The CeO2 + Cation:  Gas-Phase Reactivity and Electronic Structure

• Published in: Inorganic chemistry Vol. 35; no. 9; pp. 2463 - 2475
• Main Authors: Heinemann, Christoph, Cornehl, Hans H, Schröder, Detlef, Dolg, Michael, Schwarz, Helmut
• Format: Journal Article
• Language: English
• Published: American Chemical Society 24.04.1996
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic951322k

“Bare” CeO2 + ions can be prepared in the gas phase by consecutive oxidation of Ce+ with O2 and NO2. The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO2 + 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 CeO2 + 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 CeO2 and cationic CeO2 + is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a 2Σu + ground state for CeO2 + which is best described as a linear cerium dioxide with a resonating π bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO n + (n = 0−2) species toward hydrocarbons.