An Efficient Catalytic Route for the Synthesis of Silane Coupling Agents Based on the 1,1,3,3-Tetramethyldisiloxane Core

Article abstract of DOI:10.1002/ejic.201601341

We report herein the study of the selective mono-functionalization of 1,1,3,3-tetramethyldisiloxane (TMDSO) with vinyl-substituted silicon derivatives through the hydrosilylation reaction. An investigation of the use of platinum- and rhodium-based catalysts in the reactions between TMDSO and exemplary vinyl-containing silicon derivatives has enabled us to identify the most efficient catalyst, the application of which led to the selective partial functionalization of the disiloxane reagent and the simultaneous formation of only β regioisomers.

Full text of DOI:10.1002/ejic.201601341

A Journal of
Accepted Article
Title: An efficient catalytic route for the synthesis of silane coupling
agents based on 1,1,3,3-tetramethyldisiloxane core
Authors: Bogdan Marciniec, Rafał Januszewski, Ireneusz Kownacki,
Hieronim Maciejewski, and Anna Szymańska
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201601341
Link to VoR: http://dx.doi.org/10.1002/ejic.201601341

European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
An efficient catalytic route for the synthesis of silane coupling
agents based on 1,1,3,3-tetramethyldisiloxane core
[
a]
[b,c]
[b]
[a,c]
Rafał Januszewski, Ireneusz Kownacki,*
Hieronim Maciejewski, Bogdan Marciniec,*
Anna
[
b]
Szymańska
[
9]
Abstract: We report studies concerning the selective mono-
functionalization of 1,1,3,3-tetramethyldisiloxane (TMDSO) with
vinyl-substituted silicon derivatives via the hydrosilylation reaction.
Examinations of platinum- and rhodium-based catalysts in the
reactions between TMDSO and exemplary vinyl-containing silicon
derivatives have enabled appointing the most efficient catalyst,
whose application leads to selective partial functionalization of the
disiloxane reagent and simultaneous formation of only
β-regioisomers.
condensation of silanolates (RMe
as through partial functionalization
tetramethyldisiloxane (TMDSO) with
2
SiOLi) with HSiMe
of
various
2
Cl as well
1,1,3,3-
organic
or organosilicon unsaturated reagents via hydrosilylation
reaction. In view of literature data, the latter is the most
convenient and common protocol used for obtaining derivatives
of this type. The hydrosilylation reaction, in most cases
catalyzed by transition metal complexes, in particular Pt
(Karstedt’s catalyst,
RhCl (t-Bu S) ], allowed modification of TMDSO core, with the
functional groups, such as PEG of different lengths,
2 6
H PtCl ) and Rh (Wilkinson’s catalyst,
[
3
2
3
[
10]
3-
3-(benzophenoxy)-
[
11]
[12]
(
alkyloxy)propyl,
organic epoxides,
Introduction
[13]
[14]
[15]
propyl,
3-(methacryloxy)propyl,
3-(amino)propyl,
aryloxy-
[
16]
alkyl or arylalkyl.
The transition metal-catalyzed addition of Si-H bond to carbon-
carbon multiple bonds is a commonly used and efficient tool for
the synthesis of a wide gamut of organosilanes or polysiloxanes
The hydrosilylation protocol was successfully applied for partial
functionalization of 1,1,3,3-tetramethyldisiloxane with silicon
derivatives, however the number of the latter, which were
reported as functionalizing reagents, is limited to a few examples
of simple commercially available vinylsilanes such as
[
1]
as well as for cross-linking of silicone fluids,
including
[
2]
[3]
silylfunctionalization of unsaturated organic or organosilicon
polymers for different applications, depending on the type and
reactivity of the introduced functional groups. For instance,
1
2
[17]
[4a,7a,b,18]
H
2
C=CHSiR
n
(OR )3-n
,
H
2
C=CHSiMe
3
and vinyl
[19]
[20]
siloxanes
2 2 3
or allyl silane of the type H C=CHCH Si(OEt) .
derivatives of 1,1,3,3-tetramethyldisiloxane (TMDSO) partially
As reported in the above-cited references, in the systems in
1
modified with (alkoxy)vinyl silanes ((R O)
n
R
3-nSiCH=CH
2
) are
[12, 16]
[4a,7a,b,17-19]
which vinyl-substituted organic
or organosilicon
widely used as essential functionalizing agents of fluorinated
compounds were used as reagents, the formation of α- and β-
isomeric was observed, regardless of the platinum or rhodium
based catalysts.
[
4]
[5]
polyethers, acrylic or methacrylic esters or polysiloxane
[
6]
ingredients for heat conductive silicone composition, while the
products of one-sided TMDSO functionalization with olefins or
vinylsilanes with organic substituents at silicon atom
In view of the literature data briefly described above, in particular
the broad scope of applications of TMDSO derivatives endowed
on the one side with hydrolysable silicon functions, we decided
to develop a catalytic system allowing an efficient synthesis of
mono-functionalized 1,1,3,3-tetramethyldisiloxane derivatives via
hydrosilylation as well as selective formation of β-addition
products. This type of bifunctional compounds based on flexible
disiloxane core, bearing in its structure two reactive moieties, i.e.
SiH moiety, which can take part in hydrosilylation process, and a
silicon functional group, susceptible towards hydrolysis and
condensation, seem to be very interesting functionalizing agents
(
R
3
SiCH=CH
2
) are surfactants for production of skin-care
[
7a,b]
[7c]
cosmetics
or coatings and printing ink compositions.
