Insights into the mechanism of carbon dioxide and propylene oxide ring-opening copolymerization using a Co(III)/K(I) heterodinuclear catalyst
Author(s)
Deacy, Arron C
Phanopoulos, Andreas
Lindeboom, Wouter
Buchard, Antoine
Williams, Charlotte K
Type
Journal Article
Abstract
A combined computational and experimental investigation into the catalytic cycle of carbon dioxide and propylene oxide ring-opening copolymerization is presented using a Co(III)K(I) heterodinuclear complex (Deacy, A. C. Co(III)/Alkali-Metal(I) Heterodinuclear Catalysts for the Ring-Opening Copolymerization of CO2 and Propylene Oxide. J. Am. Chem. Soc. 2020, 142(45), 19150−19160). The complex is a rare example of a dinuclear catalyst, which is active for the copolymerization of CO2 and propylene oxide, a large-scale commercial product. Understanding the mechanisms for both product and byproduct formation is essential for rational catalyst improvements, but there are very few other mechanistic studies using these monomers. The investigation suggests that cobalt serves both to activate propylene oxide and to stabilize the catalytic intermediates, while potassium provides a transient carbonate nucleophile that ring-opens the activated propylene oxide. Density functional theory (DFT) calculations indicate that reverse roles for the metals have inaccessibly high energy barriers and are unlikely to occur under experimental conditions. The rate-determining step is calculated as the ring opening of the propylene oxide (ΔGcalc† = +22.2 kcal mol–1); consistent with experimental measurements (ΔGexp† = +22.1 kcal mol–1, 50 °C). The calculated barrier to the selectivity limiting step, i.e., backbiting from the alkoxide intermediate to form propylene carbonate (ΔGcalc† = +21.4 kcal mol–1), is competitive with the barrier to epoxide ring opening (ΔGcalc† = +22.2 kcal mol–1) implicating an equilibrium between alkoxide and carbonate intermediates. This idea is tested experimentally and is controlled by carbon dioxide pressure or temperature to moderate selectivity. The catalytic mechanism, supported by theoretical and experimental investigations, should help to guide future catalyst design and optimization.
Date Issued
2022-10-05
Date Acceptance
2022-09-01
Citation
Journal of the American Chemical Society, 2022, 144 (39), pp.17929-17938
ISSN
0002-7863
Publisher
American Chemical Society
Start Page
17929
End Page
17938
Journal / Book Title
Journal of the American Chemical Society
Volume
144
Issue
39
Copyright Statement
© 2022 The Authors. Published by American Chemical Society. This work is published under a CC BY licence.
License URL
Identifier
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000858431600001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
ALTERNATING COPOLYMERIZATION
EPOXIDE COPOLYMERIZATION
CYCLOHEXENE OXIDE
CO2
COMPLEXES
POLYCARBONATES
ACTIVATION
EFFICIENT
SYSTEMS
Publication Status
Published
Date Publish Online
2022-09-21