2026-04-19T09:43:16Zhttps://recercat.cat/oai/request

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

00925njm 22002777a 4500 dc Rusconi, Yolanda author D’Alterio, Massimo Christian author Grillo, Andrea author Poater Teixidor, Albert author de Rosa, Claudio author Talarico, Giovanni author 2024-01-19 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 http://hdl.handle.net/10256/26612 Polimerització Polymerization Estereoquímica Stereochemistry Estereoisòmers Stereoisomers Funcional de densitat, Teoria del Density functionals The metal role on the activity and stereoselectivity of ring opening polymerization of racemic lactide promoted by Salen catalysts