Menage-a-trois: single-atom catalysis, mass spectrometry, and computational chemistry

This review provides an overview and an update on how single-atom catalysis can be achieved at a strictly molecular level by performing well-designed gas-phase experiments complemented by quantum chemical calculations. Examples discussed include mechanistic aspects of (i) metal-mediated carbon-carbon bond formation (coupling of methane), (ii) the room temperature oxygen-atom transfer in the redox couple N2O/CO, and (iii) the selective oxidation of inert substrates like H-2 or CH4 by mass-selected metal oxides. While this novel approach, in principle, never accounts for many details of processes occurring in solution or on a surface, it has proved extremely useful in providing a conceptual framework.