Probing Cooperative Effects in Bimetallic Clusters:  Indications of C−N Coupling of CH4 and NH3 Mediated by the Cluster Ion PtAu+ in the Gas Phase

Author:

Koszinowski Konrad1,Schröder Detlef1,Schwarz Helmut1

Affiliation:

1. Institut für Chemie der Technischen Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany

Publisher

American Chemical Society (ACS)

Subject

Colloid and Surface Chemistry,Biochemistry,General Chemistry,Catalysis

Reference12 articles.

1. HCN synthesis from CH4 and NH3 on platinum*1

2. Hydrogen cyanide synthesis on polycrystalline platinum and 90:10 platinum[ndash ]rhodium surfaces

3. Ein Gasphasenmodell für die Pt+-katalysierte Kupplung von Methan und Ammoniak

4. HCN Synthesis from Methane and Ammonia:  Mechanisms of Pt+-Mediated C−N Coupling

5. Cationic metal clusters were generated by laser desorption/-ionization with subsequent supersonic expansion4and transferred into the cell of a CMS 47X FT-ICR.5In the case of Pt2+, the most abundant dimer withm/z= 390 (corresponding to a mixture of195Pt2+,194Pt196Pt+, and192Pt198Pt+) was isolated by means of the FERETS ion-ejection protocol,6whereas in the case of PtAu+, selection of the195Pt197Au+isotopomer required further efforts (see text). After thermalization with pulsed-in Ar buffer gas, reactions with the leaked-in substrates (p(substrate) ≈ 10-8to 10-7mbar) were studied at variable times. From the decline of the reactant ion and the increase of the product ions, bimolecular rate constants (estimated errors of ±30 and ±50% for the reactions with CH4and NH3, respectively) were derived on the basis of the pseudo-first-order approximation. To investigate the reactions of the metal carbenes, these were produced by pulsing in CH4to the mass-selected and thermalized dimer ions. Indications with respect to the structure of some of the product ions were obtained from collision-induced dissociation (CID) experiments. To this end, the ions of interest were mass-selected, kinetically excited, and fragmented by collisions with Ar gas.

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