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Heterogenisation of a Carbonylation Catalyst on Dispersible Microporous Polymer Nanoparticles

submitted on 27.04.2021, 10:01 and posted on 28.04.2021, 07:30 by Samuel Ivko, Alex James, Matthew Derry, Robert Dawson, Anthony Haynes
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 co-polymer of divinylbenzene and 4-vinylpyridine) is suspended in solution by long hydrophilic poly(ethylene glycol) chains, allowing a stable suspension of the nanoparticles to form. 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). Remarkably, the oxidative addition proceeds faster than for the homogeneous system (Bu4N+ counter-ion, CH2Cl2, 25 °C). The polymer-supported catalyst was found to be active for methanol carbonylation, with a turnover frequency similar to that of the homogeneous analogue under the same conditions (10 bar CO, MeI/MeOH/CHCl3, 120 °C). The supported catalyst is easily recovered and is shown to maintain comparable activity upon recycling.


Email Address of Submitting Author


University of Birmingham


United Kingdom

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest