Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene

Article abstract of DOI:10.1016/j.jorganchem.2009.01.028

Efficient silylative coupling of linear vinyl-substituted oligo- and polysiloxanes with styrene in the presence of [RuHCl(CO)(PPh₃)₃] (1) and particularly [RuHCl(CO)(PCy₃)₂] (2) combined with copper(I) chloride

Full text of DOI:10.1016/j.jorganchem.2009.01.028

Journal of Organometallic Chemistry 694 (2009) 1903–1906
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Functionalization of vinyl-substituted linear oligo- and polysiloxanes via
ruthenium catalyzed silylative coupling with styrene
_
*
´
Patrycja Zak, Monika Skrobanska, Cezary Pietraszuk, Bogdan Marciniec
´
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, 60-780 Poznan, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Efficient silylative coupling of linear vinyl-substituted oligo- and polysiloxanes with styrene in the pres-
ence of [RuHCl(CO)(PPh3)3] (1) and particularly [RuHCl(CO)(PCy3)2] (2) combined with copper(I) chloride
is described. Treatment of styrene, with terminal or side vinyl group at siloxane skeleton catalyzed by
[RuHCl(CO)(PCy3)2]/CuCl results in the quantitative and selective formation of respective silylative cou-
pling products.
Received 18 December 2008
Received in revised form 15 January 2009
Accepted 16 January 2009
Available online 22 January 2009
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Silylative coupling
Ruthenium hydride complexes
Vinylsiloxanes
SiR3
H
H
H
H
H
H
1. Introduction
+
R'
Substituted vinylsilanes constitute
a class of unsaturated
ð2Þ
organosilicon compounds of prospective wide applicability in or-
ganic synthesis [1], especially in the fast developing palladium-cat-
alyzed coupling of vinylsilanes with organic derivatives [2]. Many
efficient methodologies for synthesis of vinylsilanes involving clas-
sical stoichiometric routes from organometallic reagents as well as
transition metal catalyzed transformations of alkynes, silylalkynes
and alkenes have been reported [3]. Among them, catalytic hydro-
silylation of alkynes plays a crucial role [3c]. In the last two dec-
ades two universal, effective and synthetically attractive methods
for synthesis of well-defined molecular compounds with vinylsil-
icon functionality were developed in our group. Both methods
i.e. silylative coupling (Eq. (1)) and cross-metathesis, are based
on catalytic transformations of vinyl-silicon compounds with ole-
fins (Eq. (2)) and lead to synthesis of respective functionalized vi-
nyl-silicon derivatives [4]
M = Mo, Ru
[M]=CHR
SiR3
H
H
H
H
H
H
+
R'
The silylative coupling is catalyzed by complexes containing or
generating hydride or silyl ligands ([M]ꢀH or [M]ꢀSi, where
M = Ru, Rh, Ir) and proceeds by a mechanism involving the activa-
tion of @C–H and Si–C@ bonds (Eq. (1)) [5,6]. On the other hand,
cross-metathesis proceeds via the carbene mechanism and is cata-
lyzed by well-defined alkylidene complexes of W, Mo or Ru [7]. The
development of a family of ruthenium-based catalysts tolerant of
the majority of functional groups and typical organic and polymer
processing conditions has allowed a great number of new applica-
tions [7]. In the chemistry of unsaturated organosilicon compounds
effective metathesis transformations have been described by our
group for vinyltris(trimethylsiloxy)silane [8,9], chlorosubstituted
vinyldisiloxanes [9] and vinylsubstituted silsesquioxanes [10]. ViSi-
(OEt)2OSi(OEt)2Vi (Vi = H2C@CH–) can be metathetically copoly-
merized with 1,9-decadiene [11,12] or divinylbenzene [13] and
undergoes ROM/ADMET copolymerization with cyclooctadiene
[11]. Divinyldisiloxanes were effectively converted in cross-
metathesis with styrenes and 1-decene [14]. Recently, efficient
cross-metathesis of linear and cyclic vinyl-substituted oligosilox-
anes with selected olefins in the presence of Grubbs type ruthe-
nium alkylidene complexes was described [15]. On the other
hand, vinyltris(trimethylsiloxy)silane [16], methylvinylsubstituted
cyclosiloxane trimers [17] and tetramers [18], vinylsubstituted
SiR3
H
H
H
H
+
H
R'
H
M = Ru, Rh, Ir
ð1Þ
R3Si
R'
H
H
H
H
H
H
SiR3
H
H
[M]-H, [M]-Si
+
+
R'
* Corresponding author. Tel.: +48 61 8291 366; fax: +48 61 8291 508.
