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Article

Theoretical Study on Epoxide Ring-opening in CO2/Epoxide Copolymerization Catalyzed by Bifunctional Salen-Type Cobalt(III) Complexes: Influence of Stereoelectronic Factors

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Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, 30-387 Krakow, Poland
2
Department of Molecular Science and Technology, Ajou University, 206 Worldcup-ro, Yeongtong-gu, Suwon 16499, Korea
*
Author to whom correspondence should be addressed.
Academic Editors: Leonarda Francesca Liotta and Hongjing Wu
Catalysts 2021, 11(3), 328; https://doi.org/10.3390/catal11030328
Received: 17 February 2021 / Revised: 26 February 2021 / Accepted: 27 February 2021 / Published: 4 March 2021
(This article belongs to the Special Issue CO2 Capture, Utilization and Storage: Catalysts Design)
Propylene oxide (PO) binding and ring-opening reaction with the bifunctional CO2/epoxide copolymerization catalyst, based on the Co(III)-salcy complex including two quaternary ammonium salts with n-butyl substituents (N+-chains) were investigated by Density Functional Theory (DFT) calculations and compared with the model systems without the N+-chains. The importance of the different possible stereoisomers and the stereoselectivity of these processes for (S)- and (R)-enantiomers of PO were considered. To explore the conformational space for the real catalyst, a complex approach, developed previously was applied. The calculations for the model systems directly demonstrate that PO-ring opening proceeds preferentially in trans catalysts’ configuration and no participation of cis-β isomers is viable; nucleophilic attack at the methylene-carbon atom is preferred over that at methine-carbon atom. For the real bifunctional catalyst, with the (S,S)-configuration of cyclohexane, the results indicate a preference of (R)-PO ring-opening over (S)-PO ring-opening (ca. 6:5). Concerning stereoisomers resulting from the orientation of N+-chains in the real catalyst, different groups of structures participate in the ring-opening reaction for (R)-PO, and different for (S)-PO. The high population of nonreactive complexes of (R)-PO may be the key factor responsible for decreasing the activity of the analyzed catalyst in the epoxide ring-opening reaction. View Full-Text
Keywords: bifunctional Co(III) catalysts; CO2/epoxide copolymerization; epoxide opening; DFT study bifunctional Co(III) catalysts; CO2/epoxide copolymerization; epoxide opening; DFT study
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MDPI and ACS Style

Dyduch, K.; Roznowska, A.; Srebro-Hooper, M.; Lee, B.Y.; Michalak, A. Theoretical Study on Epoxide Ring-opening in CO2/Epoxide Copolymerization Catalyzed by Bifunctional Salen-Type Cobalt(III) Complexes: Influence of Stereoelectronic Factors. Catalysts 2021, 11, 328. https://doi.org/10.3390/catal11030328

AMA Style

Dyduch K, Roznowska A, Srebro-Hooper M, Lee BY, Michalak A. Theoretical Study on Epoxide Ring-opening in CO2/Epoxide Copolymerization Catalyzed by Bifunctional Salen-Type Cobalt(III) Complexes: Influence of Stereoelectronic Factors. Catalysts. 2021; 11(3):328. https://doi.org/10.3390/catal11030328

Chicago/Turabian Style

Dyduch, Karol, Aleksandra Roznowska, Monika Srebro-Hooper, Bun Yeoul Lee, and Artur Michalak. 2021. "Theoretical Study on Epoxide Ring-opening in CO2/Epoxide Copolymerization Catalyzed by Bifunctional Salen-Type Cobalt(III) Complexes: Influence of Stereoelectronic Factors" Catalysts 11, no. 3: 328. https://doi.org/10.3390/catal11030328

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