The Origin of the Efficient, Thermal Chemisorption of Methane by the Heteronuclear Metal-Oxide Cluster [Al 2 TaO 5 ]<sup/>.

The thermal gas-phase reactions of the closed-shell metal-oxide cluster [Al2 TaO5 ]+ with methane have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. Mechanistic aspects have been addressed to reveal the origins of the efficient addition process which results in activating the C-H bond of methane. The [Al2 TaO5 ]+ /CH4 couple has been compared with several other systems reported previously, and the electronic origins of their rather distinct performances are discussed.