Mechanisms of catalytic dehydrogenation of alkanes by rhodium clusters Rh n + probed by isotope labelling

The regioselectivity for the dehydrogenation of alkanes by rhodium clusters was investigated by reacting Rh n +, n = 1–20, with the isotopically labelled alkanes ethane-1,1,1- d 3 and propane-1,1,1,3,3,3- d 6. For Rh + reacting with propane a clear preference for a 1,2- over a 1,1- and 1,3-mechanism...

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Veröffentlicht in:International journal of mass spectrometry Jg. 249; S. 191 - 198
Hauptverfasser: Adlhart, Christian, Uggerud, Einar
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Elsevier B.V 01.03.2006
Schlagworte:
Catalysis
Deuterium labelling
Ion molecule reaction
Isotope effect
Metal cluster
Nanotechnology
Reaction mechanism
Rhodium cluster
Ion molecule reaction
Metal cluster
Deuterium labelling
Isotope effect
Rhodium cluster
Reaction mechanism
Catalysis
Nanotechnology
ISSN:1387-3806, 1873-2798
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Zusammenfassung:The regioselectivity for the dehydrogenation of alkanes by rhodium clusters was investigated by reacting Rh n +, n = 1–20, with the isotopically labelled alkanes ethane-1,1,1- d 3 and propane-1,1,1,3,3,3- d 6. For Rh + reacting with propane a clear preference for a 1,2- over a 1,1- and 1,3-mechanism was observed. For larger clusters, hydrogen scrambling is faster than hydrogen elimination, which essentially leads to statistical formation of the neutrals H 2, HD, and D 2. Isotope scrambling with D 2 was also used as a structural probe for the reaction products of rhodium clusters with ethane. The intactness of the C H bonds was demonstrated for ( n > 6). The studies are completed with a detailed kinetic analysis for the reaction of Rh 7 + with ethane and ethane/hydrogen and ethane/helium mixtures. An over-all picture with efficient C H bond activation and fast and reversible hydrogen rearrangements emerges on the basis of these experiments. Some of the dehydrogenation reactions appear to be reversible.
ISSN:1387-3806
1873-2798
DOI:10.1016/j.ijms.2005.12.032