The Role of Ligand Exchange in Salen Cobalt Complexes in the Alternating Copolymerization of Propylene Oxide and Carbon Dioxide
Abstract
:1. Introduction
2. Results and Discussion
2.1. Polymer Synthesis
2.2. Copolymer Microstructure
2.3. Molecular Weight Distribution of PPC
2.4. Thermal Stability of PPC
2.5. Polymerization Mechanism
3. Materials and Methods
3.1. Materials
3.2. Synthesis of the Complexes
3.3. Polymerization Procedure
3.4. Instrumentation
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Catalyst | PO | Microstructure |
---|---|---|
(R,R)-(salcy)CoBr | (rac)-PO | Regioregular atactic |
(S)-PO | Regioregular isotactic | |
(R)-PO | Regiorandom heterotactic | |
(rac)-(salcy)CoBr | (R)-PO | Regioregular isotactic |
(rac)-PO | Regioregular syndio-enriched | |
(R,R)-(salcy)CoOBzF5 | (rac)-PO | Regioregular iso-enriched |
(S)-PO | Regioregular isotactic | |
(rac)-(salcy)CoOBzF5 | (R)-PO | Regioregular isotactic |
(rac)-PO | Regioregular atactic |
Catalyst | [PO]/[Cat] | [Cat]/[[PPN]Cl] | Time, h | Selectivity, PPC% | TON | TOF, h−1 |
---|---|---|---|---|---|---|
(rac)-(salcy)CoOBzF5 | 6420 | 0.87 | 2 | >97 | 195 | 98 |
6630 | 0.86 | 4 | >97 | 440 | 110 | |
6350 | 0.86 | 6 | >97 | 630 | 105 | |
6500 | 0.86 | 24 | >50 | 1570 | 65 | |
6460 | 0.86 | 72 | >50 | 5050 | 79 | |
(rac)-(salcy)CoDNP | 6170 | 0.90 | 2 | 96.0 | 950 | 470 |
6480 | 0.88 | 4 | 97.2 | 1730 | 430 | |
7080 | 0.74 | 4.5 | 98.4 | 1930 | 430 | |
6500 | 0.81 | 24 | >75 | 4784 | 199 |
Cat/Co-Cat | [PO]/[Cat] | Conversion (PO), % | Selectivity, PPC% | TON | TOF, h−1 | Mn1/Mn2, (a) kDa | ĐM1/ĐM2 (a) |
---|---|---|---|---|---|---|---|
(rac)-(salcy)CoDNP [PPN]DNP | 6670 | 38.2 | 99.0 | 2548 | 637 | 103.2/220.6 | 1.05/1.03 |
(rac)-(salcy)CoCl [PPN]Cl | 5990 | 40.4 | 96.4 | 2422 | 605 | 60.0/121.1 | 1.04/1.03 |
(rac)-(salcy)CoCl [PPN]DNP | 6000 | 43.0 | 97.5 | 2582 | 645 | 98.2/220.8 | 1.07/1.04 |
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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
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 StyleRzhevskiy, 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