Tuning the Reactivities of the Heteronuclear [Al<sub>n</sub>V<sub>3−n</sub>O<sub>7−n</sub>]<sup> </sup> (n=1, 2) Cluster Oxides towards Methane by Varying the Composition of the Metal Centers.
The thermal gas‐phase reactions of [Al2VO5] and [AlV2O6] with methane have been explored by using Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry complemented by high‐level quantum chemical calculations. Both cluster ions chemisorbed methane as the major reaction channels at room temperature. [Al2VO5] could break only one C−H bond to liberate CH3, whereas [AlV2O6] exhibited higher oxidizing ability such that it brings about the selective generation of formaldehyde. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed. The reactivity of cluster oxides [AlnV3−nO7−n] (n=1, 2) towards methane was tuned by varying the composition of the metal centers. The thermal gas‐phase reactions of [Al2VO5] and [AlV2O6] with methane have been explored by using Fourier transform ion cyclotron resonance (FT‐ICR) mass spectrometry complemented by high‐level quantum chemical calculations. Mechanistic aspects are revealed and the crucial roles of the metal centers are discussed.