Methane Activation by [OsC3]+: Implications for Catalyst Design

Gas-phase reactions of [OsC3](+) withmethaneat ambient temperature have been studied by using quadrupole-ion trapmass spectrometry combined with quantum chemical calculations. Thecomparison of [OsC3](+) with the product clustersrevealed significant changes in cluster reactivity. In particular,with different ligands, the cluster may produce multiple productsor, alternatively, just a single product. Theoretical calculationsreveal the influence of electronic features such as molecular polarityindex, charge and spin distribution, and HOMO-LUMO gap on thereactivity of the Os complexes. Fundamentally, it is the polarityof the clusters that leads to the cluster reactivity in the methaneactivation. Furthermore, reducing the local polarity of the catalystactive site may be one means of reducing the number of byproductsin the reaction.

Automated summary

Gas-phase reactions of [OsC3](+) with methane at ambient temperature were studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Comparison with product clusters revealed significant changes in cluster reactivity. Theoretical calculations showed that electronic features such as molecular polarity index, charge and spin distribution, and HOMO-LUMO gap had an influence on the reactivity of the Os complexes. The polarity of the clusters played a fundamental role in the methane activation. Lowering the local polarity of the catalyst active site may reduce the formation of byproducts in the reaction.