E-mail address: bogdan.marciniec@amu.edu.pl (B. Marciniec).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.01.028

_
1904
P. Zak et al. / Journal of Organometallic Chemistry 694 (2009) 1903–1906
Table 1
silsesquioxanes [10] and spherosilicates [19] have been effectively
functionalized via silylative coupling with styrene and some other
olefins. Both silylative coupling and cross-metathesis provide uni-
versal and complementary routes for the synthesis of well-defined
vinylsilicon derivatives [4]. Despite the progress in the study of
silylative coupling of vinylsilanes, the area of substituted polysilox-
anes is relatively unexplored. Non-optimized protocol for silylative
coupling of linear poly(dimethylsiloxane-co-methylvinylsiloxane)
(Mn = 3200) with styrene was proposed, permitting to achieve high
conversion after long times of the reaction (up to 144 h) at a rela-
tively high temperature (100 °C) [20].
Silylative coupling of 3-vinylheptamethyltrisiloxane (3) with styrenes.
Catalyst
CuCl
H2C@CHAr Ar @
Time [h]
Yield of 4 [%]
1
1
1
–
–
+
Ph
Ph
Ph
24
24
3
18
3
18
3
3
88a
0
22
61
14
69
99
99
99
2
–
Ph
2
2
2
+
+
+
Ph
C6H4Me-4
C6H4(OMe)-4
2
Reaction conditions: CH2Cl2, reflux, [Ru]:[ViSi]:[styrene] = 1 ꢁ 10ꢀ2:1:1.5,
Now, we report the very efficient silylative coupling of linear vi-
nyl-substituted oligo- and polysiloxanes with styrene, which leads
to quantitative and stereoselective functionalization. The proce-
dure uses highly active catalytic system and requires mild condi-
tions. We discuss advantages and drawbacks of the reaction as a
general synthetic route for the synthesis of functionalized
vinylsiloxanes.
[Ru]:[CuCl] = 1:5 (if relevant).
a
Toluene, 100 °C.
average number of 13 vinyl side groups in the siloxane chain (as
calculated on the basis of 1H NMR spectroscopic analysis) was trea-
ted with styrene. In the presence of complex 2 combined with cop-
per(I) chloride, the reaction proceeds efficiently according to Eq.
(4).
2. Results and discussion
Silylative coupling of 3-vinylheptamethyltrisiloxane (3) with
styrene was chosen as a model reaction for the study of function-
alization of oligo and polysiloxanes containing side vinyl groups.
Styrene was used as a reaction partner because it is highly reactive
and does not isomerize in the reaction conditions [4]. Treatment of
a mixture of vinylheptamethyltrisiloxane and styrene in the pres-
ence of 1 mol% of ruthenium hydride complex [RuHCl(CO)(PPh3)3]
(1) in toluene at 100 °C gives rise to evolution of ethene and forma-
tion of 3-styrylheptamethyltrisiloxane (Eq. (3)) [16]. The same
experiment performed in boiling CH2Cl2 shows no detectable con-
version after 24 h. Application of 1 mol% of [RuHCl(CO)(PCy3)2] (2)
permits efficient conversion already at 45 °C. An addition of CuCl as
a co-catalyst (5 equiv. relative to catalyst) leads to a significant in-
crease in the catalytic activity, irrespective of the hydride complex
used [21].
Me
Me
+
Me Si
O
Si
O
Si Me
Ph
Me
Me
Me
n
Ph
5 n = 13 (see text)
ð4Þ
Me
Me
Me Si
Me
[Ru]-H or [Ru]-H/ CuCl
O
Si
Me
O
Si Me
Me
n
6
The results obtained are compiled in Table 2 and indicate the
tendencies similar to those observed for the model reaction (Eq.
(1)). The highest activity was observed for the complex [RuHCl-
(CO)(PCy3)2] (2) combined with CuCl, as in the model reaction. In
order to shorten the reaction time and to increase the yield the
reaction was performed with the use of threefold excess of molar
content of styrene relative to the calculated content of vinyl
groups.
