title: Evidence for C-H...O=C bonding in coadsorbed aromatic-carbonyl systems on Pt(111).
abstract: The coadsorption of ethyl formate, acetone, and methyl pyruvate with benzene and naphthalene on Pt(111) was studied with reflection absorption infrared spectroscopy (RAIRS) and thermal desorption (TPD) measurements. Coadsorbed benzene or naphthalene are found to convert eta1- and eta2-states of ethyl formate and acetone into new states displaying slightly red-shifted carbonyl bands. Similarly, coadsorption converts the enediolate state of methyl pyruvate into a new adsorption geometry in which the carbonyl bands are silent. In each case, coadsorption of the aromatic leads to significantly modified carbonyl desorption spectra. The results suggest an attractive carbonyl-aromatic interaction that weakens or removes the direct interaction of the carbonyl function with the metal surface. The aromatic-carbonyl interaction is attributed to hydrogen bonding between C-H and C=O, enhanced by the chemisorption induced polarization of the aromatic.
authors.affiliation: Département de Chimie, Université Laval, Québec (QC), Canada G1K 7P4.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Lavoie
authors.forename: Peter H
authors.initials: PH
authors.lastname: McBreen