Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 11, pp. 1962−1968.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
S.A. Andreev, M.A. Il’ina, A.M. Volkova, D.A. de Vekki, N.K. Skvortsov, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83,
No. 11, pp. 1830−1836.
AND INDUSTRIAL ORGANIC CHEMISTRY
Hydrosilylation in the Presence of Platinum(II)
and Rhodium(I) Complexes with Chloride
and Trichlorostannate(II) Anions
S. A. Andreev, M. A. Il’ina, A. M. Volkova, D. A. de Vekki, and N. K. Skvortsov
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received February 18, 2010
Abstract—Hydrosilylation of allyl butyl ether and acetophenone with 1,1,3,3-tetramethyldisiloxane in the presence
of [Pt(LL')XY] and [Rh(Ph
X] (L, L' = cod, dmso, Py, Bn
P; X, y = Cl, SnCl
) was studied.
The modern trend in the development of the
hydrosilylation reaction is characterized by a search for
comparatively inexpensive and simple catalytic systems
capable of yielding the target product in a short time
with high selectivity. Recently, a large number of reports
have been devoted to use of compounds of base metals
for this purpose. However, complexes of platinum and
rhodium still remain the most efﬁ cient catalysts and,
therefore, are in the highest demand .
is efﬁ cient in hydroformylation [2–4], alk-
oxycarbonylation , and hydrogenation and dehydro-
genation [6–9] it exerts a high trans-inﬂ uence and trans-
effect, easily dissociates, and promotes coordination of
oleﬁ ns and stabilization of pentacoordinated transition
states [5, 10–13]. At the same time, there are no unam-
biguous data on the effect of tin on the hydrosilylation
process. For example, it is known the acetylenes are
hydrosilylated in the presence of tin-containing cobalt
carbonyls , and in situ addition of tin(II) chlorides
inhibits hydrosilylation .
Therefore, the goal of our study was to examine the
effect of the trichlorostannate(II) anion on the rate and
selectivity of hydrosilylation of acetophenone and allyl
butyl ether (AllOBu).
As catalysts were chosen cyclooctadiene, dimethyl-
sulfoxide, dibenzyl sulﬁ de, and triphenylphosphine
chloride complexes of platinum(II) and Wilkinson’
Cl], which is due to the good under-
standing of their catalytic properties in hydrosilylation
of a wide variety of substrates [1, 14, 16–21], and their
trichlorostannate(II) anion derivatives. As the hydrosi-
lylating agent was chosen 1,1,3,3-tetramethyldisiloxane
(TMDS), which, on the one hand, is a model siloxane
caoutchouc with terminal SiH groups and, on the other,
possesses the most favorable combination of properties
(stability in air, low boiling point, simple NMR spec-
trum), which enables a qualitative and quantitative anal-
ysis of the reaction.
Allyl butyl ether. The hydrosilylation of allyl
butyl ether with TMDS occurs in accordance with
Farmer’s and Markovnikov’s rules (compounds I and
II, respectively), with silicon predominantly added
to the terminal carbon atom, in good agreement with
published data on the hydrosilylation of allyl ethers [1,
22, 23] (Scheme 1).
The presence of two SiH groups in TMDS
predetermines formation of double-addition products
(compounds III–V). The maximum overall yield
of siloxanes III–V is observed in the presence of
cyclooctadiene complexes of platinum(II) (18 %); with
] or [Pd(dmso)
], it reaches a value
of 15%. The minimum yield of double-addition products
is observed in the case of hydrosilylation in the presence