Spin-Selective Thermal Activation of Methane by Closed-Shell [TaO3]+

Thermal reactions of the closed-shell metal-oxide cluster [TaO3](+) with methane were investigated by using FTICR mass spectrometry complemented by high-level quantum chemical calculations. While the generation of methanol and formaldehyde is somewhat expected, [TaO3](+) remarkably also has the ability to abstract two hydrogen atoms from methane with the elimination of CH2. Mechanistically, the generation of CH2O and CH3OH occurs on the singlet-ground-state surface, while for the liberation of (CH2)-C-3, a two-state reactivity scenario prevails.