Mechanism of Surface Alkylation of a Gold Aerogel with Tetra-n-butylstannane-d(36): Identification of Byproducts

0475623 - ÚOCHB 2018 RIV US eng J - Journal Article
Benkovičová, Monika - Wen, D. - Plutnar, Jan - Čížková, Martina - Eychmüller, A. - Michl, Josef
Mechanism of Surface Alkylation of a Gold Aerogel with Tetra-n-butylstannane-d(36): Identification of Byproducts.
Journal of Physical Chemistry Letters. Roč. 8, č. 10 (2017), s. 2339-2343. ISSN 1948-7185
R&D Projects: GA ČR GA14-02337S
Institutional support: RVO:61388963
Keywords : self-assembled monolayers
OECD category: Organic chemistry
Impact factor: 8.709, year: 2017

The formation of self-assembled monolayers on surfaces is often likely to be accompanied by the formation of byproducts, whose identification holds clues to the reaction mechanism but is difficult due to the minute amounts produced. We now report a successful identification of self-assembly byproducts using gold aerogel with a large specific surface area, a procedure likely to be applicable generally. Like a thin gold layer on a flat substrate, the aerogel surface is alkylated with n-butyl-d(9) groups upon treatment with a solution of tetra-n-butylstannane-d(36) under ambient conditions. The reaction byproducts accumulate in the mother liquor in amounts sufficient for GC-MS analysis. In chloroform solvent, they are butene-d(8), butane-d(10), octane-d(18), and tributylchlorostannane-d(27). In hexane, they are the same except that tributylchlorostannane-d(27) is replaced with hexabutyldistannane-d(54). The results are compatible with an initial homolytic dissociation of a C-Sn bond on the gold surface, followed by known radical processes.
Permanent Link: http://hdl.handle.net/11104/0272297