The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide

Rzhevskiy, Sergey A.; Shurupova, Olga V.; Asachenko, Andrey F.; Plutalova, Anna V.; Chernikova, Elena V.; Beletskaya, Irina P.

doi:10.3390/ijms252010946

Open AccessArticle

The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide

by

Sergey A. Rzhevskiy

¹,

Olga V. Shurupova

¹,

Andrey F. Asachenko

^1,2,*

,

Anna V. Plutalova

²,

Elena V. Chernikova

^1,2,*

and

Irina P. Beletskaya

²

¹

Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskiy Av., 29, 119991 Moscow, Russia

²

Faculty of Chemistry, Lomonosov Moscow State University, Lenin Hills, 1, Bld. 3, 119991 Moscow, Russia

^*

Authors to whom correspondence should be addressed.

Int. J. Mol. Sci. 2024, 25(20), 10946; https://doi.org/10.3390/ijms252010946

Submission received: 25 September 2024 / Revised: 5 October 2024 / Accepted: 8 October 2024 / Published: 11 October 2024

(This article belongs to the Section Biochemistry)

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Abstract

A comparative study of the copolymerization of racemic propylene oxide (PO) with CO₂ catalyzed by racemic (salcy)CoX (salcy = N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-diaminocyclohexane; X = perfluorobenzoate (OBzF₅) or 2,4-dinitrophenoxy (DNP)) in the presence of a [PPN]Cl ([PPN] = bis(triphenylphosphine)iminium) cocatalyst is performed in bulk at 21 °C and a 2.5 MPa pressure of CO₂. The increase in the nucleophilicity of an attacking anion results in the increase in the copolymerization rate. Racemic (salcy)CoX provides a high selectivity of the copolymerization, which can be higher than 99%, and the living polymerization mechanism. Poly(propylene carbonate) (PPC) with bimodal molecular weight distribution (MWD) is formed throughout copolymerization. Both modes are living and are characterized by low dispersity, while their contribution to MWD depends on the nature of the attacking anion. The racemic (salcy)CoDNP/[PPN]DNP system is found to be preferable for the production of PPC with a high yield and selectivity.

Keywords: ring-opening copolymerization; polycarbonates; carbon dioxide; salen complexes of cobalt; living polymerization

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MDPI and ACS Style

Rzhevskiy, S.A.; Shurupova, O.V.; Asachenko, A.F.; Plutalova, A.V.; Chernikova, E.V.; Beletskaya, I.P. The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide. Int. J. Mol. Sci. 2024, 25, 10946. https://doi.org/10.3390/ijms252010946

AMA Style

Rzhevskiy SA, Shurupova OV, Asachenko AF, Plutalova AV, Chernikova EV, Beletskaya IP. The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide. International Journal of Molecular Sciences. 2024; 25(20):10946. https://doi.org/10.3390/ijms252010946

Chicago/Turabian Style

Rzhevskiy, Sergey A., Olga V. Shurupova, Andrey F. Asachenko, Anna V. Plutalova, Elena V. Chernikova, and Irina P. Beletskaya. 2024. "The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide" International Journal of Molecular Sciences 25, no. 20: 10946. https://doi.org/10.3390/ijms252010946

APA Style

Rzhevskiy, S. A., Shurupova, O. V., Asachenko, A. F., Plutalova, A. V., Chernikova, E. V., & Beletskaya, I. P. (2024). The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide. International Journal of Molecular Sciences, 25(20), 10946. https://doi.org/10.3390/ijms252010946

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The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide

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