As indicated by the number of patents that have appeared over
the bygone 20 years, particularly those concerning the synthesis
[
2-7]
and utilization of organic and oganosilicon polymers
equipped
with reactive functional groups of various types, the interest in
the synthesis of different multifunctional silicon hydrides for such
purposes is growing.
Unsymmetrically substituted siloxanes, i.e. those having on the
one side Si-H moiety, and on the opposite side a reactive or
specific functional group, can be prepared by two routes, namely,
(
modifiers) of a wide range of vinyl containing molecular or
macromolecular organosilicon materials as well as polyene
by
hydrolysis
and
co-condensation
SiCl and
of
appropriate
[21]
macromolecules.
[
8]
monochlorosilanes
(RMe
2
HSiMe
2
SiCl)
or
Results and Discussion
[a]
[b]
[c]
Department of Organometallic Chemistry, Faculty of Chemistry,
Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614
Poznan, Poland,
Therefore, considering the above, our work presented in
this paper was focused on the development of an efficient
catalytic method of 1,1,3,3-tetramethyldisiloxane mono-
functionalization via hydrosilylation process leading to the
corresponding bifunctional organosilicon modifiers having in its
structure simultaneously HSi≡ bond and other reactive groups.
E-mail: Bogdan.marciniec@amu.edu.pl
The Laboratory of the Chemistry and Technologies of Inorganic
Polymers, Adam Mickiewicz University in Poznań, Umultowska 89b,
61-614 Poznan, Poland,
E-mail: Ireneusz.Kownacki@amu.edu.pl
Center for Advanced Technologies, Adam Mickiewicz University in
Poznań, St. Umultowska 89c, 61-614 Poznań
Accepted Article
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
Therefore, in order to find the best conditions for efficient
synthesis of mono-functionalized 1,1,3,3-tetramethyldisiloxane,
the initial work was focused on optimization of hydrosilylation
process. At the beginning, catalytic examinations were carried
out in the model reaction of 1,1,3,3-tetramethyldisiloxane and
vinyltrimetoxysilane at the equimolar ratio (Scheme 1) with
employment of three homogeneous catalysts, namely Pt-
Karstedt’s complex (C1), the most active and commonly used in
dehydrocoupling
products
such
as
1,1,3,3,5,5,7,7-
octamethyltetrasiloxane.
Furthermore, catalytic tests carried out with the use of
most promising rhodium complex (C2) in the model reagents
system (Scheme 1), in hexane as reaction environment,
revealed only a moderate influence of reduced concentration of
reagents on the increase in the reaction selectivity towards
product A (see Table 1). Moreover, dilution of the reagents
resulted in a significant decrease in the selectivity towards β-
regioisomer, in comparison with the results obtained for the
reaction in the solvent-free systems (see Table 1).
[
1]
industrial processes based on hydrosilylation and rhodium
[
1]
[1]
complexes [{Rh(μ-Cl)(COD)}
2
]
(C2) and [RhCl(PPh
3
)
3
]
(C3)
also known as efficient hydrosilylation catalysts as well as two
heterogeneous metallic catalysts such as Pt/SDB (styrene-
divinylbenzene co-polymer) (C4) and Rh/SDB (C5) for the sake
of comparison.
Table
1.
Hydrosilylation
of
vinyltrimethoxysilane
by
1,1,3,3-
tetramethyldisiloxane in stoichiometric ratio.
Conversion
Yield of products
(%)
Product A
regioselectivity
(%)
Vinylsilane
Catalyst
of ViSiR
3
[g]
Me
H
O
Me
Si
Si
(
%)
Si(OMe)
3
Me
Me
Me
H
O
Me
H
Cat.
A
B
α
β
Si
Si
+
Si(OMe)3
β-isomer
+
[a]
Me
Me
C1
100
100
99
73.0
83.8
81.7
82.8
4.7
27.0
16.2
18.3
17.8
0
30.7
21.5
29.2
37.5
29.4
26.7
30.3
32.3
69.3
78.5
70.8
62.5
70.6
73.3
69.7
67.7
Me
H
O
Me
[b]
C2
C3
Si
Si
Si(OMe)3
[b]
Me
Me
[
c]
Me
1
C4
C5
93
19
α-isomer
[c]
[
d]
e]
A
C2
C2
100
100
100
90.6
90.7
91.8
9.4
9.3
[
Me
O
Me
Si
[
f]
+
Si
C2
8.2
(
MeO)
3
Si
Si(OMe)
3
Me
Me
mixture of α/β-isomers
C1 = Pt-Karstedt; C2 = [{Rh(μ-Cl)(COD)}
2 3 3
]; C3 = [RhCl(PPh ) ]; C4 = Pt/SDB
o
B
(1% Pt); C5 = Rh/SDB (1% Rh). Reaction conditions: T=50 C, t= 24 h,
[
a]
-5
[b]
[
]
H C=CH-] : [HSi≡] = 1 : 2, - [Pt] : [H C=CH-] = 2x10 : 1, - [Rh] : [H C=CH-
2
2
2
-4 [c] -3 [d] -4
= 2x10 : 1, - [M] : [H
2
C=CH-] = 10 : 1, - [Rh] : [H
2
2
2
C=CH-] = 2x10 : 1,
Scheme 1. Products distribution on the model reaction.
