Publikationstyp: Beitrag in wissenschaftlicher Zeitschrift
Art der Begutachtung: Peer review (Publikation)
Titel: Mechanisms for the dehydrogenation of alkanes on platinum : insights gained from the reactivity of gaseous cluster cations, Pt(n)+, n = 1-21
Autor/-in: Adlhart, Christian
Uggerud, Einar
DOI: 10.1002/chem.200700501
Erschienen in: Chemistry - A European Journal
Band(Heft): 13
Heft: 24
Seiten: 6883
Seiten bis: 6890
Erscheinungsdatum: 17-Aug-2007
Verlag / Hrsg. Institution: Wiley
ISSN: 0947-6539
Sprache: Englisch
Schlagwörter: Cluster compounds; Heterogeneous catalysis; Isotope scrambling; Gas-phase reactions
Fachgebiet (DDC): 540: Chemie
Zusammenfassung: Rates for the dihydrogen elimination of methane, ethane, and propane with cationic platinum clusters, Ptn+ (1≤n≤21), were measured under binary collision conditions in a Fourier transform ion cyclotron resonance mass spectrometer (FTICR). The reaction rate for a given cluster, Ptn+, follows the trend k(CH4)<k (C2H6)<k(C3H8). Methane is particular in the sense that reactivity is highly variable; some clusters (n=1–3, 5–9, 11, 12, 15) are very reactive towards methane, while all other clusters react with low efficiency or not at all. For propane, all clusters react efficiently, while the reactivity of ethane lies in‐between that of methane and propane. By necessity, dihydrogen elimination of methane occurs according to a 1,1‐elimination mechanism. Ethane dehydrogenation takes place according to both a 1,1‐ and a 1,2‐mechanism. The difference between the 1,1‐ and 1,2‐mechanisms is well displayed in specifically increased rates for those clusters that were inefficient in the reaction with methane, as well as in the observed selectivity for H2, HD, and D2 elimination in the reaction with [D3]‐1,1,1‐ethane. Some twofold dihydrogen elimination is observed as well. The outcome of reactions with C2H6 in the presence of D2 demonstrates exchange of all hydrogen atoms in [PtnC2H4]+ with deuterium atoms. A potential energy diagram with a high barrier for the second H2 elimination summarizes these observations. For propane twofold dihydrogen elimination is dominating, and for these reactions a far less regiospecific and more random loss of the hydrogens can be inferred, as was demonstrated by the reactions with [D6]‐1,1,1,3,3,3‐propane.
Volltext Version: Publizierte Version
Lizenz (gemäss Verlagsvertrag): Lizenz gemäss Verlagsvertrag
Departement: Life Sciences und Facility Management
Organisationseinheit: Institut für Chemie und Biotechnologie (ICBT)
Enthalten in den Sammlungen:Publikationen Life Sciences und Facility Management

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