Origin of the Different Reactivity of the Triatomic Anions HMoN-and ZrNH-toward Alkane: Compositions of the Active Orbitals.
The reactivity of the triatomic anions HMoN-and ZrNH-toward alkanes was investigated by means of mass spectrometry in conjunction with density functional theory calculations. HMoN-can activate C-H bond of ethane with the liberation of ethene and hydrogen molecules, and the generation of hydrogen molecules is the major reaction channel; however, no C-H bond activation of ethane was observed over ZrNH-ion, and the density functional theory calculations suggest this pathway is hampered by intrinsic energy barrier. In sharp contrast, another triatomic anion HNbN-can bring about methane activation under thermal conditions, as reported previously. A strong dependence of the chemical reactivity of alkane activation on compositions of active orbitals in the above-mentioned systems is discussed. This combined experimental/computational study may provide new insights into the importance of compositions of active orbitals and their essential role in the reactions of related systems with alkanes.
The Institute for Chemical Physics, Key Laboratory of Cluster Science, School of Chemistry Beijing Institute of Technology , 100081 Beijing, People's Republic of China.
Ji-Chuang
JC
Hu
The Institute for Chemical Physics, Key Laboratory of Cluster Science, School of Chemistry Beijing Institute of Technology , 100081 Beijing, People's Republic of China.
Lin-Lin
LL
Xu
The Institute for Chemical Physics, Key Laboratory of Cluster Science, School of Chemistry Beijing Institute of Technology , 100081 Beijing, People's Republic of China.
Xiao-Yu
XY
Hou
State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences , 100190 Beijing, People's Republic of China.
Hai-Fang
HF
Li
The Institute for Chemical Physics, Key Laboratory of Cluster Science, School of Chemistry Beijing Institute of Technology , 100081 Beijing, People's Republic of China.
Jia-Bi
JB
Ma
State Key Laboratory for Structural Chemistry of Unstable and Stable Species Institute of Chemistry, Chinese Academy of Sciences , 100190 Beijing, People's Republic of China.
Sheng-Gui
SG
He