[
e]
-4
concentration of reagents in hexane – 50%,
concentration of reagents in hexane – 25%,
concentration of reagents in hexane
- [Rh] : [H
- [Rh] : [H
C=CH-] = 2x10 : 1,
[
f]
-4
C=CH-] = 2x10 : 1,
[
g]
– 10%, Conversion yield were
The results summarized in Table 1, demonstrate that the
homogeneous promoters C1-C3 and exemplary platinum
heterogeneous catalyst C4 proved to be active in the studied
model reaction and catalyzed efficiently the conversion of initial
substrates to hydrosilylation products. However, irrespectively of
the catalyst used, always monohydrosilylation derivative A was
accompanied by bishydrosilylation product B, even at the mild
determined by GC analysis and calculated on the basis of ViSiR , using the
solvent peak as a standard.
3
Therefore, it seemed obvious to us that the increase in the molar
ratio of TMDSO to vinyl compound from 1 : 1 to 2 : 1, should
have a significant impact on the products distribution in the
reaction systems in which the molar ratio of HSi≡ bond to vinyl
reagent formally is 4 : 1. Moreover, it is also expected that in
some cases, particularly for more sterically hindered vinyl
reagents, better distribution of β/α-regioisomers should be
observed especially with predominance of mono-substituted β-
isomeric products.
o
reaction conditions (50 C). Furthermore, in both types of
1
hydrosilylation products the GCMS and H NMR analyzes
revealed the presence of α and β regioisomers. Nevertheless,
comparing the results of hydrosilylation tests, conducted for all
catalysts (see Table 1), the most advantageous ratio between
products A (monohydrosilylation) and B (bishydrosilylation) was
found in the post-reaction mixture obtained with the use of pre-
catalyst C2. Additionally, in the presence of this complex the
contribution of α-isomer in product A was also significantly
smaller than for the other catalysts. Surprisingly, in view of our
Therefore, at the subsequent step, the efficiency of C1 -
C5 was examined in the model reaction, using this time 2
2 3
equivalents of TMDSO with respect to H C=CHSi(OMe) . The
data obtained with the use of in situ IR technique, showed (see
Table 2), that unlike the heterogeneous catalysts, the molecular
ones operate quite rapidly under given conditions and they
catalyzed the conversion of initial reagents to hydrosilylation
products in a relatively short time. However, only with complex
C2, the reaction proceeded towards the selective formation of
[
22]
earlier experience,
C4 proved to be less effective than the
homogeneous TM-pre-catalysts and much less selective, as one
would expect of this heterogeneous catalyst. (see Table 1). The
analogous rhodium catalyst (C5) proved to be poorly effective in
the studied model reaction giving both, low conversion of the
initial silicon reagent and less than 5% yield of derivative A,
the monohydrosilylation product A. The use of lower
-7
concentrations of catalyst C1 ([Pt] : [H
2
C=CH-] = 2x10 : 1) also
gave good result in terms of selectivity towards partial
hydrosilylation product (A), but unfortunately, it resulted in a
deterioration of the ratio of regioisomers formed, i.e. in the
which
was
additionally
accompanied
with
TMDSO
Accepted Article
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European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
increased content of the α-addition product. Unfortunately, in
the presence of the other homogeneous TM-complexes, i.e. C1
and C3 as well as the heterogeneous catalyst C4, the product A
was always accompanied by the second derivative B. Similarly,
as in the model reaction with the reagents at equimolar ratio
was observed. However, unlike with the platinum promoter C1,
the employment of the rhodium catalyst C2 resulted in the
selective formation of monohydrosilylation product A. As
expected, employment of C2 in the reactions of TMDSO with the
vinylsilanes 6 and 7 bearing at silicon atom one or two phenyl
rings, respectively, besides ethoxy substituents, resulted in
selective formation of β-isomeric products. We did not expect
that in the same reaction conditions that were applied for
transformation of vinyl derivatives 2–5 to the corresponding
products (see Table 2), the complete conversion of silanes 6
and 7 will require much more time, in comparison to that needed
for vinyl derivatives 2-5, moreover it surprising that for
compound 7 unexpected product B will be also observed.
Moreover, when the higher molar ratio of TMDSO with respect to
7 was applied, e.g. 2.5 : 1, the formation of product B was not
prevented, but instead, the undesired product of the siloxane
dehydrocoupling process was detected. Therefore, it seems that
in the studied reagent systems, the steric effects play a crucial
role in the selective formation of β-regioisomeric products.
(
see Table 1), heterogeneous catalyst C5 proved to be selective
towards the formation of product A, but poorly active in this
process giving this product with merely 7.8 % yield.
Therefore, taking into account the values of the selectivity and
yield of product A formed in the presence of the studied
catalysts (C1-C5), the most promising for further studies seemed
to be catalysts C1 and C2, because their use lead to the
formation of the monohydrosilylation product A with high yield,
and with predominance of β-isomer.
Thus, at subsequent steps the selected catalysts (C1, C2) were
examined in the reactions of TMDSO with exemplary vinyl-
functionalized silicon derivatives functionalized with silyl groups
of different sizes, as shown in Scheme 2.
Generally, in the reaction systems containing an organosilicon
reagent bearing in its structure two chemically equivalent Si-H
bonds, as in TMDSO, formation of either partially functionalized
or bisubstituted TMDSO derivatives takes place.
Me
H
O
Me
Si
Si
SiR3
Me
Me
Me
H
O
Me
H
Cat.
2
Si
Si
+
β-isomer
SiR3
+
Me
Me
Me
H
O
Me
SiR3
Si
Si
Table 2. Results of the reaction between TMDSO and vinyl-silicon derivatives
in the molar ratio 2 : 1.
