Suisse, Isabelle [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Capet, Frederic [Auteur]
Trivelli, Xavier [Auteur]
Unité de Glycobiologie Structurale et Fonctionnelle UMR 8576 [UGSF]
Unité de Glycobiologie Structurale et Fonctionnelle (UGSF) - UMR 8576
Sauthier, Mathieu [Auteur]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Unité de Catalyse et Chimie du Solide (UCCS) - UMR 8181
Macgregor, Stuart A. [Auteur]
Titre de la revue :
ACS Catalysis
Numéro :
7
Pagination :
6915-6923
Date de publication :
2017-08-30
Discipline(s) HAL :
Chimie/Catalyse
Chimie/Chimie de coordination
Chimie/Chimie de coordination
Résumé en anglais : [en]
The [Ni(0)(cod)2]/P∩P-catalyzed hydroalkoxylation of butadiene to form butenyl ethers is studied mechanistically, where P∩P = 1,4-bis(diphenylphosphino)butane (dppb) and 1,2-bis(diphenylphosphinomethyl)benzene (dppmb). ...
Lire la suite >The [Ni(0)(cod)2]/P∩P-catalyzed hydroalkoxylation of butadiene to form butenyl ethers is studied mechanistically, where P∩P = 1,4-bis(diphenylphosphino)butane (dppb) and 1,2-bis(diphenylphosphinomethyl)benzene (dppmb). Experimental studies suggest the intermediacy of [(P∩P)Ni(0)(butadiene)] and [(P∩P)Ni(II)(allyl)] intermediates and rule out the involvement of Ni–H species. The related species [(dppb)Ni(0)(1,4-diphenylbutadiene)], 1, and [(P∩P)Ni(II)(crotyl)(Cl)] complexes 2 (P∩P = dppmb) and 3 (P∩P = dppb) have been synthesized and characterized on the basis of VT NMR spectroscopy and X-ray crystallographic studies. Compounds 2 and 3 are shown to be catalytically competent for the hydroalkoxylation reaction. Computational studies on [(dppmb)Ni(0)(butadiene)] indicate a facile protonation that forms a cationic allylic intermediate [(dppmb)Ni(II)(η-C4H7)]OMe. C–O bond formation then occurs via external attack by the solvent-stabilized methoxide nucleophile. Hydroalkoxylation proceeds with modest computed barriers of ca. 18 kcal/mol, and the butenyl ether product formation is only marginally exergonic. Overall, the results are consistent with initial kinetic control leading to the major branched isomer followed by a reversible isomerization process operating under thermodynamic control.Lire moins >
Lire la suite >The [Ni(0)(cod)2]/P∩P-catalyzed hydroalkoxylation of butadiene to form butenyl ethers is studied mechanistically, where P∩P = 1,4-bis(diphenylphosphino)butane (dppb) and 1,2-bis(diphenylphosphinomethyl)benzene (dppmb). Experimental studies suggest the intermediacy of [(P∩P)Ni(0)(butadiene)] and [(P∩P)Ni(II)(allyl)] intermediates and rule out the involvement of Ni–H species. The related species [(dppb)Ni(0)(1,4-diphenylbutadiene)], 1, and [(P∩P)Ni(II)(crotyl)(Cl)] complexes 2 (P∩P = dppmb) and 3 (P∩P = dppb) have been synthesized and characterized on the basis of VT NMR spectroscopy and X-ray crystallographic studies. Compounds 2 and 3 are shown to be catalytically competent for the hydroalkoxylation reaction. Computational studies on [(dppmb)Ni(0)(butadiene)] indicate a facile protonation that forms a cationic allylic intermediate [(dppmb)Ni(II)(η-C4H7)]OMe. C–O bond formation then occurs via external attack by the solvent-stabilized methoxide nucleophile. Hydroalkoxylation proceeds with modest computed barriers of ca. 18 kcal/mol, and the butenyl ether product formation is only marginally exergonic. Overall, the results are consistent with initial kinetic control leading to the major branched isomer followed by a reversible isomerization process operating under thermodynamic control.Lire moins >
Langue :
Anglais
Audience :
Internationale
Vulgarisation :
Non
Établissement(s) :
ENSCL
Université de Lille
CNRS
Centrale Lille
Univ. Artois
Université de Lille
CNRS
Centrale Lille
Univ. Artois
Collections :
Équipe(s) de recherche :
Catalyse et synthèse éco-compatible (CASECO)
Méthodologie organométallique pour la catalyse homogène (MOCAH)
Méthodologie organométallique pour la catalyse homogène (MOCAH)
Date de dépôt :
2019-09-25T14:06:02Z
2021-06-25T07:50:49Z
2021-06-25T07:50:49Z