ja5b07672_si_001.pdf (2.57 MB)
The Scope of Direct Alkylation of Gold Surface with Solutions of C1–C4 n‑Alkylstannanes
journal contribution
posted on 2016-01-06, 16:49 authored by Eva Kaletová, Anna Kohutová, Jan Hajduch, Jiří Kaleta, Zdeněk Bastl, Lubomír Pospíšil, Ivan Stibor, Thomas F. Magnera, Josef MichlTreatment
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 oxide 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 THF 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.