A study of the role of chiral defect sites at supported platinum nanoparticles in the enantioselective hydrogenation of a-ketoesters

COLL 492

Gary A. Attard, Department of Chemistry, Department of Chemistry, Cardiff University, P.O.Box 912, Cardiff, CF10 3TB, United Kingdom
A supported 5%Pt on graphite catalyst has been used to study the enantioselective hydrogenation of ethyl pyruvate in the presence of cinchona alkaloids. Selective decoration of chiral defect sites by bismuth adatoms affords a method of decoupling enantioselective surface reactions at chiral kinks from other enantioselective reactions associated with the reaction at 30 bar hydrogen. Using a combination of cyclic voltammetry and STM measurements together with measurements of kinetic data as a result of bismuth adsorption, it is concluded that the presence of chiral defect sites is the most important structural feature of the catalyst surface necessary to impart chirality to the final products. STM data of the cinchona alkaloid adsorbed at the platinum nanoparticle surface showing various chiral template phases and strong interactions with particle edges will be used to elucidate a mechanism for the enantioselective aspects of the hydrogenation reaction.
 

Chiral Surfaces

Division of Colloid and Surface Chemistry
The 225th ACS National Meeting, New Orleans, LA, March 23-27, 2003