New catalytic route to silylene-vinylene-boronate systems

Article abstract of DOI:10.1016/j.jorganchem.2010.02.019

Cross-coupling of divinylorganosilicon compounds with vinylboranes in the presence of complexes containing Ru-H bonds (preferably [Ru(CO)ClH(PCy₃)₂]) leads to formation of borylfunctionalized dienes, which can be potentially used as

Full text of DOI:10.1016/j.jorganchem.2010.02.019

Journal of Organometallic Chemistry 695 (2010) 1287–1292
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
New catalytic route to silylene–vinylene–boronate systems
*
Je˛drzej Walkowiak, Bogdan Marciniec , Magdalena Jankowska–Wajda
Adam Mickiewicz University, Faculty of Chemistry, Grunwaldzka 6, 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:
Cross-coupling of divinylorganosilicon compounds with vinylboranes in the presence of complexes con-
taining Ru–H bonds (preferably [Ru(CO)ClH(PCy3)2]) leads to formation of borylfunctionalized dienes,
which can be potentially used as monomers for polymerization reactions or reagents in Pd-catalyzed cou-
pling. The influence of the catalyst, temperature, time and molar ratio of substrates and Ru-complex on
the yields and selectivities of the obtained products were tested.
Received 19 January 2010
Accepted 17 February 2010
Available online 21 February 2010
Keywords:
Cross-coupling
Silyldiene
Ó 2010 Elsevier B.V. All rights reserved.
Vinylborane
Ruthenium complex
1. Introduction
(halogen, aryl, alkenyl, hydroxyl) via demetallation processes, with
a special inclusion of palladium catalyzed coupling reactions based
In the last two decades we have developed a new type of
TM-catalyzed reaction of vinyl-substituted organosilicon com-
pounds with a variety of olefins called the silylative coupling (SC)
or trans-silylation, which takes place in the presence of complexes
containing or generating the M–H and M–Si (silicometallics) where
M = Ru, Rh, Ir (for a recent review see [1,2]). This model of vinyl-sil-
icon reactivity has been recently found to be general and also
exhibited by vinyl derivatives of other p-block elements (e.g. vinyl-
boronates [3] and vinylgermanes [4] and perhaps, vinyl derivatives
of other p-block elements). The general scheme of this reaction
occurring in the presence of the Ru–H complex is as follows
[1–4]. (Fig. 1).
While silylative coupling of various olefins catalyzed by Ru–H
complexes leads predominantly to trans-product accompanied by
1,1-geminal derivatives, trans-borylation of olefins gives exclu-
sively a mixture of E + Z products [3,5]. Catalytic and mechanistic
studies on heterocoupling of vinylsilanes with vinylboronates in
the presence of ruthenium hydride catalyst show that the reaction
occurs according to the silylative coupling mode i.e. vinylsilane
was used as a silylative agent [5]. (Fig. 2).
on the formation of the new C–C bonds (Suzuki, Hiyama cou-
plings). This unsymmetrical functionalization opens the possibility
for selective replacement of one of the metalloid groups with
retention of the other and the use of the latter for further function-
alization in a different process. The compounds obtained having
two boryl groups in terminal positions can be used as monomers
in many types of polymerization, for example polycondensation
with polyols or via Suzuki coupling with organodiodides giving
products of different kinds. Organometallic compounds, which
contain silicon and boron atom are used as precursors for special
materials and ceramics, because the presence of these atoms has
a significant influence on mechanical, thermal and chemical resis-
tance of these new materials. Such polymers depending on the
structure have different applications (for example as photosensitis-
ers) [11].
In this paper we report catalytic transformations of vinylbor-
anes (2-vinyl-1,3,2-dioxaborinane and 2-vinyl-1,3,2-dioxaboro-
lane) with divinylsubstituted organosilicon compounds occurring
especially in the presence of ruthenium complex containing the
Ru–H bond [Ru(CO)ClH(PCy3)2].
However, under optimum conditions the reaction offers a selec-
tive route to 1-silyl-1-boryl(ethenes) which can be attractive inter-
mediates in organic synthesis and precursors of advanced
materials [5].
Borylsilyl substituted alkenes, dienes and alkynes play an
important role in organic synthesis [6–10] because silyl and boryl
moieties can be easily converted into other functional groups
2. Results and discussion
The coupling reactions of vinylboranes with divinylsubstituted
silicon compounds were examined particularly in the presence of
[Ru(CO)ClH(PCy3)2] (2 mol%) which is well-known as the most
effective catalyst in the silylative coupling reactions of vinylbor-
anes with vinylsilanes [5] and trans-borylation process [3]. A
range of catalytic tests of the silylative coupling reaction of divi-
nylsilicon compounds with vinylboranes were carried out using
* 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 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.02.019

