Nickel nanoparticles modified by the adsorption of chiral amino acids are known to be effective enantioselective heterogeneous catalysts. The leaching of nickel by amino acids has a number of potential effects including the induction of chirality in the nickel atoms left behind in the nanoparticle and the creation of catalytically active nickel complexes. The adsorption of (S)-proline onto Au(111) precovered by two-dimensional nickel nanoclusters was investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and high-resolution electron energy loss spectroscopy. Adsorption of (S)-proline at 300 K resulted in the corrosion of the nickel clusters, the oxidation of the leached nickel, and the on-surface formation of bioinorganic complexes, which are concluded to contain three prolinate species in an octahedral arrangement around the central Ni ion. Two distinguishable forms of nickel prolinate complexes were identified. One form self-assembles into 1-D chains, and the other form gives rise to porous 2-D islands. Octahedral complexes of the type M(AB)3 are intrinsically chiral, resulting in two pairs of enantiomers. The mirror symmetry of each pair of enantiomers is broken when, as in this study, the bidentate ligand itself possesses a chiral center. DFT calculations are used to examine the relative energies of each Ni(prolinate)3 complex as isolated gas phase species and isolated adsorbed species.

STM imaging following the adsorption of (S)-lysine on Au{111} leads to the observation of Au nanofingers whose growth directions correlate with the unit cell vectors of ordered 2-D phases of lysine. The likely mechanism of surface restructuring is discussed.

Enantioselective catalysis is an increasingly important method of providing enantiomeric compounds for the pharmaceutical and agrochemical industries. To date, heterogeneous catalysts have failed to match the industrial impact achieved by homogeneous systems. One successful approach to the creation of heterogeneous enantioselective catalysts has involved the modification of conventional metal particle catalysts by the adsorption of chiral molecules. This article examines the contribution of effects such as chiral recognition and amplification to these types of system and how insight provided by surface science model studies may be exploited in the design of more effective catalysts.

The asymmetric hydrogenation of methylacetoacetate to R-methyl-3-hydroxybutyrate over R,R-tartaric acid modified Ni catalysts is a well known example of heterogeneous enantioselective catalysis. Using STM, RAIRS and TPD, we investigate the adsorption of methylacetoacetate on Ni{1 1 1} and R,R-TA modified Ni{1 1 1} in order to shed light on the molecular mechanisms underlying the enantioselective catalysis. We show that methylacetoacetate adsorption can only occur in regions of low R,R-tartaric acid coverage. Once adsorption occurs, methylacetoacetate is able to locally rearrange the tartrate modifiers to produce a two-dimensional co-crystal. We consider the implications of our work in explaining the mechanism of enantioselective hydrogenation in this type of system.

STM imaging following the adsorption of (S)-lysine on Au{111} leads to the observation of Au nanofingers whose growth directions correlate with the unit cell vectors of ordered 2-D phases of lysine. The likely mechanism of surface restructuring is discussed.