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

Authors (5): W. Lindeboom, A. C. Deacy, A. Phanopoulos, A. Buchard, C. K. Williams

Themes: Circular Economy (2023)

DOI: 10.1002/anie.202308378

Citations: 7

Pub type: journal-article

Publisher: Wiley

Issue: 37

License: [{"start"=>{"date-parts"=>[[2023, 8, 7]], "date-time"=>"2023-08-07T00:00:00Z", "timestamp"=>1691366400000}, "content-version"=>"vor", "delay-in-days"=>0, "URL"=>"http://creativecommons.org/licenses/by/4.0/"}]

Publication date(s): 2023/09/11 (print) 2023/08/07 (online)


Volume: 62 Issue: 37

Journal: Angewandte Chemie International Edition

Link: [{"URL"=>"https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202308378", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

URL: http://dx.doi.org/10.1002/anie.202308378

AbstractCarbon 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.

Name Description Publised
CCDC 2222739: Experimental Crystal Structure Determination Wouter Lindeboom, Arron C. Deacy, Andreas Phanopoulos, Antoine Buchard, ... 2022