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Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides.
Nat Chem. 2020 Apr; 12(4):372-380.NC

Abstract

Carbon dioxide and epoxide copolymerization is an industrially relevant means to valorize waste and improve sustainability in polymer manufacturing. Given the value of the polymer products-polycarbonates or polyether carbonates-it could provide an economic stimulus to capture and storage technologies. The process efficiency depends upon the catalyst, and previously Zn(II)Mg(II) heterodinuclear catalysts showed good performances at low carbon dioxide pressures, attributed to synergic interactions between the metals. Now, a Mg(II)Co(II) catalyst is reported that exhibits significantly better activity (turnover frequency > 12,000 h-1) and high selectivity (>99% CO2 utilization and polycarbonate selectivity) for carbon dioxide and cyclohexene oxide copolymerization. Detailed kinetic investigations show a second-order rate law, independent of CO2 pressure from 1-40 bar, to produce polyols. Kinetic data also reveal that synergy arises from differentiated roles for the metals in the mechanism: epoxide coordination occurs at Mg(II), with reduced transition state entropy, while the Co(II) centre accelerates carbonate attack by lowering the transition state enthalpy. This rare insight into intermetallic synergy rationalizes the outstanding catalytic performance and provides a new feature to exploit in other homogeneous catalyses.

Authors+Show Affiliations

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, UK.Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, UK.Department of Chemistry, University College London, London, UK.Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, UK. charlotte.williams@chem.ox.ac.uk.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32221501

Citation

Deacy, Arron C., et al. "Understanding Metal Synergy in Heterodinuclear Catalysts for the Copolymerization of CO2 and Epoxides." Nature Chemistry, vol. 12, no. 4, 2020, pp. 372-380.
Deacy AC, Kilpatrick AFR, Regoutz A, et al. Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides. Nat Chem. 2020;12(4):372-380.
Deacy, A. C., Kilpatrick, A. F. R., Regoutz, A., & Williams, C. K. (2020). Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides. Nature Chemistry, 12(4), 372-380. https://doi.org/10.1038/s41557-020-0450-3
Deacy AC, et al. Understanding Metal Synergy in Heterodinuclear Catalysts for the Copolymerization of CO2 and Epoxides. Nat Chem. 2020;12(4):372-380. PubMed PMID: 32221501.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO2 and epoxides. AU - Deacy,Arron C, AU - Kilpatrick,Alexander F R, AU - Regoutz,Anna, AU - Williams,Charlotte K, Y1 - 2020/03/27/ PY - 2019/05/30/received PY - 2020/02/27/accepted PY - 2020/3/30/pubmed PY - 2020/3/30/medline PY - 2020/3/30/entrez SP - 372 EP - 380 JF - Nature chemistry JO - Nat Chem VL - 12 IS - 4 N2 - Carbon dioxide and epoxide copolymerization is an industrially relevant means to valorize waste and improve sustainability in polymer manufacturing. Given the value of the polymer products-polycarbonates or polyether carbonates-it could provide an economic stimulus to capture and storage technologies. The process efficiency depends upon the catalyst, and previously Zn(II)Mg(II) heterodinuclear catalysts showed good performances at low carbon dioxide pressures, attributed to synergic interactions between the metals. Now, a Mg(II)Co(II) catalyst is reported that exhibits significantly better activity (turnover frequency > 12,000 h-1) and high selectivity (>99% CO2 utilization and polycarbonate selectivity) for carbon dioxide and cyclohexene oxide copolymerization. Detailed kinetic investigations show a second-order rate law, independent of CO2 pressure from 1-40 bar, to produce polyols. Kinetic data also reveal that synergy arises from differentiated roles for the metals in the mechanism: epoxide coordination occurs at Mg(II), with reduced transition state entropy, while the Co(II) centre accelerates carbonate attack by lowering the transition state enthalpy. This rare insight into intermetallic synergy rationalizes the outstanding catalytic performance and provides a new feature to exploit in other homogeneous catalyses. SN - 1755-4349 UR - https://www.unboundmedicine.com/medline/citation/32221501/Understanding_metal_synergy_in_heterodinuclear_catalysts_for_the_copolymerization_of_CO2_and_epoxides_ L2 - http://dx.doi.org/10.1038/s41557-020-0450-3 DB - PRIME DP - Unbound Medicine ER -
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