Rationalizing the Reactivity of Mixed Allyl Rare-Earth Borohydride Complexes with DFT Studies

Autor:	Sami Fadlallah, Jashvini Jothieswaran, Iker Del Rosal, Laurent Maron, Fanny Bonnet, Marc Visseaux
Jazyk:	angličtina
Rok vydání:	2020
Předmět:	rare earth allyl borohydride ring-opening polymerization cyclic esters DFT Chemical technology TP1-1185 Chemistry QD1-999
Zdroj:	Catalysts, Vol 10, Iss 8, p 820 (2020)
Druh dokumentu:	article
ISSN:	2073-4344
DOI:	10.3390/catal10080820
Popis:	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.
Databáze:	Directory of Open Access Journals
Externí odkaz:	https://doaj.org/article/8b5c682f7f344011a900a2fd86563ef8 Zobrazit plný text záznamu View record in DOAJ Plný text ve formátu PDF Plný text ve formátu HTML
Nepřihlášeným uživatelům se plný text nezobrazuje	K zobrazení výsledku je třeba se přihlásit.