A density functional theory study of the 'mythic' Lindlar hydrogenation catalyst
authors Garcia-Mota, M; Gomez-Diaz, J; Novell-Leruth, G; Vargas-Fuentes, C; Bellarosa, L; Bridier, B; Perez-Ramirez, J; Lopez, N
nationality International
journal THEORETICAL CHEMISTRY ACCOUNTS
author keywords Hydrogenation; Acetylenic compounds; Lindlar catalyst; Selectivity; DFT
keywords AUGMENTED-WAVE METHOD; SELECTIVE HYDROGENATION; PALLADIUM CATALYSTS; ALKYNE HYDROGENATION; STEPPED PD; METAL; LEAD; ACETYLENE; ADSORPTION; SURFACE
abstract A Lindlar catalyst is a popular heterogeneous catalyst that consists of 5 wt.% palladium supported on porous calcium carbonate and treated with various forms of lead and quinoline. The additives strategically deactivate palladium sites. The catalyst is widely used for the partial hydrogenation of acetylenic compounds in organic syntheses. Alkyne reduction is stereoselective, occurring via syn addition to give the cis-alkene. Even if it has been employed for about 60 years, there is a lack of molecular level understanding of the Lindlar catalyst. We have applied density functional theory simulations to understand the structure and the nature of the interplay between the multiple chemical modifiers in the Lindlar catalyst. Indeed, the poisons influence different parameters controlling selectivity to the alkene: Pb modifies the thermodynamic factor and hinders the formation of hydrides, while quinoline isolates Pd sites thus minimizing oligomerization.
publisher SPRINGER
issn 1432-881X
year published 2011
volume 128
issue 4-6
beginning page 663
ending page 673
digital object identifier (doi) 10.1007/s00214-010-0800-0
web of science category Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000287748900028
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