Me
Me
Me
α-isomer
Conver
sion of
Yield of
Product A
A
SiR
3
Cat.
Time
products (%)
regioselectivity (%)
ViSiR
3
d]
[h:min]
Me
O
Me
[
+
Si
Si
Me
(%)
R Si
SiR3
3
Me
A/B
α
β
mixture of α/β-isomers
[a]
C1
C1
C2
C3
100.0
94.6
100.0
98.8
00:02
18:00
00:42
02:21
24:00
24:00
00:02
00:04
00:02
00:04
00:02
00:04
00:04
00:04
02:08
07:53
92.4/7.6 (93)
94.6/0
100/0 (92)
96.2/3.8
27.0
30.8
18.8
23.3
26.6
26.5
15.1
19.0
20.3
10.9
0
73.0
69.2
81.2
76.7
73.4
73.5
84.9
81.0
79.7
89.1
100
B
[b]
[c]
t
R3 = (OMe)3 (1); (OEt)3 (2); Me(OMe)2 (3); (O Bu) (4);
3
1
[
c]
d]
d]
SiMe N(SiMe ) (5); (OEt) Ph (6); (OEt)Ph (7)
2
3 2
2
2
[
[
C4
C5
C1
C2
C1
C2
92.7
96.0/4.0
22.0
7.8/0
Scheme 2. Products distribution in the reaction of TMDSO with selected
[a]
[c]
2
3
4
5
100.0
100.0
100.0
100.0
99.0
89.6/10.4
100/0 (98)
91.8/8.2
vinylsilanes in the molar ratio 2 : 1.
[
a]
[
c]
100/0 (96)
79.3/20.7
99/0 (98)
56.8/43.2
100/0 (96)
100/0 (99)
93.2/6.8
[
a]
C1
C2
C1
C2
C2
C2
The results summarized in Table
2
show that both
[
c]
99.0
0
0
100
100
homogeneous TM-precursors efficiently catalyze the addition of
HSi≡ to the C-C double bond in the selected vinyl-substituted
silicon reagents. , Nonetheless, in contrast to the Pt-Karstedt’s
catalyst (C1), the rhodium binuclear precursor C2 proved to be
significantly more selective towards the monohydrosilylation
process, leading exclusively to the formation of product A for
[a]
100.0
100.0
100.0
100.0
[
[
[
c]
c]
c]
0
0
100
100
6
7
0
100
C1 = Pt-Karstedt; C2 = [{Rh(μ-Cl)(COD)}
1% Pt); C5
C=CH-] : [HSi≡] = 1 : 4, - [Pt] : [H
2
3 3
]; C3 = [RhCl(PPh ) ]; C4 = Pt/SDB
o
(
[
=
Rh/SDB (1% Rh). Reaction conditions: T=50 C,
vinyl-silicon derivatives
2
–
5, under the same reaction
a
-
5
b
H
2
2
-4
C=CH-] = 2x10 : 1, - [Pt] : [H
2
C=CH-] =
-
7
c
d
-3
conditions. None of the complexes applied in hydrosilylation
tested exhibited any differences in the formation of α and β
regioisomers in the catalytic systems obtained on the basis of
vinyl-functionalized silicon derivatives 2 and 3, giving a mixture
of isomers, of course, with predominance of β-product.
Surprisingly, for the remaining vinyl-silicon compounds with
2x10 : 1, - [Rh] : [H C=CH-] = 2x10 : 1, - [M] : [H C=CH-] = 10 : 1. Time of
reactions was determined by in situ IR technique and calculated using the
2
2
[
d]
intensity of Si-H bond. Conversion yield were determined by GC analysis and
calculated on the basis of ViSiR , using the solvent as a standard. Yield of the
3
isolated product is given in parentheses.
In view of the data reported in publications and patents, in most
reactions conducted with unsaturated reagents (organic or
organosilicon) at the equimolar ratio with TMDSO or close to this
significantly more sterically crowded structure, i.e. bearing in
t
their structure bulky substituents at silicon (-O Bu or
–
SiMe
2
N(SiMe
3
)
2
(compounds 4 and 5), in the presence of both
ratio (e.g.
1 : 1.33 or 1.5), selective formation of the
catalysts (C1 and C2), the exclusive formation of β regioisomers
monofunctionalized derivatives was problematic, irrespectively
Accepted Article
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
of the catalyst used. The employment of rhodium- (RhCl
3
,
purchased from Gelest Inc. All chemicals were used without any further
1
13
purification. The H NMR and C NMR spectra were recorded on a
Bruker Ultrashield 300 MHz spectrometer using CDCl as solvent. The
Si NMR spectra were recorded using Bruker Ascend 400 spectrometer.
[
RhCl(PPh
platinum-based catalysts (H
etc.) always led to the formation both, mono- and
3
)
3
], [{Rh(μ-Cl)(COD)}
2
], [RhCl
3
(t-Bu
2
S)
3
], etc.), or
3
2
PtCl
6
, Pt-Karstedt, PtCl
2
(PPh
3 2
) ,
2
9
The mass spectra were obtained by GCMS analysis (Bruker MS320
Triple quad, equipped with a VF-5 Factor four capillary column (30 m)
and a quadrupole detector). In-situ FT-IR measurements were performed
on a Mettler Toledo ReactIR 15 equipped with a DS 6.3mm AgX DiComp
Fiber Probe with a diamond sensor, and a Hg-Cd telluride detector. For
[
7a,17b,17d,17e,18,23]
bishydrosilylation products.
