Origin of the Different Reactivity of the Triatomic Anions HMoN- and ZrNH- toward Alkane: Compositions of the Active Orbitals.

ABSTRACT

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.