Understanding the reaction mechanism of the CO2 and cyclohexene oxide copolymerization catalyzed by zinc(II) and magnesium(II) catalysts: a DFT approach

• Published in: Journal of molecular modeling Vol. 28; no. 10; p. 314
• Main Authors: de Lima, Lucas W., de Alcântara Morais, Sara Figueirêdo, Braga, Ataualpa A. C.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.10.2022; Springer Nature B.V
• Subjects: Carbon dioxide; Catalysts; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Copolymerization; Cyclohexene; Density functional theory; Magnesium; Molecular Medicine; Original Paper; Reaction mechanisms; Substrates; Theoretical and Computational Chemistry; XXI-Brazilian Symposium of Theoretical Chemistry (SBQT2021); Zinc; DFT; CO; Bimetallic catalyst; ROCOP
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-022-05293-7

The reaction mechanisms of carbon dioxide and cyclohexene oxide copolymerization catalyzed by four different zinc(II)-magnesium(II) (labeled as M1-M2) catalysts were computationally studied using density functional theory at the BP86-D3(BJ)/def2-TZVP/SMD//BP86-D3(BJ)/def2-SVP/SMD level of theory. The results showed that the most effective catalyst was the ZnMg system, in which poly(cyclohexene carbonate) was the preferred product, followed by the side product cis -cyclohexene carbonate. The QTAIM, NCI and ELF analysis performed to understand the role of metals in the reaction showed that ligands and substrates interact more strongly with zinc(II) centers compared to magnesium(II) centers. Furthermore, the Zn-I interaction at the M 1 position was stronger than the Mg-I interaction at the same position. All these results indicate a synergism between the metals Zn and Mg, which makes Zn(II)Mg(II) the best combination for the reaction.