Thus, in order to
quench the reaction at the stage of monofunctionalized product
formation, the use of at least twofold, and in some cases, even a
tenfold molar excess of TMDSO with respect to the unsaturated
[
6,11b,12b,17a,17c]
-1
reagents was required.
However, regardless of the
all the spectra 125 scans were recorded with the resolution of 1 cm in
[
25]
3
0 s intervals. The [{Rh(μ-Cl)(COD)}
2
], [RhCl(PPh
3
)
3
] complexes
as
were
type of catalyst employed, as well as the ratio of the reagents,
the reaction of mono hydrosilylation with use of TMDSO, in
[
22]
well as was Pt/SDB (1 w% Pt); C5 = Rh/SDB (1 w% Rh)
[
17c,17e,19,23]
prepared according to the published methods.
particular with vinylsilanes or vinylsiloxanes,
led to the formation of two isomeric products, which are a result
always
[
24]
Synthesis of tris(tert-butoxy)vinylsilane (3): To a suspension of 10 g
of α- or β-addition process
.
(
(
89.1 mmol) of potassium tert-butoxide in 150 mL of hexane 4.79 g
Selected derivatives of TMDSO presented in Table 2 were
isolated and characterized by spectroscopic methods (see
Experimental section and Supporting information), to show the
scope of this new versatile and efficient synthetic method
enabling the synthesis of coupling agents on the basis of
TMDSO – a commercially available and commonly used silicone
reagent.
29.66 mmol) of trichlorovinylsilane was added dropwise at room
temperature. After addition of the silicon derivative the resulted mixture
was stirred for 24h at room temperature and then refluxed for 2h. After
t
filtration and evaporation of the solvent desired H
2
C=CHSi(O Bu)
3
was
, δ,
], C NMR
), 72.77 [OC(CH ],
, δ, ppm): -74.25. MS (EI, m/z): 259.3
1
obtained with a yield 95% (7.73 g, 28.17 mmol). H NMR (CDCl
3
1
3
ppm): 6.02-5.85 (m, 3H, CH=CH
CDCl , δ, ppm): 137.19 (CH=CH
1.85 [OC(CH
2
), 1.32 [s, 27H, OC(CH
), 133.06 (CH=CH
]. Si NMR (CDCl
3 3
)
(
3
2
2
3 3
)
2
9
3
3
)
3
3
+
(
(
35) [M -15], 203.1 (15.9), 147.0 (52.9), 145.0 (29.4), 89.0 (100), 79.0
20.2), 63.0 (30), 57.1 (64.7).
Conclusions
Synthesis of dimethylvinylsilylbis(trimethylsilyl)amine (5):
To a suspension of 1.636 g (68.2 mmol) NaH in 100 mL of anhydrous
toluene 10.2 g (61.9 mmol) of hexamethyldisilazane was added, then the
mixture was refluxed for 24h and cooled to room temperature. Next,
In this report we have presented results of the studies aimed at
establishment
of
the
conditions
enabling
selective
8
.216 g (68.1 mmol) of chlorodimethylvinylsilane was added dropwise
monofunctionalization of TMDSO via hydrosilylation reaction.
Catalytic trials conducted in the reaction systems made of
TMDSO and selected vinylsilanes, as well as with use of various
homogeneous or heterogeneous platinum and rhodium
hydrosilylation promoters (C1 - C5), and additionally monitored
by in situ IR technique, have allowed the selection of the most
promising catalysts, which showed good selectivity toward the
desired products, namely Pt-Karstedt (C1) and [{Rh(μ-
and reaction was continued under reflux for 4 and 6 hours at room
temperature. After filtration volatile ingredients including solvent were
removed under reduced pressure. Product was purified by the trap-to-
trap distillation. Desired product was obtained with yield 78.6 % (12.23 g,
1
49.8 mmol). H NMR (CDCl
3
, δ, ppm): 6.30-6.23 (m, 1H CH=CH
2
), 5.91-
Si). C NMR (CDCl , δ,
), 5.68 [(CH Si], 4.06
, δ, ppm): 3.07 [(CH Si], -6.63 [(CH Si].
MS (EI, m/z): 231.3 (19.2) [M -15], 230.2 (100), 203.2 (15.3), 202.1
67.1), 188.1 (16.0), 142.0 (21.5), 130.0 (35.0), 100.0 (26.6), 73.1(48),
1
3
5
.64 (dd, 2H, CH=CH
2
), 0.32-0.06 (m, 24H, CH
), 130.34 (CH=CH
Si]. Si NMR (CDCl
3
3
ppm): 143.69 (CH=CH
2
2
3 3
)
2
9
[
(CH
3
)
2
3
3
)
3
3 2
)
+
Cl)(COD)}
RhCl(PPh
is much less active than the binuclear rhodium precursor C1
[{Rh(μ-Cl)(COD)} ]). Furthermore, the latter proved to be
2
] (C2). Additionally, we found that the complex
(
[
3
)
3
] (C3), a commonly applied hydrosilylation catalyst,
59.0 (32.0).
(
2
Synthesis of (Ethoxy)diphenylvinylsilane (7): To a mixture containing
regioselective towards the formation of β-addition products,
0.564 g (12.24 mmol) of ethanol, 1.65 g (16.30 mmol) of trimethylamine
and 10 mL of anhydrous tetrahydrofuran,
2 g (8.17 mmol) of
when used in the reactions of vinyl-silicon compounds with
chlorodiphenylvinylsilane was added dropwise at room temperature.
