title: Structure of the oxygen-rich cluster cation Al2O7+ and its reactivity toward methane and water.
abstract: The oxygen-rich cluster Al(2)O(7)(+) is generated in the gas phase and investigated with respect to both its structure and its reactivity toward small, inert molecules using Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry and DFT-based calculations. Al(2)O(7)(+) reacts with CH(4) under ambient conditions via hydrogen atom transfer (HAT), and with H(2)O a ligand exchange occurs which gives rise to the evaporation of two O(2) molecules. The resulting product ion Al(2)O(4)H(2)(+) is also capable of abstracting a hydrogen atom from both H(2)O and CH(4). As indicated in the H(2)O/2O(2) ligand exchange and supported by collision-induced dissociation (CID) experiments, two O(2) units constitute structural elements of Al(2)O(7)(+). Further insight is provided by DFT calculations, performed at the unrestricted B3LYP/TZVP level, and reaction mechanisms are suggested on the basis of both the experimental and theoretical results.
authors.affiliation: Institut für Chemie der Technischen Universität Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany.
authors.forename: Zhe-Chen
authors.initials: ZC
authors.lastname: Wang
authors.forename: Thomas
authors.initials: T
authors.lastname: Weiske
authors.forename: Robert
authors.initials: R
authors.lastname: Kretschmer
authors.forename: Maria
authors.initials: M
authors.lastname: Schlangen
authors.forename: Martin
authors.initials: M
authors.lastname: Kaupp
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz