Hybridization of Phenylthiolate- and Methylthiolate-Adatom Species at Low Coverage on the Au(111) Surface

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• 作者：Petro Maksymovych ; Dan C. Sorescu ; Oleksandr Voznyy ; John T. Yates ; Jr.
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：April 3, 2013
• 年：2013
• 卷：135
• 期：13
• 页码：4922-4925
• 全文大小：293K
• 年卷期：v.135,no.13(April 3, 2013)
• ISSN：1520-5126

文摘

Using scanning tunneling microscopy we observed reaction products of two chemisorbed thiolate species, methylthiolate and phenylthiolate, on the Au(111) surface. Despite the apparent stability, organometallic complexes of methyl- and phenylthiolate with the gold-adatom (RS-Au-SR, with R as the hydrocarbon group) undergo a stoichiometric exchange reaction, forming hybridized CH₃S-Au-SPh complexes. Complementary density functional theory calculations suggest that the reaction is most likely mediated by a monothiolate RS-Au complex bonded to the gold surface, which forms a trithiolate RS-Au-(SR)-Au-SR complex as a key intermediate. This work therefore reveals the novel chemical reactivity of the low-coverage 鈥渟triped鈥?phase of alkanethiols on gold and strongly points to the involvement of monoadatom thiolate intermediates in this reaction. By extension, such intermediates may be involved in the self-assembly process itself, shedding new light on this long-standing problem.