title: Gold(III) Mediated Activation and Transformation of Methane on Au1-Doped Vanadium Oxide Cluster Cations AuV2O6(.).
abstract: Gold in the +III oxidation state (Au(III)) has been proposed as a promising species to mediate challenging chemical reactions. However, it is difficult to characterize the chemistry of individual Au(III) species in condensed-phase systems mainly due to the interference from the Au(I) counterpart. Herein, by doping Au atoms into gas-phase vanadium oxide clusters, we demonstrate that the Au(III) cation in the AuV2O6(+) cluster is active for activation and transformation of methane, the most stable alkane molecule, into formaldehyde under mild conditions. In contrast, the AuV2O6(+) cluster isomers with the Au(I) cation can only absorb CH4. The clusters were generated by laser ablation and mass selected to react with CH4, CD4, or CH2D2 in an ion trap reactor. The reactivity was characterized by mass spectrometry and quantum chemistry calculations. The structures of the reactant and product ions were identified by using collision-induced and 425 nm photo-induced dissociation techniques.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
authors.forename: Zi-Yu
authors.initials: ZY
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.|University of Chinese Academy of Sciences , Beijing 100049, People's Republic of China.
authors.forename: Hai-Fang
authors.initials: HF
authors.lastname: Li
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
authors.forename: Yan-Xia
authors.initials: YX
authors.lastname: Zhao
authors.affiliation: Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences , Beijing 100190, People's Republic of China.
authors.forename: Sheng-Gui
authors.initials: SG
authors.lastname: He