Hybridization of Phenylthiolate- and Methylthiolate-Adatom Species at Low Coverage on the Au(111) Surface
VIRGINIA UNIV CHARLOTTESVILLE
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Using scanning tunneling microscopy we observed reaction products of two chemisorbed thiolate species, methylthiolate and phenylthiolate, on the Au111 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 striped 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.
- Organic Chemistry