Then mixture was stirred at ambient conditions and controlled by GCMS
technique. Next, trimethylamine hydrochloride was separated by filtration
and washed with cooled THF. Filtrate was placed in the flask and
significantly more sterically crowded structure, i.e. bearing in
t
their structure bulky substituents at silicon (-O Bu or
–
2 3 2
SiMe N(SiMe ) . Selected compounds were also isolated and
characterized by spectroscopic methods.
evaporation of solvent and excess of ethanol and trimethylamine gave
1
pure product with yield a 92 % (1.912 g, 7.52 mmol). H NMR (CDCl
3
, δ,
ppm): 7.68-7-66 (d, 4H), 7.47-7.40 (m, 6H), 6.60-6.48 (m, 1H), 6.35-6.28,
1
3
5
1
5
.99-5.91 (dd, 2H), 3.88 (q, 2H), 1.29 (t, 3H), ( C NMR (CDCl
37.00 (CH=CH ), 135.11, 134.52, 133.78 (CH=CH ), 130.07, 127.97,
9.70 (OCH ), 18.55 (CH , δ, ppm): -14.89; MS (EI,
3
, δ, ppm):
Experimental Section
2
2
2
9
2
3 3
), Si NMR (CDCl
Methods and Materials: Vinyltrimethoxysilane, sodium hydride, Pt-
Karstedt catalyst, 1,1,3,3-tetramethyldisiloxane, 1,1,1,3,3,3-
+
m/z): 254.3 (30.5) [M ], 227.3 (14.7), 225.3 (22.3), 209.3 (17.8), 208.2
56.5), 199.2 (17.6), 184.2 (18.8), 183.2 (100), 182.4 (21.9), 181.2 (38.3),
77.2 (21.3), 176.2 (74.8), 150.1 (57.5), 149.1 (28.8), 133.1 (31.6), 132
16.0), 123.1 (55.1), 105.1 (51.6), 104.0 (53.0), 78.0 (16.8), 77.0 (35.5),
3.1 (21.0).
(
hexamethyldisilazane, chlorodimethylvinylsilane, potassium tert-butoxide,
1
rhodium(III) chloride hydrate, COD, anhydrous toluene, pentane, ethanol
(
were
purchased
from
Sigma
Aldrich.
Vinyltriethoxysilane,
7
chlorodiphenylvinylsilane and vinyltrichlorosilane were obtained from
ABCR. Vinylmethyldimethoxysilane and diethoxyphenylvinylsilane were
Accepted Article
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
1
3
General procedure for hydrosilylation of vinyl-substituted silicon
6H, (CH
[(CH Si], 3.19, 1.09, 0.45 (CH
[HSi(CH ], 5.07 [OSi(CH CH ], 2.27 [(CH
3
)
2
SiN]. C NMR (CDCl
3
, δ, ppm): 12.03, 10.53 (SiCH
2
), 5.74
, δ, ppm): 10.63
Si], -6.83 [(CH SiN]. MS
2
9
compounds by 1,1,3,3-tetramethyldisiloxane: A mixture containing 2 g
3
)
3
3 3
Si). Si NMR (CDCl
(
14.88 mmol) of 1,1,3,3-tetramethyldisiloxane and (7.44 mmol) of
3
)
2
3
)
2
2
3
)
3
3 2
)
o
vinylsilane was placed in a glass tube (25 mL) and heated at 50 C, then
(EI, m/z): βisomer: 220.3 (11.5), 219.3 (21.7), 218.2 (100), 216.2 (22.3),
202.3 (11.6), 134.2 (7.5), 133.1 (48.2), 132.2 (8.2), 131.1 (7.0), 130.0
(31.0), 100.0 (7.6), 73.1 (28.6), 59.0 (8.4).
-
4
-5
the catalyst [Rh] : [C=C] = 2 x 10 : 1, [Pt] : [C=C] = 10 : 1 was added.
o
Reaction mixture was stirred at 50 C and monitored by in situ FT-IR
spectroscopy to designate the endpoint of process. Then GCMS analysis
was performed to calculate conversion of vinylsilane. After cooling to
room temperature excess of disiloxane and unreacted vinylsilane were
evaporated under vacuum to obtain products. Ratio between mono- and
bishydrosilylation products as well as regioisomers were calculated on
the basis of GCMS analysis. Signals from α isomers are highlighted in
italics.
Spectroscopic data for HSiMe
2
OSiMe
, δ, ppm): 7.64-7.61 (d, 4H), 7.43-7.40 (m,
H), 4.72 (m, JH-Si = 201 Hz, 1H, SiH), 3.80 (q, 2H, OCH ), 1.24 (t, 3H,
CH ), 1.11, 0.57 (m, 4H, SiCH CH ), 0.18-0.09 (m, 12H, Si(CH
3C NMR (CDCl , δ, ppm): 135.26, 134.91, 129.86, 127.94 (Cphenyl),
9.41 (OCH ), 19.06 (OCH CH ), 9.34, 5.21 (SiCH CH ), 1.05, 0.49
Si NMR (CDCl δ, ppm): 10.51 [HSi(CH ], -3.57
CH ], -6.56 [(Ph) Si], MS (EI, m/z): βisomer: 359.2 [M-Et] (5.2),
2 2 2 2
CH CH SiPh OEt: (Yield 99%,
1
7
6
.36mmol). H NMR (CDCl
3
2
OCH
2
3
2
2
3 2
) .
1
5
3
2
2
3
2
2
2
9
(
CH
3
Si).
