Enantiospecific desorption of chiral compounds from chiral Cu(643) and achiral Cu(111) surfaces.
Temperature-programmed desorption (TPD) experiments have been conducted to investigate enantiospecific desorption from chiral single-crystal surfaces. The (643) and (six four three) planes of face-centered cubic metals such as Cu have kinked and stepped structures which are nonsuperimposable mirror images of one another and therefore are chiral. These chiral surfaces are denoted Cu(643)(R) and Cu(643)(S). We have observed that the desorption energies of (R)-3-methylcyclohexanone and (R)- and (S)-propylene oxides from the Cu(643)(R) and Cu(643)(S) surfaces depend on the relative handedness of the adsorbate/substrate combination. Since the (643) surface is comprised of terraces with local (111) orientation which are separated by kinked monatomic steps, it is instructive to perform TPD experiments with these chiral compounds on the achiral Cu(111) surface. These experiments have given some insight into the adsorption sites for the chiral molecules on the Cu(643) surfaces. There are several high-temperature features in the TPD spectra of the chiral compounds that only appear in the spectra from the (643) surfaces and thus are attributed to molecules adsorbed at or near the kinked steps. In addition there are lower temperature desorption features observed on the Cu(643) surfaces which occur in the same temperature range as desorption features observed on the Cu(111) surface. These features observed on the (643) surfaces are attributed to desorption from the flat (111) terraces.
Horvath
Joshua D
JD
Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
Gellman
Andrew J
AJ
D000327:Adsorption; D003300:Copper / Q000737:chemistry*; D003512:Cyclohexanones / Q000737:chemistry; D013057:Spectrum Analysis / Q000379:methods; D013237:Stereoisomerism; D013499:Surface Properties
D003512:Cyclohexanones; D003300:Copper