Enabling Semihydrogenation of Alkynes to Alkenes by Using a Calcium Palladium Complex Hydride

Abstract

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, CaPdH₂, featured by electron-rich [PdH₂]^δ- sites that are surrounded by Ca cations that interacts with C₂H₂ and C₂H₄ 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 H₂ and hydrogenation of C₂H_<i>x</i> (<i>x</i> = 2-4) species experience significant energy barriers over CaPdH₂, which is fundamentally different from those reported Pd-based catalysts. Such a unique catalytic environment enables CaPdH₂, the very first complex transition-metal hydride catalyst, to afford a high alkene selectivity for the semihydrogenation of alkynes.