Generation of free hydrogen atoms in thermal reaction of ethane with AuNbO3+ cluster cations

• The generation of free H atoms during thermal reaction of simple alkane molecules has been identified.
• The AuNbO3+ ion serves as the first hetero-nuclear oxide cluster species to activate hydrocarbons to produce the free H atoms.
• The conversion of one AuO bond into one AuNb bond drives the H-atom generation.

Single gold-atom doped niobium oxide cluster AuNbO3+ has been prepared and mass-selected to react with C2H6 in an ion trap reactor under thermal collision conditions. The reaction has been characterized by mass spectrometry with isotopic substitution (C2H6 → CH3CD3 and C2D6) and density functional theory calculations. In addition to hydrogen atom abstraction channels identified in a previous fast-flow reactor experiment, a rather unexpected channel of generating the free H atom was observed. The computational study revealed that the gold atom plays an important role in the reaction and the conversion of one AuO bond to one AuNb bond drives the generation of the free H atom. This study enriches the chemistry of gold atoms doped in atomic clusters and provides an ideal model reaction to generate the free H atom that can be a very important intermediate in hydrocarbon transformation.

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