Carbonylation of Dimethyl Ether on Solid Rh-Promoted Cs-Salt of Keggin 12-H3PW12O40: A Solid-State NMR Study of the Reaction Mechanism | Sciact - CRIS-system of Boreskov Institute of Catalysis

Carbonylation of Dimethyl Ether on Solid Rh-Promoted Cs-Salt of Keggin 12-H3PW12O40: A Solid-State NMR Study of the Reaction Mechanism Full article

Journal

Journal of Catalysis
ISSN: 0021-9517 , E-ISSN: 1090-2694

Output data

Year: 2011, Volume: 277, Number: 1, Pages: 72-79 Pages count : 8 DOI: 10.1016/j.jcat.2010.10.015

Tags

12-Tungstophosphoric acid, Carbon monoxide, Carbonylation, Dimethyl ether, Mechanism, Methoxy species, Rhodium carbonyls, Solid-state NMR

Authors

Luzgin Mikhail V. ^1,2 , Kazantsev Maxim S. ^1,2 , Volkova Galina G. ¹ , Wang Wei ³ , Stepanov Alexander G. ^1,2

Affiliations

1	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
2	Department of Natural Sciences, Novosibirsk State University, Pirogova Street 2, Novosibirsk 630090, Russia
3	State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu 730000, PR China

Funding (4)

1	Russian Foundation for Basic Research	08-03-92210
2	National Natural Science Foundation of China	20602016
3	Siberian Branch of the Russian Academy of Sciences	111
4	The Ministry of Education and Science of the Russian Federation	П253

The carbonylation of dimethyl ether (DME) with carbon monoxide on Rh-promoted cesium salt of 12-tungstophosphoric acid, Rh/Cs2HPW12O40 (HPA), has been studied with 13C solid-state NMR. The bi-functional character of Rh/Cs2HPW12O40 catalyst in halide-free carbonylation of DME has been directly demonstrated. The activation of the C–O bond of DME proceeds on Brønsted acid sites of HPA with the formation of the methyl group attached to the surface of HPA (methoxy species), whereas the role of rhodium consists in trapping carbon monoxide from gaseous phase and a transfer of CO to the center of DME activation, acidic OH-group of the catalyst, in the form of rhodium carbonyls. The lattice of Cs2HPW12O40 makes it possible to locate these two different active centers in close proximity to each other, e.g., on two adjacent oxygen atoms, terminal and bridging, of one Keggin anion, thus facilitating the insertion of carbon monoxide from rhodium carbonyl into the C–O bond of methoxy-group to produce the acetate group bound to the Keggin anion. The latter offers finally methyl acetate under the interaction with DME, the intermediate surface methoxy-groups being restored.

Luzgin M.V. , Kazantsev M.S. , Volkova G.G. , Wang W. , Stepanov A.G.
Carbonylation of Dimethyl Ether on Solid Rh-Promoted Cs-Salt of Keggin 12-H3PW12O40: A Solid-State NMR Study of the Reaction Mechanism
Journal of Catalysis. 2011. V.277. N1. P.72-79. DOI: 10.1016/j.jcat.2010.10.015 WOS Scopus РИНЦ

Submitted:	Aug 9, 2010
Accepted:	Oct 18, 2010
Published online:	Nov 20, 2010
Published print:	Jan 3, 2011

Web of science	WOS:000286700300008
Scopus	2-s2.0-78650172022
Elibrary	16683918
Chemical Abstracts	2010:1549193
Chemical Abstracts (print)	154:234185
OpenAlex	W2018367291