The Scope of Direct Alkylation of Gold Surface with Solutions of C-1-C-4 n-Alkylstannanes

0450212 - ÚOCHB 2016 RIV US eng J - Journal Article
Kaletová, Eva - Kohutová, Anna - Hajduch, Jan - Kaleta, Jiří - Bastl, Zdeněk - Pospíšil, Lubomír - Stibor, Ivan - Magnera, T. F. - Michl, Josef
The Scope of Direct Alkylation of Gold Surface with Solutions of C-1-C-4 n-Alkylstannanes.
Journal of the American Chemical Society. Roč. 137, č. 37 (2015), s. 12086-12099. ISSN 0002-7863. E-ISSN 1520-5126
R&D Projects: GA ČR GA14-02337S
EU Projects: European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY
Institutional support: RVO:61388963 ; RVO:61388955
Keywords : self-assembled monolayers * single-molecule junctions * spectroscopy
Subject RIV: CC - Organic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W)
Impact factor: 13.038, year: 2015
http://pubs.acs.org/doi/10.1021/jacs.5b07672

Treatment of cleaned gold surfaces with dilute tetrahydrofuran or chloroform solutions of tetraalkylstannanes (alkyl = methyl, ethyl, n-propyl, n-butyl) or di-n-butylmethylstannyl tosylate under ambient conditions causes a self-limited growth of disordered monolayers consisting of alkyls and tin oxide. Extensive use of deuterium labeling showed that the alkyls originate from the stannane and not from ambient impurities, and that trialkylstannyl groups are absent in the monolayers, contrary to previous proposals. Methyl groups attached to the Sn atom are not transferred to the surface. Ethyl groups are transferred slowly, and propyl and butyl rapidly. In all cases, tin wide is codeposited in submonolayer amounts. The monolayers were characterized by ellipsometry, contact angle goniometry, polarization modulated IR reflection absorption spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy with ferrocyanide/ferricyanide, which revealed a very low charge-transfer resistance. The thermal stability of the monolayers and their resistance to solvents are comparable with those of an n-octadecanethiol monolayer. A preliminary examination of the kinetics of monolayer deposition from a THE solution of tetra-n-butylstannane revealed an approximately half-order dependence on the bulk solution concentration of the stannane, hinting that more than one alkyl can be transferred from a single stannane molecule. A detailed structure of the attachment of the alkyl groups is not known, and it is proposed that it involves direct single or multiple bonding of one or more C atoms to one or more Au atoms.
Permanent Link: http://hdl.handle.net/11104/0251694