Figure 4.

DFT calculations of the reaction mechanisms. a–d) Computed reaction pathways and e) the corresponding free energy diagrams with the most stable state set to zero in each case. Comparison of olefin isomerization on Ru₁/CeO₂ and Rh₁/CeO₂ single‐atom sites stabilized at the step‐edge of the corrugated CeO₂ (211) surface, prior to (a,b) and after (c,d) activation by oxidative addition of HSiMe₃. f) Computed free energy diagram of the tandem olefin isomerization/hydrosilylation process. Olefin isomerization is catalyzed by Ru₁/CeO₂ while subsequent hydrosilylation with HSiMe₃ is catalyzed by Rh₁/CeO₂ single‐atom sites. Reactants considered: propene as model olefin, HSiMe₃ as silylating agent. T=393 K, P=10 bar (see computational details in the SI).