Russian Journal of General Chemistry, Vol. 74, No. 3, 2004, p. 469. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 3, 2004, p. 517.
Original Russian Text Copyright
2004 by Timokhin, Zaborovskii, Ferreri, Chatgilialoglu.
LETTERS
TO THE EDITOR
Liquid-Phase Oxidation of Pentamethyldisilane with Oxygen
V. I. Timokhin, A. B. Zaborovskii, K. Ferreri, and C. Chatgilialoglu
Department of Physical Chemistry and Technology of Fossil Fuels, Pisarzhevskii Institute of Physical Chemistry,
National Academy of Sciences of Ukraine, Lvov, Ukraine
Institute of Organic Synthesis and Photoreactions, National Scientific Council of Italy, Bologna, Italy
Received December 17, 2002
Tris(trimethylsilyl)silane reacts with oxygen to
products of pentamethyldisilane at 25 65 C are
pentamethyldisiloxanol (I), pentamethyldisilanol (II),
and pentamethyldisiloxane (III). The IR spectra of
oxidized pentamethyldisilane samples contained ab-
form
bis(trimethylsiloxy)(trimethylsilyl)silane
(Me3SiO)2Si(H)SiMe3 as a major reaction product [1].
Oxidation of pentamethyldisilane can be used as a
model reaction for studying oxidative conversions of
silane polymers [2]. However, this reaction has not
yet been studied.
1
sorption bands at 1060 and 3200 3600 cm , charac-
teristic of Si O and O H bonds, respectively. The
silylhydroperoxide Me3SiSi(OOH)Me2 was not found
among the reaction products. The formation of the
major reaction products can be represented by the
following scheme.
Using IR spectroscopy, gas chromatography, and
mass spectrometry we found that the major oxidation
O2
O2
pentamethyldisilane
Me3SiSi(H)Me2
Me3SiSi Me2
Me3SiSi(OO )Me2
Me3SiSi(OOH)Me2
Me3SiOSi(O )Me2
Me3SiOSi(OH)Me2,
pentamethyldisilane
pentamethyldisilane
Me3SiSi(OO )Me2
Me3SiSi(O )Me2
Me3SiSi(HO)Me2,
II
pentamethyldisilane
Me3SiSi(O )Me2
Me3SiOSi Me2
Me3SiOSi(H)Me2.
III
Pentamethyldisilane was prepared from chloro-
pentamethyldisilane [3]. Pentamethyldisilanol (II) and
pentamethyldisiloxanol (I) were synthesized starting
from chloropentamethyldisilane and 3-acetoxy-1,1,1,
3,3-pentamethyldisiloxane, respectively [4, 5]. Penta-
methyldisiloxane (III) is a commercial product
(ABCR).
70 280 C (10 deg/min).
ACKNOWLEDGMENTS
The authors are grateful to National Academy of
Sciences of Ukraine and National Scientific Council
of Italy for financial support of this work.
REFERENCES
The oxidation of pentamethyldisilane with oxygen
was performed in a temperature-controlled glass
reactor with a magnetic stirrer. The temperature of the
reaction mixture was maintained constant to within
1 C. Oxygen was fed from a rubber balloon at 1 atm.
1. Chatgilialoglu, C., Guarini, A., Guerrini, A., and Se-
coni, G., J. Org. Chem., 1992, vol. 57, no. 8, p. 2207.
2. Chatgilialoglu, C., Guerrini, A., Lucarini, M., Pe-
dulli, G.F., Carrozza, P., Da Roit, G., Borzatta, V., and
Lucchini, V., Organometallics, 1998, vol. 17, no. 11,
p. 2169.
3. Kumada, M., Ishikawa, M., and Maeda, S., J. Organo-
met. Chem., 1964, vol. 2, no. 6, p. 478.
4. Cella, J.A. and Carpenter, J.C., J. Organomet. Chem.,
1994, vol. 480, nos. 1 2, p. 23.
Thin-layer chromatography was performed on Si-
licagel-60 F254 plates (Merck). The IR spectra were
obtained on a Nicolet-205 FT IR spectrophotometer
in a NaCl cell (0.5 mm) with a standard resolution of
1
1
2 cm in the range 400 4000 cm . Gas chromato-
graphy mass spectrometry was performed on an HP-
5890 gas chromatograph with an HP-5972 mass-
selective detector, column HP-5, temperature program
5. Ban, H. and Sukegawa, K., J. Appl. Polym. Sci., 1987,
vol. 33, no. 8, p. 2787.
1070-3632/04/7403-0469 2004 MAIK Nauka/Interperiodica
Timokhin
