title: Direct observation of molecular preorganization for chirality transfer on a catalyst surface.
abstract: 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.
authors.affiliation: Centre de recherche sur les propriétés des interfaces et la catalyse (CERPIC) and Département de chimie, Université Laval, Québec, QC G1V 0A6, Canada.
authors.forename: Vincent
authors.initials: V
authors.lastname: Demers-Carpentier
authors.forename: Guillaume
authors.initials: G
authors.lastname: Goubert
authors.forename: Federico
authors.initials: F
authors.lastname: Masini
authors.forename: Raphael
authors.initials: R
authors.lastname: Lafleur-Lambert
authors.forename: Yi
authors.initials: Y
authors.lastname: Dong
authors.forename: Stéphane
authors.initials: S
authors.lastname: Lavoie
authors.forename: Gautier
authors.initials: G
authors.lastname: Mahieu
authors.forename: John
authors.initials: J
authors.lastname: Boukouvalas
authors.forename: Haili
authors.initials: H
authors.lastname: Gao
authors.forename: Anton M H
authors.initials: AM
authors.lastname: Rasmussen
authors.forename: Lara
authors.initials: L
authors.lastname: Ferrighi
authors.forename: Yunxiang
authors.initials: Y
authors.lastname: Pan
authors.forename: Bjørk
authors.initials: B
authors.lastname: Hammer
authors.forename: Peter H
authors.initials: PH
authors.lastname: McBreen