In another experiment polymer (5) was heated in a CH2Cl2 solu-
tion of [RuHCl(CO)(PCy3)2] (1 mol%) and CuCl (5 mol%) (relative to
the number of vinyl groups) in the absence of styrene. Analysis of
the reaction mixture by 1H NMR spectroscopy did not indicate any
transformation of vinyl groups in the polymer, which demon-
strates that in the reaction conditions applied, no homo-coupling
of vinylsilyl groups takes place.
OSiMe3
Si Me
OSiMe3
OSiMe3
Me
[Ru]-H or [Ru]-H/ CuCl
Si
OSiMe3
+
Ar
Ar
toluene, 100oC
or CH2Cl2, reflux
3
4a Ar = Ph
4b Ar = C6H4Me-4
4c Ar = C6H4(OMe)-4
ð3Þ
When an excess (1.5 equiv.) of styrene was used relative to the
molar content of vinylsilane, the complete conversion of vinylsi-
lane and nearly quantitative yield of silylstyrene were observed
after 3 hours. The excess of styrene was applied in order to retard
formation of bis(silyl)ethenes [4]. In the conditions used, the reac-
tion is highly regio- and stereoselective. Only E-isomer of silylsty-
rene was observed by the 1H NMR spectroscopy. The reaction was
found to proceed efficiently also in the presence of substituted sty-
renes. The results of the catalytic study are summarized in Table 1.
The results obtained have proved a considerably higher cata-
lytic activity of [RuHCl(CO)(PCy3)2] (2) than [RuHCl(CO)(PPh3)3]
(1). The system [RuHCl(CO)(PCy3)2]/CuCl was proved the most cat-
alytically active and permits nearly quantitative transformation for
all styrenes tested. The fact that the reaction is conducted at the
boiling point of the reaction mixture on intense stirring facilitates
the migration of ethene from the reaction system, so influences the
course of the reaction.
Moreover, an attempt to check the possibility of using this reac-
tion for modification of polymers of higher molecular weights was
made. For this purpose the reaction of the commercially available
trimethylsiloxy-terminated poly(dimethylsiloxane-co-methylvinyl-
Table 2
Silylative coupling of trimethylsiloxy-terminated poly(vinylmethyl)siloxane (5) with
styrene.
Catalyst
CuCl
Time [h]
Yield of 6 [%]
1 (1 mol%)
1 (1 mol%)
2 (1 mol%)
2 (1 mol%)
2 (3 mol%)
–
+
+
–
+
24
24
8
8
3
60a
0
100
60
100
Encouraged by the successful results obtained for 3-vinyl-
trisiloxane (3), we have decided to test the reactivity of styrene to-
wards vinylsubstituted polysiloxanes. Therefore, commercially
available poly(methylvinyl)siloxane (5) (Mn = 1280) containing an
Reaction conditions: CH2Cl2, reflux, [ViSi]:[styrene] = 1:3, [Ru]:[CuCl] = 1:5 (if
relevant).
a
Benzene, 80 °C.

_
P. Zak et al. / Journal of Organometallic Chemistry 694 (2009) 1903–1906
1905
siloxane) (7) (Mn = 26000) containing 4.5 mol% of vinyl-
methylsiloxane unit (as calculated on the basis of 1H NMR
spectrum) was performed with styrene in the presence of [RuHCl
(CO)(PCy3)2]/CuCl. The high molecular weight poly(methylvi-
nyl)siloxanes have been found to exhibit lower reactivity in the
reaction and their satisfactory conversion requires prolonged reac-
tion time and increased catalyst concentration. A complete conver-
sion of 7 was observed after 18 h of the reaction performed in
the presence threefold excess of styrene and 3 mol% of [RuHCl
(CO)(PCy3)2] (2) (in relation to the number of vinyl groups in the
co-polymer). Analysis of the reaction mixture by 1H NMR spectros-
copy indicates exclusive formation of silylative coupling product
(Eq. (5)).
inhibitors. This effect was achieved thanks to the use of styrene
in the possibly lowest excess and application of the mild reaction
conditions (45 °C). The mechanism explaining the effect of addition
of copper(I) chloride on the reaction course was not examined. The
reasonable explanation reported in literature for similar systems
indicates that copper salt acts as a phosphine scavenger and thus
facilitates formation of catalytically active species [22].
3. Conclusions
Linear oligo- and polysiloxanes with terminal or side vinyl
groups at siloxane skeleton undergo efficient silylative coupling
with styrene in the presence of [RuHCl(CO)(PCy3)2]/CuCl. The reac-
tions proceed quantitatively and lead exclusively to formation of E
isomers. The procedures proposed ensure elimination of the com-
petitive formation of polystyrene. Making use of substituted sty-
renes, the silylative coupling permits introduction of a wide
range of functional groups into the polymer chain.
Me
Me
Me Si
Me
Me
+
O
Si
O
Si O Si Me
Ph
Me
Me
Me
m
n
7
Ph
4. Experimental
Me
Si
Me
Me Si
Me
Me
[RuHCl(CO)(PCy3)2] / CuCl
CH2Cl2, reflux, 18h
O
O
Si O Si Me
4.1. General methods and chemicals
Me
Me
Me
n
m
All syntheses and catalytic tests were carried out under dry
argon. 1H NMR and 13C NMR spectra were recorded in C6D6 on a
Varian Gemini 300 at 300 and 75 MHz, respectively. Mass spectra
of the products were obtained by the GC–MS analysis (Varian Sat-
urn 2100T, equipped with a DB-1 capillary column – 30 m and ion
trap detector). GC analyses were performed on a Varian CP 3800
with a 30 m column and TCD. The chemicals were obtained from
the following sources: styrene, dichloromethane, benzene-d6 and
copper(I) chloride from Aldrich, vinylmethylbis(trimethyl-
siloxy)silane, polymethylvinylsiloxane (VMS-T11), trimethylsil-
8 (isolated yield = 80%)
ð5Þ
Finally, we evaluated the applicability of silylative coupling
for functionalization of (poly)siloxanes bearing terminal vinyl
groups. For this purpose the commercially available 1,5-divin-
ylhexamethyltrisiloxane (9) and vinyldimethylsilyl-terminated
poly(dimethylsiloxane) (10) (Mn = 6000) containing an average
number of 78 dimethylsiloxy units in the siloxane chain (as calcu-
lated on the basis of 1H NMR spectrum) were treated with styrene
in the presence of [RuHCl(CO)(PCy3)2] (2) combined with copper(I)
chloride in boiling CH2Cl2. A complete conversion of vinyl groups in
compound 9 and quantitative formation of silylative coupling
product (11) (Eq. (6)) was observed already after 3 h. Standard
work-up and purification on column chromatography gave 11 with
92% of isolated yield. Efficient functionalization of vinyl groups in
polymer 10 required the reaction to be performed for 18 h. Then
full conversion and selective formation of 12 was observed (Eq.
(6)). In both cases reactions result in exclusive formation of the
E,E-isomers.
oxy-terminated
poly(dimethylsiloxane-co-methylvinylsiloxane
(VDT-431) and vinyldimethylsiloxy terminated poly(dimethylsi-
loxane) (DMS-V21) from Gelest/ABCR, toluene, benzene and
hexane from Chempur. [RuHCl(CO)(PPh3)3] (1) [23] and [RuHCl
(CO)(PCy3)2] (2) [24] were prepared according to the literature pro-
cedures. All solvents were dried prior to use over CaH2 and stored
under argon. CH2Cl2 was additionally passed through a column
with alumina and after that it was degassed by repeated freeze-
pump-thaw cycles.
4.2. Silylative coupling of vinylheptamethyltrisiloxane (3)
with styrene
Me
Si
Me
Si
Me
Si
+
O
O
Ph
The oven dried 10 mL glass reactor equipped with a condenser
and a magnetic stirring bar was charged under argon with CH2Cl2
2 mL, vinylheptamethyltrisiloxane 0.035 mL (1.18 ꢁ 10ꢀ4 mol),
Me
Me
Me
n
9 n = 1
10 n = 78 (see text)
decane or dodecane 20 lL (internal standard) and styrene
0.02 mL (1.77 ꢁ 10ꢀ4 mol). The reaction mixture was stirred and
heated in an oil bath to maintain a gentle reflux (ca. 45 °C). Then
a ruthenium complex [RuHCl(CO)(PPh3)3] or [RuHCl(CO)(PCy3)2]
(1.18 ꢁ 10ꢀ6 mol) and after 5 min CuCl 0.0006 g (6.0 ꢁ 10ꢀ6 mol)
were added under argon. The reaction progress was monitored
by gas chromatography. The product was isolated and purified by
liquid chromatography (silica gel, hexane). Spectral data for (4a)
1H NMR (C6D6, d, ppm): 6.46 (d, J = 19.2 Hz, 1H) @CHSi, 7.19 (d,
J = 19.2 Hz, 1H) @CHPh, 0.30 (s, 6H) SiMe, 0.22 (s, 18H) OSiMe3;
13C NMR (C6D6, d, ppm): 1.4 (SiMe), 2.1 (OSiMe3), 126.6 (@CHSi),
145.9 (@CHPh), 127.0, 128.6, 128.9, 138.5 (Ph); MS: m/z (rel. inten-
sity): 45 (7), 73 (14), 133 (5), 145 (8), 159 (5), 161 (8), 205 (6), 207
(6), 219 (6), 221 (6), 265 (5), 267 (12), 293 (18), 294 (6), 308 (6),
309 (100), 310 (30), 311 (15), 324 (6, M+).
