Stéphane Lavoie

Direct observation of molecular preorganization for chirality transfer on a catalyst surface.

Scanning tunneling microscopy and theoretical calculations shed light on an asymmetric heterogeneous catalyst. The chemisorption of specific optically active compounds on metal surfaces can create catalytically active chirality transfer sites. However, the mechanism through which these sites bias the stereoselectivity of reactions (typically hydrogenations) is generally assumed to be so complex that continued progress in the area is uncertain. We show that the investigation of heterogeneous asymmetric induction with single-site resolution sufficient to distinguish stereochemical conformations at the submolecular level is finally accessible. A combination of scanning tunneling microscopy and density functional theory calculations reveals the stereodirecting forces governing preorganization into precise chiral modifier-substrate bimolecular surface complexes. The study shows that the chiral modifier induces prochiral switching on the surface and that different prochiral ratios prevail at different submolecular binding sites on the modifier at the reaction temperature.

Activation in prochiral reaction assemblies on Pt(111).

Trifluoroacetophenone (TFAP) forms C O...H-C bonded dimers and trimers at room temperature on Pt(111). It is proposed that these systems mimic the prochiral carbonyl-chiral modifier interaction in the enantioselective hydrogenation of TFAP on cinchona-modified Pt catalysts. That is, the activation of TFAP in homomolecular assemblies at racemic sites is expected to be roughly the same as in the diastereomeric complex formed at chiral sites. This interpretation suggests a reason why alpha-phenyl ketones do not display a strong measured rate enhancement effect in the Orito reaction.

Thermal chemistry of methylene- and phenyl-functionalized carbon nanotubes.

Thermal desorption of covalently functionalized SWNT was followed using Raman, X-ray photoemission (XPS), and thermodesorption (TDS) spectroscopies. By functionalizing different sources of SWNT, we assess the thermal stability of phenyl- and methylene-SWNT derivatives in relation to the source diameter and helicity distribution. For all samples, broad desorption features were observed at approximately 600 K for the phenyl-SWNT and at approximately 500 K for the methylene-SWNT derivatives. In both cases, no influence on helicity and on diameter was observed for the range studied. The study shows that the stability of methylene addends on SWNT is inferior to that of the phenyl and proves that the main desorption pathway of phenyl addends is a phenyl-phenyl coupling reaction.