3
,
3 2
)
Spectroscopic data for HSiMe
2
OSiMe
, δ, ppm): 4.66 (m, JH-Si = 198 Hz, 1H, SiH),
), 1.07, 0.54 (4H, SiCH , SiCHCH ) 0.17-0.03 (m, 12H,
Si). C NMR (CDCl , δ, ppm): 50.67(OCH ), 8,99, 0.96, (SiCH ),
),0.66, 0.37, 0.15, -0.64 (CH , δ,
ppm): 10.21, 9.58 [HSi(CH ], -6.65, -7.16 [OSi(CH ], -41.55, -
]. MS (EI, m/z): βisomer: 267.2 (27.3) [M -15], 193.0 (25.5),
63.2 (24.3), 133.0 (100), 121.1 (16.8), 91.0 (20.7), 89.1 (24.1), 73.1
2
CH
2
CH
2
Si(OMe)
3
: (Yield 93%,
[OSi(CH
3
)
2
2
2
1
6
.91 mmol). H NMR (CDCl
.56 (s, 9H, OCH
3
311.2 (5.2), 281.2 (13.1), 229.3 (5.3), 228.3 (19.7), 227.2 (100), 199.2
(9.8), 197.2 (5.4), 184.2 (11.2), 183.1 (65.5), 160.1 (6.0), 145.1 (8.9),
135.1 (13.1), 133.1 (31.5), 132.4 (7.5), 123.0 (40.2), 121.0 (9.5), 105.0
(12.8), 103.0 (6.8), 77.1 (15.8), 73.1 (20.5), 59.0 (8.5).
3
3
2
3
1
3
CH
3
3
3
2
2
9
7
.60, 5.35 (SiCHCH
3
3
Si). Si NMR (CDCl
CH
3
3
)
2
3
+
)
2
2
4
2.37 [Si(OMe)
3
1
+
Acknowledgements
(
22.0), 59.0 (35,4). MS (EI, m/z): αisomer: 268.2 (21.9), 267.2 (100) [M -15],
93.0 (27.8), 164.1 (16.3), 163.0 (25.2), 133.0 (60.1), 117.0 (17), 91.1
22.9), 90.1 (22.0), 89.1 (23.0), 73.1 (22.5), 59.0 (45.6).
Spectroscopic data for HSiMe OSiMe CH CH Si(OEt)
, δ, ppm): 4.66 (m, JH-Si = 201 Hz, 1H, SiH),
), 1.21 (t, 9H, OCH CH ), 1.05, 0.54 (4H, SiCH2,
Si). C NMR (CDCl , δ, ppm): 58.50
), 9.14, 1.88, (SiCH ), 7.75, 6.06
). Si NMR (CDCl , δ, ppm):
), -6.73, -7.45 (OSi(CH CH ], -44.66, -45.89
]. MS (EI, m/z): βisomer: 221.2 (22.3), 207.1 (18.7), 205.1 (33.3),
93 (50.5), 163.1 (22.9), 133.0 (100) 119.0 (21.9), 79.0 (15.4), 73.1
1
(
The authors gratefully acknowledge financial support from the
National Center of Research and Development (Poland) Project
No. INNOTECH-K3/IN3/39/22131/NCBR/14. This research was
supported by Synthos S.A.
2
2
2
2
3
: (Yield 98%,
1
7
.29 mmol). H NMR (CDCl
.80 (q, 6H, OCH CH
), 0.02-0.17 (m, 12H, CH
CH ), 18.42 (OCH CH
SiCHCH3), 0.98, 0.74, 0.08, -0.61 (SiCH
0.40, 9.90 (HSi(CH
Si(OEt)
3
3
2
3
2
3
1
3
SiCHCH
3
3
3
(
(
OCH
2
3
2
3
2
2
9
Keywords: TM-catalyzed hydrosilylation • rhodium complexes •
3
3
1
3
)
2
3
)
2
2
siloxanes • coupling agents • catalysis
[
3
1
[
1]
a) B. Marciniec, J. Guliński, W. Urbaniak, Z.W. Kornetka,
Comprehensive Handbook on Hydrosilylation, (Ed.: B. Marciniec),
Pergamon Press, Oxford, 1992, pp. 754; b) B. Marciniec,
H. Maciejewski, C. Pietraszuk, P. Pawluć, Hydrosilylation.
A Comprehensive Review on Recent Advances, (Ed.: B. Marciniec),
Springer, 2009, pp. 410.
+
(
(
25.2). MS (EI, m/z): αisomer: 310.3 (18.5), 309.2 (72.8) [M -15], 251.2
21.9), 237.2 (17.6), 236.2 (18.3), 235.2 (87.2), 223.2 (20.4), 221.2 (41.2),
2
07.1 (30.0), 206.2 (21.6), 205.1 (100), 195.1 (18.1), 194.2 (20.9), 193.1
98.8), 192.3 (19.9), 179.0 (61.1), 177.0 (32.1), 163.0 (37.4), 147.1 (16.0),
35.0 (20.9), 133.0 (93.5), 119.1 (36.1), 117.0 (23.5), 103.0 (21.0), 91.1
20.3), 79.1 (23.6), 73.1 (51.2), 63.0 (15.9), 59.0 (26.5).
