Reactivity of sulfur-containing molecules on noble metal surfaces. 4. Benzenethiol on Au(110)

Article abstract of DOI:10.1021/ja00086a035

The adsorption of benzenethiol on clean and sulfided Au(110) surfaces has been investigated with temperature programmed reaction spectroscopy. The monolayer is saturated at an benzenethiol coverage of 0.25 monolayers. About one-half of the thiol adsorbed at 100 K undergoes S-H bond cleavage below 300 K to form phenyl thiolate; H₂ and H₂S are evolved between 150 and 350 K. Phenyl thiolate decomposes above 400 K on clean Au(110) to yield mainly biphenyl, together with diphenyl sulfide, benzenethiol, and dibenzothiophene. With sulfidation of the Au(110) surface, the yield of biphenyl drops, while that of diphenyl sulfide rises. The range of products formed arises from competing C-S bond cleavage and C-H bond cleavage processes.