Methane Activation by the Heteronuclear Cluster [TiAlO4]+: Direct Hydrogen Abstraction by a Nonradical Oxygen

The gas-phase reactions of [TiAlO4](+) with methane have been explored by using FTICR mass spectrometry complemented by quantum chemical calculations. Interestingly, the [TiAlO4](+) ions can activate two methane molecules continuously. Moreover, in contrast to the previous reports on gas-phase methane activation by metal oxide clusters, in which hydrogen-atom transfer and/or proton-coupled electron transfer prevail, a hydride transfer process dominates the [TiAlO4](+)/CH4 system. The associated electronic origins have been discussed, and such a terminal metal-oxo active center as addressed in the [TiAlO4](+) cluster has proven to be promising in the construction of efficient catalysts concerning methane conversion.