Reactivity of sulfur-containing molecules on noble metal surfaces. 2. tert-Butyl thioalcohol on Au(110)

Article abstract of DOI:10.1021/ja00086a034

The adsorption of tert-butyl thioalcohol on clean and sulfided Au(110) surfaces has been investigated with temperature programmed reaction spectroscopy. About half of the thiol adsorbed at 100 K undergoes S-H bond cleavage below 300 K to form tert-bulyl thiolate; H₂ and H₂S are evolved between 150 and 350 K, the relative amounts depending on the surface sulfur coverage. tert-Butyl thiolate decomposes above 400 K on both clean and sulfided Au(110) surfaces via several competing processes to yield tert-butyl thioalcohol, isobutene, and H₂S in the gas phase, together with adsorbed sulfur. The mechanism by which this reaction occurs is dominated by γ-H transfer to either coadsorbed tert-butyl thiolate or sulfur-organometallic reactions which may be unique to surfaces.