title: On the Origin of the Remarkably Variable Reactivities of [AlCeOx]+(x=2-4) towards Methane as a Function of Oxygen Content.
abstract: The thermal gas-phase reactions of the closed-shell heteronuclear metal-oxide clusters [AlCeOx]+(x=2-4) with methane have been explored by FT-ICR mass spectrometry and high-level quantum-chemical calculation. Whereas [AlCeO2]+and [AlCeO4]+are inert towards methane under ambient conditions, [AlCeO3]+spontaneously abstracts one hydrogen atom from methane. Mechanistic aspects have been addressed to reveal the reasons for the rather distinct reactivities of the [AlCeOx]+/CH4couples, and the electronic origins of the unprecedented single hydrogen-atom abstraction from methane by closed-shell [AlCeO3]+are discussed.
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Shaodong
authors.initials: S
authors.lastname: Zhou
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.|Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, P.R. China.
authors.forename: Jilai
authors.initials: J
authors.lastname: Li
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.affiliation: Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 135, 10623, Berlin, Germany.
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz
keywords: gas-phase reactions; metal-oxide clusters; methane activation; quantum-chemical calculation