Me
Si
Me
Me
Si
Ph
[RuHCl(CO)(PCy3)2] / CuCl
CH2Cl2, reflux
O
O
Si
Ph
Me
Me
Me
n
11 n = 1 (isolated yield 92%)
12 n = 78 (isolated yield 90%)
ð6Þ
In all tests performed, particular attention was paid to detect
the possible formation of the product of the undesirable styrene
polymerization. The procedures presented here ensure the efficient
progress of silylative coupling and permit avoidance of the un-
wanted styrene polymerization without the need of addition of

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P. Zak et al. / Journal of Organometallic Chemistry 694 (2009) 1903–1906
4.3. Silylative coupling of trimethylsiloxy-terminated
poly(vinylmethyl)siloxane (5) with styrene
SiHC@CHPh), 7.0–7.4 (m, 4H, Ph); 13C NMR (C6D6, d, ppm): 1.0
(SiMe, terminal), 1.7 (SiMe, internal), 128.3 (@CHSi), 127.0, 128.5,
128.8, 138.5 (Ph), 145.2 (@CHPh); MS: m/z (rel. intensity): 59
(16), 73 (33), 75 (11), 91 (10), 103 (10), 115 (11), 133 (20), 135
(11), 145 (52), 146 (12), 173 (10), 191 (32), 193 (17), 205 (20),
206 (13), 207 (49), 208 (13), 223 (10), 251 (18), 265 (13), 280
(11), 281 (12), 284 (11), 291 (19), 293 (99), 294 (35), 295 (16),
296 (15), 305 (14), 309 (14), 319 (21), 321 (100), 322 (36), 323
(16), 397 (13), 412 (10, M+).
The oven dried 10 mL glass reactor equipped with a condenser
and a magnetic stirring bar was charged under argon with 2 mL
CH2Cl2, trimethylsiloxy-terminated poly(vinylmethyl)siloxane
0.32 mL (3.195 ꢁ 10ꢀ3 mol of vinyl groups) and styrene 1.1 mL
(9.60 ꢁ 10ꢀ3 mol). The reaction mixture was stirred and heated
in an oil bath to maintain a gentle reflux (ca. 45 °C). Then a ruthe-
nium hydride complex ([RuHCl(CO)(PPh3)3] or [RuHCl-
(CO)(PCy3)3]) (3.195 ꢁ 10ꢀ5 mol) and after 5 min CuCl 0.0159 g
(1.598 ꢁ 10ꢀ4 mol) were added under argon. The mixture was stir-
red and heated at 45 °C under an argon flow for a certain time.
Then the solvent was evaporated and conversion was calculated
on the basis of 1H NMR spectrum. The resulting polymeric product
was isolated and purified by liquid chromatography (silica gel,
hexane:CH2Cl2 = 10:1). Spectral data for (6). 1H NMR (C6D6, d,
ppm): 0.2–0.5 (m, SiMe3), 6.8–7.4 (m, H, CH@CH).
Acknowledgements
Financial support from the Ministry of Science and Higher Edu-
cation (Poland), (Project No. PBZ-KBN 118/T09/17) is gratefully
_
acknowledged. P. Zak wishes to acknowledge the grant from the
Operational Programme of Human Resources, Action 8.2., co-fi-
nanced by EU European Social Fund and Polish State.
