The metal role on the activity and stereoselectivity of ring opening polymerization of racemic lactide promoted by Salen catalysts

The stereoselective rac-lactide ring opening polymerization (ROP) promoted by enantiopure Salen catalysts has been studied by Density Functional Theory calculations with the aim of understanding the role of the metal atom in both the stereoselectivity and the activity of the process. The results obt...

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Detalles Bibliográficos
Autores: Rusconi, Yolanda, D’Alterio, Massimo Christian, Grillo, Andrea, Poater Teixidor, Albert, De Rosa, Claudio, Talarico, Giovanni
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2024
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:10256/26612
Acceso en línea:http://hdl.handle.net/10256/26612
Access Level:acceso abierto
Palabra clave:Polimerització
Polymerization
Estereoquímica
Stereochemistry
Estereoisòmers
Stereoisomers
Funcional de densitat, Teoria del
Density functionals
Descripción
Sumario:The stereoselective rac-lactide ring opening polymerization (ROP) promoted by enantiopure Salen catalysts has been studied by Density Functional Theory calculations with the aim of understanding the role of the metal atom in both the stereoselectivity and the activity of the process. The results obtained with M = Al, Sc, Y, La were compared to identify the steric and electronic effects deriving from the metal centre by combining a molecular descriptor based on the buried volume percentage (%VBur) and calculations of electronic parameters, including chemical hardness and electrophilicity. Our analysis gave insight into the parameters affecting the outcome of the ROP and we concluded that steric and electronic effects promoting stereoselective polymerization suppress catalyst activity and viceversa