Rationalizing the Reactivity of Mixed Allyl ...
Document type :
Article dans une revue scientifique: Article de synthèse/Review paper
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Title :
Rationalizing the Reactivity of Mixed Allyl Rare-Earth Borohydride Complexes with DFT Studies
Author(s) :
Fadlallah, Sami [Auteur]
Jothieswaran, Jashvini [Auteur]
Del Rosal, Iker [Auteur]
Laboratoire de physique et chimie des nano-objets [LPCNO]
Maron, Laurent [Auteur correspondant]
Laboratoire de physique et chimie des nano-objets [LPCNO]
Bonnet, Fanny [Auteur correspondant]
Unité Matériaux et Transformations - UMR 8207 [UMET]
Visseaux, Marc [Auteur correspondant]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Jothieswaran, Jashvini [Auteur]
Del Rosal, Iker [Auteur]
Laboratoire de physique et chimie des nano-objets [LPCNO]
Maron, Laurent [Auteur correspondant]
Laboratoire de physique et chimie des nano-objets [LPCNO]
Bonnet, Fanny [Auteur correspondant]
Unité Matériaux et Transformations - UMR 8207 [UMET]
Visseaux, Marc [Auteur correspondant]
Unité de Catalyse et Chimie du Solide - UMR 8181 [UCCS]
Journal title :
Catalysts
Volume number :
10
Pages :
820
Publisher :
MDPI
Publication date :
2020-07-22
English abstract : [en]
The reactivity of rare-earth complexes RE(BH4)2(C3H5)(THF)x (RE = La, Nd, Sm, Y, Sc) toward the Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) was rationalized by Density Functional Theory (DFT) calculations. ...
Show more >The reactivity of rare-earth complexes RE(BH4)2(C3H5)(THF)x (RE = La, Nd, Sm, Y, Sc) toward the Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) was rationalized by Density Functional Theory (DFT) calculations. Even if the polymerization reaction can be initiated by both RE-(BH4) and RE-allyl bonds, experimental investigations have shown that the initiation via the borohydride ligand was favored, as no allyl group could be detected at the chain-end of the resulting polymers. DFT studies could confirm these observations, as it was highlighted that even if the activation barriers are both accessible, the allyl group is not active for the ROP of ε-CL due to the formation of a highly stable intermediate that disfavors the subsequent ring-opening.Show less >
Show more >The reactivity of rare-earth complexes RE(BH4)2(C3H5)(THF)x (RE = La, Nd, Sm, Y, Sc) toward the Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) was rationalized by Density Functional Theory (DFT) calculations. Even if the polymerization reaction can be initiated by both RE-(BH4) and RE-allyl bonds, experimental investigations have shown that the initiation via the borohydride ligand was favored, as no allyl group could be detected at the chain-end of the resulting polymers. DFT studies could confirm these observations, as it was highlighted that even if the activation barriers are both accessible, the allyl group is not active for the ROP of ε-CL due to the formation of a highly stable intermediate that disfavors the subsequent ring-opening.Show less >
Language :
Anglais
Peer reviewed article :
Oui
Audience :
Internationale
Administrative institution(s) :
Université de Lille
CNRS
INRA
ENSCL
CNRS
INRA
ENSCL
Collections :
Research team(s) :
Ingénierie des Systèmes Polymères
Submission date :
2020-07-22T10:35:11Z
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