Ivko, S., James, A.M., Derry, M.J. et al. (2 more authors) (2022) Heterogenisation of a carbonylation catalyst on dispersible microporous polymer nanoparticles. Catalysis Science & Technology, 12 (2). pp. 664-673. ISSN 2044-4753
Abstract
The methanol carbonylation catalyst, cis-[Rh(CO)2I2]–, has been heterogenised within a dispersible microporous polymer support bearing cationic functionality. The microporous polymer has a core-shell structure in which the porous and insoluble core (a cross-linked co-polymer of divinylbenzene and 4-vinylpyridine) is sterically stabilised by long hydrophilic poly(ethylene glycol) chains, allowing a stable nanoparticle dispersion . Incorporation of 4-vinylpyridine as a co-monomer allows post-synthetic modification to generate N-methylpyridinium sites for electrostatic attachment of the anionic rhodium(I) complex. The dispersibility of the polymer-supported catalyst material facilitates the use of in situ transmission IR spectroscopy to obtain kinetic data for the oxidative addition of iodomethane to immobilised cis-[Rh(CO)2I2]– (the rate-limiting step of the carbonylation cycle). The kinetic data followed a double exponential decay, with an initial fast phase having a rate constant k21 that is ~5× greater than k22 for the slow phase (where k22 is similar to the homogeneous system using N-methylpyridinium counter-ions, CH2Cl2, 25 °C). The polymer-supported catalyst was found to be active for carbonylation of MeOH/MeI to give methyl acetate, with an initial rate ca. double that of the homogeneous analogue under the same conditions (10 bar CO, MeI/MeOH, 120 °C). Activity is lost over longer periods due to leaching of Rh from the support.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2021. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. (http://creativecommons.org/licenses/by/3.0/) |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 14 Dec 2021 16:57 |
Last Modified: | 15 Mar 2022 13:21 |
Status: | Published |
Publisher: | Royal Society of Chemistry (RSC) |
Refereed: | Yes |
Identification Number: | 10.1039/d1cy01989a |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:181586 |
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