Selective hydrogenation of alkynes to alkenes requires a catalytic site with suitable electronic properties for modulating the adsorption and conversion of alkyne, alkene as well as dihydrogen. Here, we report a complex palladium hydride, CaPdH, featured by electron-rich [PdH] sites that are surrounded by Ca cations that interacts with CH and CH via σ-bonding to Pd and unusual cation-π interaction with Ca, resulting in a much weaker chemisorption than those of Pd metal catalysts. Concomitantly, the dissociation of H and hydrogenation of CH ( = 2-4) species experience significant energy barriers over CaPdH, which is fundamentally different from those reported Pd-based catalysts. Such a unique catalytic environment enables CaPdH, the very first complex transition-metal hydride catalyst, to afford a high alkene selectivity for the semihydrogenation of alkynes.
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