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Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO₂ and epoxides

Deacy, AC; Kilpatrick, AFR; Regoutz, A; Williams, CK; (2020) Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO₂ and epoxides. Nature Chemistry , 12 pp. 372-380. 10.1038/s41557-020-0450-3. Green open access

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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.

Type: Article
Title: Understanding metal synergy in heterodinuclear catalysts for the copolymerization of CO₂ and epoxides
Open access status: An open access version is available from UCL Discovery
DOI: 10.1038/s41557-020-0450-3
Publisher version: https://doi.org/10.1038/s41557-020-0450-3
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher's terms and conditions.
Keywords: Catalytic mechanisms, Chemistry, Polymerization mechanisms
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10095913
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