Title: Co(III)/Alkali-Metal(I) Heterodinuclear Catalysts for the Ring-Opening Copolymerization of CO2 and Propylene Oxide

Authors (4): A. C. Deacy, E. Moreby, A. Phanopoulos, C. K. Williams

Themes: Circular Economy (2020)

DOI: 10.1021/jacs.0c07980

Citations: 136

Pub type: journal-article

Publisher: American Chemical Society (ACS)

Issue: 45

License: [{"start"=>{"date-parts"=>[[2020, 10, 27]], "date-time"=>"2020-10-27T00:00:00Z", "timestamp"=>1603756800000}, "content-version"=>"vor", "delay-in-days"=>0, "URL"=>"http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html"}]

Publication date(s): 2020/11/11 (print) 2020/10/27 (online)

Pages: 19150-19160

Volume: 142 Issue: 45

Journal: Journal of the American Chemical Society

Link: [{"URL"=>"http://pubs.acs.org/doi/pdf/10.1021/jacs.0c07980", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/jacs.0c07980", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

URL: http://dx.doi.org/10.1021/jacs.0c07980

The ring-opening copolymerization of carbon dioxide and propene oxide is a useful means to valorize waste into commercially attractive poly(propylene carbonate) (PPC) polyols. The reaction is limited by low catalytic activities, poor tolerance to a large excess of chain transfer agent, and tendency to form byproducts. Here, a series of new catalysts are reported that comprise heterodinuclear Co(III)/M(I) macrocyclic complexes (where M(I) = Group 1 metal). These catalysts show highly efficient production of PPC polyols, outstanding yields (turnover numbers), quantitative carbon dioxide uptake (>99%), and high selectivity for polyol formation (>95%). The most active, a Co(III)/K(I) complex, shows a turnover frequency of 800 h–1 at low catalyst loading (0.025 mol %, 70 °C, 30 bar CO2). The copolymerizations are well controlled and produce hydroxyl telechelic PPC with predictable molar masses and narrow dispersity (Đ < 1.15). The polymerization kinetics show a second order rate law, first order in both propylene oxide and catalyst concentrations, and zeroth order in CO2 pressure. An Eyring analysis, examining the effect of temperature on the propagation rate coefficient (kp), reveals the transition state barrier for polycarbonate formation: ΔG‡ = +92.6 ± 2.5 kJ mol–1. The Co(III)/K(I) catalyst is also highly active and selective in copolymerizations of other epoxides with carbon dioxide.

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ja0c07980_si_001.pdf Supl. data for Co(III)/Alkali-Metal(I) Heterodinuclear Catalysts for the... 2020
ja0c07980_si_002.cif Supl. data for Co(III)/Alkali-Metal(I) Heterodinuclear Catalysts for the... 2020


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