Characterization of mononuclear oxygen-centered radical (O(-*)) in Zr(2)O(8)(-) cluster.
Zirconium oxide cluster anions Zr(x)O(y)(-) are prepared by laser ablation and are reacted with n-butane in a fast flow reactor under near room temperature conditions. A time-of-flight mass spectrometer is used to detect the cluster distribution before and after the reactions. Observation of a hydrogen atom pickup product Zr(2)O(8)H(-) indicates a C-H activation reaction: Zr(2)O(8)(-) + n-C(4)H(10) → Zr(2)O(8)H(-) + C(4)H(9). Density functional theory calculations predict that the oxygen-very-rich cluster Zr(2)O(8)(-) contains one mononuclear oxygen-centered radical (O(-)(•)), which leads to a high C-H activation reactivity, in agreement with the experiments. This study provides one example for how the highly oxidative O(-)(•) radical may be generated by adsorption of O(2) onto unreactive metal oxide clusters.
Ma
Jia-Bi
JB
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.
Wu
Xiao-Nan
XN
Zhao
Yan-Xia
YX
Ding
Xun-Lei
XL
He
Sheng-Gui
SG