Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization

Wouter Lindeboom, Arron C Deacy, Andreas Phanopoulos, Antoine Buchard, Charlotte Katherine Williams

Research output: Contribution to journalArticlepeer-review

6 Citations (SciVal)

Abstract

Carbon dioxide copolymerization is a front-runner CO2 utilization strategy but its viability depends on improving the catalysis. So far, catalyst structure-performance correlations have not been straightforward, limiting the ability to predict how to improve both catalytic activity and selectivity. Here, a simple measure of a catalyst ground-state parameter, metal reduction potential, directly correlates with both polymerization activity and selectivity. It is applied to compare performances of 6 new heterodinuclear Co(III)K(I) catalysts for propene oxide (PO)/CO2 ring opening copolymerization (ROCOP) producing poly(propene carbonate) (PPC). The best catalyst shows an excellent turnover frequency of 389 h-1 and high PPC selectivity of >99% (50 °C, 20 bar, 0.025 mol% catalyst). As demonstration of its utility, neither DFT calculations nor ligand Hammett parameter analyses are viable predictors. It is proposed that the cobalt redox potential informs upon the active site electron density with a more electron rich cobalt centre showing better performances. The method may be widely applicable and is recommended to guide future catalyst discovery for other (co)polymerizations and carbon dioxide utilizations.

Original languageEnglish
Article numbere202308378
Number of pages11
JournalAngewandte Chemie (International ed. in English)
Volume62
Issue number37
Early online date7 Aug 2023
DOIs
Publication statusPublished - 11 Sept 2023

Bibliographical note

The EPSRC (EP/S018603/1; EP/R027129/1), Research England (RED, RE-P-2020-04), Econic Technologies (CASE studentship WL), the Oxford Martin School (Future of Plastics) and Royal Society (UF/160021 and URF\R\221027, fellowship to AB) are acknowledged for research funding

Keywords

  • Carbon Dioxide
  • Catalysis
  • Epoxide
  • Ring Opening Copolymerization
  • Structure-Activity

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis

Fingerprint

Dive into the research topics of 'Correlating Metal Redox Potentials to Co(III)K(I) Catalyst Performances in Carbon Dioxide and Propene Oxide Ring Opening Copolymerization'. Together they form a unique fingerprint.

Cite this