Carbonylation of Dimethyl Ether on Rh/Cs2HPW12O40: Solid-State NMR Study of the Mechanism of Reaction in the Presence of a Methyl Iodide Promoter Full article
Journal |
Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694 |
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Output data | Year: 2012, Volume: 291, Pages: 9-16 Pages count : 8 DOI: 10.1016/j.jcat.2012.03.024 | ||
Tags | 12-Tungstophosphoric acid, 13C solid-state NMR, Carbon monoxide, Carbonylation, Dimethyl ether, Mechanism, Methyl iodide promoter, Rh methyl, Rhodium carbonyls | ||
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Abstract:
Using C-13 solid-state nuclear magnetic resonance, the carbonylation of dimethyl ether (DME) with carbon monoxide has been studied on solid Rh/Cs2HPW12O40 in the presence of a methyl iodide promoter. The observed decrease in the reaction temperature in comparison with halide-free systems is caused by a change of the reaction mechanism. At first, the activation of the promoter and CO on Rh/Cs2HPW12O40 produces methyl rhodium carbonyl species. Carbon monoxide is then embedded into the Rh-CH3 bond to afford Rh acetyl. Rapid migration of the acetyl group from the Rh center to a Bronsted acid site of Rh/Cs2HPW12O40 gives rise to an acetate group attached to the Keggin unit (Keggin acetate). Bronsted acid sites provide dimethyl ether activation with the formation of a surface methoxy group. The latter, through reaction with hydrogen iodide, which is produced at the stage of Rh acetyl-to-Keggin acetate transformation, restores methyl iodide for subsequent carbonylation stages. Methyl acetate formation from a Keggin acetate and DME closes a catalytic cycle.
Cite:
Kazantsev M.S.
, Luzgin M.V.
, Volkova G.G.
, Stepanov A.G.
Carbonylation of Dimethyl Ether on Rh/Cs2HPW12O40: Solid-State NMR Study of the Mechanism of Reaction in the Presence of a Methyl Iodide Promoter
Journal of Catalysis. 2012. V.291. P.9-16. DOI: 10.1016/j.jcat.2012.03.024 WOS Scopus РИНЦ
Carbonylation of Dimethyl Ether on Rh/Cs2HPW12O40: Solid-State NMR Study of the Mechanism of Reaction in the Presence of a Methyl Iodide Promoter
Journal of Catalysis. 2012. V.291. P.9-16. DOI: 10.1016/j.jcat.2012.03.024 WOS Scopus РИНЦ
Dates:
Submitted: | Jan 17, 2012 |
Accepted: | Mar 29, 2012 |
Published online: | May 7, 2012 |
Published print: | Jul 1, 2012 |
Identifiers:
Web of science | WOS:000306779600002 |
Scopus | 2-s2.0-84862008872 |
Elibrary | 17989961 |
Chemical Abstracts | 2012:841364 |
Chemical Abstracts (print) | 157:197452 |
OpenAlex | W2015601363 |