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Hybridization of phenylthiolate- and methylthiolate-adatom species at low coverage on the Au(111) surface

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja4000905· OSTI ID:1127493

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 CH{sub 3}S-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.

Research Organization:
National Energy Technology Laboratory - In-house Research; National Energy Technology Laboratory (NETL), Pittsburgh, PA, and Morgantown, WV (United States)
Sponsoring Organization:
USDOE Office of Fossil Energy (FE)
OSTI ID:
1127493
Report Number(s):
A-NETL-PUB-004
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 13 Vol. 135; ISSN 0002-7863
Country of Publication:
United States
Language:
English

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