December 2011   (Technical report   )

Scanning Tunneling Microscopy Measurements of the Full Cycle of a Heterogeneous Asymmetric Hydrogenation Reaction on Chirally Modified Pt(111)

Vincent Demers-Carpentier, Guillaume Goubert, Federico Masini, Yi Dong, Anton Rasmussen, Bjørk Hammer, Peter McBreen

The hydrogenation of a prochiral substrate, 2,2,2-trifluoroacetophenone (TFAP), on Pt(111) was studied using room-temperature scanning tunneling microscopy (STM) measurements. The experiments were carried out both on a clean surface and on a chirally modified surface, using chemisorbed (R)-(+)-1-(1-naphthyl)ethylamine, ((R)-NEA), as the modifier. On the nonmodified surface, introduction of H2 at a background pressure of ~1 × 10–6 mbar leads to the rapid break-up of TFAP dimer structures followed by the gradual removal of all TFAP-related images. During the latter step, some monomers display an extra protrusion compared to TFAP in dimer structures. They are attributed to a half-hydrogenated intermediate. The introduction of H2 to a mixture of (R)-NEA and TFAP on Pt(111) leads to the removal of TFAP without any change in the population of the modifier, as required for an efficient chirally modified catalyst.

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http://pubs.acs.org/doi/abs/10.1021/jz2013853