Spectroscopic data for HSiMe OSiMe CH CH SiMe(OMe)
, δ, ppm): 4.66 (m, JH-Si = 204 Hz, 1H,
), 1.03, 0.5 (4H, SiCH , SiCHCH ), 0.02-0.16 (m,
Si), C NMR (CDCl , δ, ppm): 50.31 (OCH ), 8.99, 4.34
), 0.99, 0.63, -6.51 (CH , δ, ppm): 10.35
HSi(CH ], 0.70 [OSi(CH CH ]. MS (EI, m/z):
(
1
(
[
[
[
2]
3]
4]
J. Hazziza-Laskar, G. Helay and G. Sauvet, Makromol. Chem.,
Macromol. Symp. 1991, 47, 383-391.
2
2
2
2
2
: (Yield
1
9
6%, 7.14 mmol). H NMR (CDCl
3
a) M.E. Cifuentes, M.R. Strong, B. Vanwert, EP0686435B1 1999;
b) R.K. King, C. Lee, US 5,276,123 1994.
SiH), 3.49 (s, 6H, OCH
3
2
3
1
3
1
5H, CH
3
3
3
a) Y. Yamane, N. Koike, K. Yamaguchi, H. Kishita, EP 1,813,640 B1
2
9
(
SiCH
2
3
Si). Si NMR (CDCl
3
2
010; b) Y. Yamane, N. Koike, H. Kishita, K. Yamaguchi, US 8,420,763
B2 2013; (c) Y. Yamane, N. Koike, K. Yamaguchi, US 7,829,649 B2
010.
T. Sakamoto, A. Fujiwara, N. Kameda, T. Kimura, US 7,405,316 B2
008.
[
3
)
2
3
)
2
2
], -6.71 [CH Si(OCH )
3
3 2
+
β
1
isomer: 251.2 (23.0) [M -15], 177.1 (23.1), 176.1 (16.9), 163.1(26.6),
2
61.1 (15.4), 133.0 (100), 105.0 (46.1), 89.0 (25.1), 75.1 (29.7), 73.2
[
[
5]
6]
+
(
28.6), 59.0 (29.9). MS (EI, m/z): αisomer: 252.2 (23.9), 251.2 (100) [M -15],
2
1
77.1 (30.9), 176.0 (18.6), 163.1 (26.1), 133.1(53.7) 119.1 (16.1), 117.0
16.3), 105.1 (26.8), 103.0 (19.7), 102.0 (22.7), 89.0 (33.4), 75.1 (30.7),
4.1 (28.6), 73.1 (34.6), 59.0 (42.3),
Spectroscopic data for HSiMe OSiMe
, δ, ppm): 4.71 (m, JH-Si = 201 Hz, 1H, SiH),
], 0.60-0.36 (m, 4H, SiCH ), 0.19-0.07 (m, 12H,
], 31.84 [OC(CH ],
Si). Si NMR (CDCl , δ, ppm): 10.94
]. MS (EI, m/z):
a) M. Nobuaki, M. Kei, Y. Kunihiro, US 2007/0293624 A1 2007;
(
b) I. Sakurai, N. Matsumoto, K. Miyoshi, K. Yamada, US 8,119,758 B2
7
2
012.
t
2
2 2 2
CH CH Si(O But): (Yield 98%,
[
7]
a) D. I. Farris, C. J. Rinard.; M. I. Leatherman, US 7,259,220 B1 2007;
1
7
.29 mmol). H NMR (CDCl
.30 [s, 27H, OC(CH
3
b) M. D. Leatherman, G. A. Policello, K. Rajaraman, US 7,645,720 B2
1
3
)
3
2
2
010; c) S.K. Rajaraman, A. Lejeune, A. Borovik, G.A. Policello, M.D.
1
3
CH
3
Si). C NMR (CDCl
3
, δ, ppm): 72,13 [OC(CH
3
)
3
3 3
)
Leatherman US 7,399,350 B2 2008.
2
9
1
0.41, 8.84 (SiCH
2
), 1.01, 0.42 (CH
3
3
[
[
[
[
8]
9]
a) L. A. Haluska, US 3,576,029 1971; b) Y. Isoda; K. Ayama, US
t
[
HSi(CH ) ], -7.06 [OSi(CH ) CH ], -59.86 [Si(O But)
3 2 3 2 2 3
5
,831,110 1998.
H. Friedrich, I. Jansen, K. Ruhlmann, Polym. Degrad. Stab. 1994, 46,
-18.
10] K. J. Shepperson , T. Meyer, G. H. Mehl, Mol. Cryst. Liq. Cryst. 2004,
11, 185-191.
β
isomer: 247.3 (9.4), 239.2 (5.1), 221.1 (9.4), 205.1 (12.2), 191.1 (9.5),
36.2 (7.7), 135.0 (84.7), 133.0 (16.3) 121.0 (6.2), 119.1 (5.1), 79.0
1
9
(
31.5), 73.1 (5.8), 57.1 (100).
Spectroscopic data for HSiMe
2
OSiMe
Yield 96%, 7.14 mmol). H NMR (CDCl , δ, ppm): 4.7 (m, JH-Si = 201 Hz,
H, SiH), 0.56-0.38 (m, 4H, SiCH ), 0.194-0.165 (m, 30H, CH Si), 0.07 [s,
2 2 2 2 3 2
CH CH Si(Me) N(SiMe ) :
4
1
(
3
11] a) N. A. Novozhilova, Yu. N. Malakhova, M. I. Buzin, A. I. Buzin, E. A.
1
2
3
Tatarinova, N. G. Vasilenko, A. M. Muzafarov, Rus. Chem. Bull., Intern.
Accepted Article
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201601341
FULL PAPER
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Macromolecules 2015, 48, 6251−6262; b) P. Ortega, B. M. Cobaleda,
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Accepted Article
This article is protected by copyright. All rights reserved.