2026-04-17T16:06:20Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/266122025-03-23T00:42:22Zcom_2072_452955com_2072_2054col_2072_453073

The metal role on the activity and stereoselectivity of ring opening polymerization of racemic lactide promoted by Salen catalysts Rusconi, Yolanda D’Alterio, Massimo Christian Grillo, Andrea Poater Teixidor, Albert de Rosa, Claudio Talarico, Giovanni Polimerització Polymerization Estereoquímica Stereochemistry Estereoisòmers Stereoisomers Funcional de densitat, Teoria del Density functionals 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 This work was financially supported by the Italian Ministry of University and Research (PRIN 2022, CUP E53D23008360006). This study was carried out within the MICS (Made in Italy–Circular and Sustainable) Extended Partnership funded from the European Union Next-Generation EU (Piano Nazionale di Ripresa e Resilienza (PNRR) – Missione 4 Componente 2, Investimento 1.3 –D.D. 1551.11-10-2022, PE00000004). A.P. is a Serra Húnter Fellow. A.P. received ICREA Academia Prize 2019. We thank the Spanish Ministerio de Ciencia e Innovación for project PID2021-127423NB-I00 and the Generalitat de Catalunya for project 2021SGR623 2025-03-23T00:42:21Z 2025-03-23T00:42:21Z 2025-03-23T00:42:21Z 2024-01-19 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed http://hdl.handle.net/10256/26612 info:eu-repo/semantics/altIdentifier/doi/10.1016/j.polymer.2023.126639 info:eu-repo/semantics/altIdentifier/issn/0032-3861 info:eu-repo/semantics/altIdentifier/eissn/1873-2291 PID2021-127423NB-I00 info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127423NB-I00/ES/CATALISIS PREDICTIVA PARA CAMBIAR EL ODEN SECUENCIAL ENTRE EXPERIMENTOS I CALCULOS/ Attribution 4.0 International http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Elsevier Polymer, 2024, vol. 292, art. núm. 126639 Articles publicats (D-Q)