Single-Molecule and Single-Catalytic-Site Studies of Chiral Surface Chemistry

This multidisciplinary area deals with stereoselective heterogeneous catalysis. It is based on the idea of selectively holding one enantioface of a prochiral molecule toward a catalyst surface. Catalytic bond formation then occurs stereoselectively at the surface to form a single enantiomer product. We use scanning tunneling microscopy (STM), catalytic tests and a variety of surface spectroscopy techniques including reflection-FTIR and XPS. Two collaborations are key to the development of this project: we work with the J. Boukouvalas organic synthesis group at Université Laval and with a DFT (density functional theory) group led by B. Hammer at iNano, Aarhus, Denmark.

Examples of ongoing single-molecule and single-catalytic-site studies are given in the following publications.

V. Demers-Carpentier, G. Goubert, F. Masini, R. Lafleur-Lambert, Y. Dong, S. Lavoie, G. Mahieu, J. Boukouvalas, H. Gao, A. M. Havelund Rasmussen, L. Ferrighi, Y. Pan, B. Hammer, Peter H. McBreen. Direct Observation of Molecular Preorganization for Chirality Transfer on a Catalyst Surface. Science 2011, 334, 776-780.http://www.sciencemag.org/content/334/6057/776.abstract

V. Demers-Carpentier, G. Goubert, F. Masini, Y. Dong, A. H. Rasmussen, B. Hammer and P. H. McBreen. STM Measurements of the Full Cycle of an Heterogeneous Asymmetric Hydrogenation Reaction on Chirally Modified Pt(111). J. Phys. Chem. Lett. http://dx.doi.org/10.1021/jz2013853 A presentation of the article is available online in the Virtual Issue of « The Journal of Physical Chemistry Letters». http://www.slideshare.net/jpcoffice/jpcl-jz2013853-mcbreen-presentation

More information on these studies is provided in the following links.

http://inano.au.dk/news-events/news/artikel/new-knowledge-about-asymmetric-synthesis-provides-better-opportunity-for-controlling-chemical-proces/

http://cen.acs.org/articles/89/i47/Deciphering-Surface-Enantioselectivity.html

http://www.aufil.ulaval.ca/articles/boite-noire-boite-verte-33182.html