References
4.4. Silylative coupling of trimethylsiloxy-terminated
poly(dimethylsiloxane-co-methylvinylsiloxane (7) with styrene
[1] (a) T.H. Chan, I. Fleming, Synthesis (1979) 761;
(b) W.P. Weber, Silicon Reagents for Organic Synthesis, Springer, Berlin, 1983
(Chapter 7);
The oven dried 10 mL glass reactor equipped with a condenser
and a magnetic stirring bar was charged under argon with 2 mL
CH2Cl2, trimethylsiloxy-terminated poly(dimethylsiloxane-co-
methylvinylsiloxane) 0.46 mL (2.40 ꢁ 10ꢀ4 mol vinyl group) and
styrene 0.14 mL (1.22 ꢁ 10ꢀ3 mol). The reaction mixture was stir-
red and heated in an oil bath to maintain a gentle reflux (ca.
45 °C). Then ruthenium complex [RuHCl(CO)(PCy3)2] 0.0052 g
(7.16 ꢁ 10ꢀ6 mol) and after 5 min. CuCl 0.0036 g (3.58 ꢁ 10ꢀ5 mol)
were added under argon. The mixture was stirred and heated at
45 °C under argon flow for 18 h. After that time, the solvent was
evaporated and complete conversion was confirmed by 1H NMR
spectroscopy. The resulting polymeric product was isolated and
(c) E.W. Colvin, Silicon Reagents in Organic Synthesis, Academic Press, London,
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(d) T.-Y. Luh, S.-T. Liu, in: Z. Rappoport, Y. Apeloig (Eds.), The Chemistry of
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(c) B. Marciniec, H. Maciejewski, C. Pietraszuk, P. Pawluc´, in: B. Marciniec
(Ed.), Hydrosilylation, Springer, 2009.
purified
by
liquid
chromatography
(silica
gel,
hex-
ane:CH2Cl2 = 10:1). Isolated yield 80%. Spectral data for (8). 1H
NMR (C6D6, d, ppm): 0.10–0.53 (SiMe), 6.53 (broad d, J = 19.3 Hz,
@CHSi), 7.29 (broad d, J = 19.3 Hz, @CHPh), 7.43–7.45 (m, Ph),
7.06–7.14 (m, Ph); 13C NMR (C6D6, d, ppm): 0.3-2.0 (SiMe), 126.0
(@CHSi), 127.0, 128.7, 128.9, 138.4 (Ph), 146.3 (@CHPh).
[4] [a] B. Marciniec, C. Pietraszuk, Metathesis of Silicon-Containing Olefins, in:
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(Chapter 2.13);
(b) B. Marciniec, C. Pietraszuk, Curr. Org. Chem. 7 (2003) 691–743.
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4.5. Silylative coupling of vinyldimethylsiloxy-terminated
polydimethylsiloxane (10) with styrene
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The oven dried 10 mL glass reactor equipped with a condenser
and a magnetic stirring bar was charged under argon with 2 mL
CH2Cl2, vinyldimethylsiloxy-terminated polydimethylsiloxane
(10) 0.97 g (1.6 ꢁ 10ꢀ4 mol) and styrene 0.0056 g (4.85 ꢁ 10ꢀ4
mol). The reaction mixture was stirred and heated in an oil bath
to maintain a gentle reflux (ca. 45 °C). Then ruthenium complex
[RuHCl(CO)(PCy3)2] 0.0023 g (3.23 ꢁ 10ꢀ6 mol) was added under
argon. After 5 min CuCl 0.0016 g (1.6 ꢁ 10ꢀ6 mol) was added under
argon. The mixture was stirred and heated at 45 °C under argon
flow for 18 h. Then the solvent was evaporated. The resulting poly-
meric product was isolated and purified by use of chromatography
column (silica gel, hexane:CH2Cl2 = 10:1). Spectral data for (12). 1H
NMR (C6D6, d, ppm): 7.36–7.43 (m, 4H, Ph), 7.06–7.17 (m, 6H, Ph),
7.11 (d, J = 19.2 Hz, 2H, @CHPh), 6.53 (d, J = 19.2 Hz, 2H, @CHSi),
0.12–0.55 (SiMe); 13C NMR (C6D6, d, ppm): 145.2 (@CHPh), 127.0
(@CSi), 128.2, 128.5, 128.8 (Ph), 0.9, 1.4, 1.5, 1.9 (SiMe). An analo-
gous procedure was used for silylative coupling of 1,5-divin-
yltetramethyltrisiloxane (9) with styrene. Spectral data for (11).
1H NMR (C6D6, d, ppm): 0.26 (s, 6H, SiMe2), 0.35 (s, 12H, SiMe2),
6.55 (d, J = 18.9, 2H, SiHC@CHPh), 7.15 (d, J = 18.9, 2H,
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