title: The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure.
abstract: "Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.
authors.affiliation: Institut für Organische Chemie der Technischen Universität Berlin, Strasse des 17. Juni 135, D-10623 Berlin, Germany, and Max-Planck-Institut für Physik komplexer Systeme, Bayreuther Strasse 40, Haus 16, D-01187 Dresden, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Heinemann
authors.forename: Hans H.
authors.initials: HH
authors.lastname: Cornehl
authors.forename: Detlef
authors.initials: D
authors.lastname: Schröder
authors.forename: Michael
authors.initials: M
authors.lastname: Dolg
authors.forename: Helmut
authors.initials: H
authors.lastname: Schwarz