AVS 58th Annual International Symposium and Exhibition
    Surface Science Division Tuesday Sessions
       Session SS-TuP

Paper SS-TuP1
Oxidative-Coupling Reactions via Nucleophilic Attack on Gold Surface

Tuesday, November 1, 2011, 6:00 pm, Room East Exhibit Hall

Session: Surface Science Poster Session
Presenter: Bingjun Xu, Harvard University
Authors: B. Xu, Harvard University
C.M. Friend, Harvard University
R.J. Madix, Harvard University
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Metallic gold owes its centuries-old mystique and intrinsic value to its chemical inertness toward bulk compound formation. In the past decade, however, it has been discovered that the surface of gold is far from inert, and that gold can catalyze important chemical transformations – particularly with the assistance of molecular oxygen or other oxidizing agents. These processes are of particular significance because they may occur at remarkably low temperatures and pressures, suggesting the possibility of energy efficient and environmentally benign reaction conditions using metallic gold catalysts. Recently, there has been a focus on selective oxidation of alcohols to aldehydes, oxidative self-coupling of alcohols to form esters and, most recently, acylation via amine-formaldehyde coupling. Our work under ultra-high vacuum (UHV) condition on the well defined model system of Au(111) surface has unequivocally proved that surface adsorbed atomic oxygen is critical in facilitating a range of nucleophilic coupling-reactions among alcohols, aldehydes and amines. A general reaction mechanism for this class of coupling-reactions is established: surface alkoxy or amide is formed via the deprotonation of the corresponding alcohol or amine by surface atomic oxygen, which can subsequently nucleophilically attack the aldehydes (formed in situ from alkoxy or introduced directly) and produce the corresponding ester or amide. The product distribution of our low-pressure experiments match remarkably well with gas phase reactions carried out in the ambient condition as well as liquid phase reactions, proves the generality of the mechanism.