
Authors (4): F. Fiorentini, K. H. S. Eisenhardt, A. C. Deacy, C. K. Williams
Themes: Circular Economy DOI: 10.1021/jacs.4c07405
Citations: 17
Pub type: journal-article
Pub year: 2024
Publisher: American Chemical Society (ACS)
Issue: 33
License: [{"start"=>{"date-parts"=>[[2024, 8, 9]], "date-time"=>"2024-08-09T00:00:00Z", "timestamp"=>1723161600000}, "content-version"=>"unspecified", "delay-in-days"=>0, "URL"=>"https://creativecommons.org/licenses/by/4.0/"}]
Publication date(s): 2024/08/21 (print) 2024/08/09 (online)
Pages: 23517-23528
Volume: 146 Issue: {"issue"=>"33", "published-print"=>{"date-parts"=>[[2024, 8, 21]]}}
Journal: Journal of the American Chemical Society
URL:
Dinuclear polymerization catalysts can show high activity and control. Understanding how to design for synergy between the metals is important to improving catalytic performances. Three heterodinuclear Co(III)K(I) catalysts, featuring very similar coordination chemistries, are prepared with different intermetallic separations. The catalysts are compared for the ring-opening copolymerization (ROCOP) of propene oxide (PO) with CO2 or with phthalic anhydride (PA). The catalyst with a fixed, wide intermetallic separation, LwideCoK(OAc)2 (Co–K = 8.06 Å), shows very high activity for PO/PA ROCOP, but is inactive for PO/CO2 ROCOP. On the other hand, the catalyst with a fixed, narrow intermetallic separation, LshortCoK(OAc)2 (Co–K, 3.59 Å), shows high activity for PO/CO2 ROCOP, but is much less active for PO/PA ROCOP. A bicomponent catalyst system, comprising a monometallic complex LmonoCoOAc used with an equivalent of KOAc[18-crown-6], shows high activity for both PO/CO2 and PO/PA ROCOP, provided the catalyst concentration is sufficiently high, but underperforms at low catalyst loadings. It is proposed that the two lead catalysts, LwideCoK(OAc)2 and LshortCoK(OAc)2, operate by different mechanisms for PO/PA and PO/CO2 ROCOP. The new wide separation catalyst, LwideCoK(OAc)2, shows some of the best performances yet reported for PO/PA ROCOP, and suggests other catalysts featuring larger intermetallic separations should be targeted for epoxide/anhydride copolymerizations.
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