Atomically dispersed palladium catalyzes H/D exchange and isomerization of alkenes via reversible insertion and elimination

H/D exchange and hydrogen-mediated isomerization (HMI) of alkenes require the reversible alkene insertion and elimination process. However, heterogeneous metal catalysts with ubiquitous, active hydrogen species involved in the hydrogenation reactions inevitably result in alkane production. We demonstrate in this work that H₂ can be heterolytically activated into H⁺ and H⁻ on the atomically dispersed Pd₁/Cu₂O for the selective H/D exchange and HMI of alkenes. While the hydride can selectively mediate the H/D exchange and the HMI of alkenes, the proton transfer for the production of alkanes is inhibited due to the basicity of oxygen atoms on Cu₂O. Moreover, with enhanced stability at an elevated temperature, the atomically dispersed Pd catalyst supported on Cu₃N not only shows outstanding selectivity and stability in the HMI of various alkenes, but also exhibits about one order higher activity than the reported homogeneous and heterogeneous catalysts.