A comprehensive density functional theory study of the key role of fluorination and dual hydrogen bonding in the activation of the epoxide/CO2 coupling by fluorinated alcohols
[en] The activation mechanism of the CO2/propylene oxide coupling catalysed by a bicomponent organocatalyst combining the use of TBABr with (multi)phenolic or fluorinated hydrogen bond donors (HBDs) was investigated using the Density Functional Theory (DFT). Thus, it was shown that increasing the number of electron withdrawing trifluoromethyl substituents in HBDs strengthens their proton donor capability and allows a better stabilization by hydrogen bonding of the intermediates and transition states. In addition, the high efficiency of fluorinated monoalcohol activators is related to a dual hydrogen bonding mechanism by two fluorinated molecules that cooperatively contribute to the CO2/propylene oxide coupling.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Alves, Margot ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Méreau, Raphaël; University of Bordeaux, Institute of Molecular Sciences, France
Grignard, Bruno ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine ; University of Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Tassaing, Thierry; University of Bordeaux, Institute of Molecular Sciences, France
Language :
English
Title :
A comprehensive density functional theory study of the key role of fluorination and dual hydrogen bonding in the activation of the epoxide/CO2 coupling by fluorinated alcohols
Publication date :
2016
Journal title :
RSC Advances
eISSN :
2046-2069
Publisher :
Royal Society of Chemistry Publishing, Cambridge, United Kingdom
Volume :
6
Issue :
43
Pages :
36327-36335
Peer reviewed :
Peer Reviewed verified by ORBi
Name of the research project :
IDEX program CO2Green, Sinopliss and Flycoat programs
Funders :
University of Bordeaux [FR] The International Doctoral School IDS-Funmat Conseil Général d'Aquitaine [FR] MESRI - Ministère de l’Enseignement supérieur, de la Recherche et de l’Innovation [FR] Walloon region [BE] BELSPO - Politique scientifique fédérale [BE] F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]