Phosphine ligand-coated Cu nanoparticle-catalyzed selective semihydrogenation of alkynes: electronic or hindrance effects of the ligand?

Physical Chemistry Chemical Physics : PCCP
Yafei LuoDianyong Tang

Abstract

Understanding the mechanism of a catalytic reaction is of fundamental importance not only scientifically but also technologically to the design of high-performance catalysts. In this work, the mechanisms of 1-phenyl-1-propyne and cis-β-methylstyrene hydrogenations catalyzed by Cu55 and ligand-coated Cu55 are explored in detail by means of density functional theory (DFT). The calculated results indicate that the semihydrogenation selectivity of the catalyst can be effectively controlled by employing a suitable ligand. That is, the PCy3 and PPh3 ligands used to coat Cu55 can largely raise the energy barrier of the rate-determining step for cis-β-methylstyrene hydrogenation. By the study of energy decomposition analysis (EDA) and charge density difference, it can be found that the deformation energies of the substrate fragments play a crucial role in the energy barriers of the rate-determining steps. The large hindrance effect of the ligands is beneficial for improving the semihydrogenation selectivity of the catalysts. This study provides significant information for future catalyst design and on the physical origin of the phosphine ligand-coated nanoparticle catalysis for semihydrogenation.

References

Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Sep 28, 2004·Physical Review Letters·Hannu HäkkinenBernd von Issendorff
Jul 13, 2006·Journal of the American Chemical Society·Céline DupontDavid Loffreda
Mar 5, 2009·Physical Review Letters·Alexandre Tkatchenko, Matthias Scheffler
Dec 14, 2011·Journal of Computational Chemistry·Tian Lu, Feiwu Chen
Mar 25, 2014·Physical Chemistry Chemical Physics : PCCP·Xinrui CaoYi Luo
Sep 3, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Emma OaktonChristophe Copéret
Dec 22, 2016·Journal of the American Chemical Society·Alexey FedorovChristophe Copéret

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scanning transmission microscopy

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