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J. Walkowiak et al. / Journal of Organometallic Chemistry 695 (2010) 1287–1292
Fig. 4. Homocoupling of divinyl substituted organosilicon compounds – the side
reaction.
Fig. 1. General scheme of trans-metallation reaction of vinylmetatalloids with
olefins.
1,2-isomer). When tetraetoxydivinylsiloxane and tetramethyldivi-
nyldisilazane were used as reagents in the silylative coupling reac-
tion, only isomers with trans configuration of all double bonds
were obtained as products.
The presence of geminal isomers in the reaction mixture proves
that the reaction proceeds via silylative coupling reaction, with
activation of the Si–C bond in vinylsilane and the C–H bond in
vinylborane. We have previously reported that in the borylative
coupling only 1,2-disubstituted ethenes were formed [3].
We also observed that the conversions and selectivities of the
reactions were lower when 2-vinyl-1,3-dioxaborolane was used in-
stead of 2-vinyl-1,3-dioxaborinane, which can be explained by the
fact, that the reactions with five-member ring were conducted in
closed system. Ethylene was not removed from the reaction envi-
ronment and the equilibrium was shifted to the substrates.
Some of the borylsilyl dienes were isolated and characterized
spectroscopically (1H, 13C, NMR and GC–MS). Unisolated com-
pounds were identified by GC–MS spectroscopy.
The cross-coupling of divinylsilicon compound with vinylbora-
ne involves insertion of vinylsilane into the Ru–H bond followed
by b-Si elimination of ethylene and migratory insertion of vinylbo-
rane into the Ru–Si bond. The last step of the mechanism is the b-H
elimination of silylboryldiene and regeneration of the Ru–H bond.
The product obtained, which contains the second unsubstituted vi-
nyl group, undergoes insertion into the regenerated Ru–H bond.
The mechanism was previously proved for Ru–H and Ru–Si cata-
lyzed reaction of vinyltrisubstituted silanes with 2-vinyl-1,3,2-
dioxaborinane [5].
Fig. 2. Silylative coupling of vinylboranes with vinylsilanes.
ruthenium(II) complexes: [Ru(CO)ClH(PCy3)2] and [Ru(CO)ClH
(PPh3)3] as catalysts. The model substrates were methylphenyl-
divinylsilane and tetramethyldivinyldisiloxane for which the opti-
mizations of the process were performed. (Fig. 3).
The side reaction of homocoupling of divinylsilicon compounds
was also detected in some processes (product (d)), but only if high
concentration of Ru catalyst was used (see Fig. 4). However, we did
not observe polymerization of divinylsilicon compounds via silyla-
tive coupling reaction under the conditions studied.
The effects of the kind of catalyst and its amount, temperature,
time and molar ratio of reagents were examined.
The activity of ruthenium complex with tricyclohexylphosphine
was much higher then for the [Ru(CO)ClH(PPh3)3] complex, which
was in agreement with the previously presented results of the sily-
lative coupling of vinylsilanes with vinylboranes [5]. The molar ra-
tios of substrates and catalyst also had great influence on the
conversion of silane and the selectivity of these processes. 2
mol% of the catalyst was found as the optimal amount for effective
trans-silylation. These conditions ensure high conversion of sub-
strates and the lack of side-products of homocoupling of silicon
compounds. Lower concentration of the catalyst did not provide
the high reagents conversion. On the other hand, in the presence
of 5 molar% of ruthenium complex more side-products (d) of the
divinysilicon coupling were obtained, up to 15% of all products.
The regioselectivity of the silylative coupling of vinylboranes
with divinylsilicon compounds depends on temperature. The effect
of high temperature of the process on the formation of 1-boryl-1-
silyl or 1-boryl-2-silylsubstituted ethenes was previously reported
[5]. If the reaction is carried out at room temperature, the forma-
tion of 1,1-isomer increases. At elevated temperatures the yields
are higher, whereas the selectivity is lower (higher amount of
The plane drawn cycle shows two routes of monoborylsubsti-
tuted silyldienes formation, where boryl and silyl atoms are linked
to the same or to different carbon atoms. The formation of geminal
or trans isomer is highly dependent on the temperature of the pro-
cess. Room temperature favors the synthesis of geminal isomer.
Elevated temperatures shifted the selectivity of the process to
compound with trans configuration. High temperatures have also
positive influence for the synthesis of diborylsubstituted silyldi-
enes (the bolded cycle in the mechanism). In this case mono-
borysubsitutedsilyldiene obtained in the first catalytic cycle is
inserted into the Ru–H bond of the regenerated complex and then
subsequent steps of the cycle are repeated giving bisborylsubsti-
tuted silyldiene as the final product (Scheme 1).
In conclusion, in the paper we report the catalytic activity of
vinylboranes in silylative coupling reactions with divinylsilicon
compounds catalyzed by Ru–H complexes. The products obtained
can be potentially used as monomers for polymerization to obtain
organic–inorganic hybrid polymers and precursors of new materi-
als, especially ceramic or reagents in palladium catalyzed cross-
coupling reactions.
Fig. 3. Silylative coupling of vinylboranes with divinyl substituted organosilicon compounds.

J. Walkowiak et al. / Journal of Organometallic Chemistry 695 (2010) 1287–1292
1289
Scheme 1. Mechanism of the catalytic silylation of vinylborane with divinylsilicon compounds.
silica gel column chromatography with hexane ethyl acetate as
eluent.
3. Experimental
3.1. General methods
3.2.1. 1-Methylphenylvinylsilyl-1-(10,30,20-dioxaborinan-20-yl)ethene
(1a)
1H (300 MHz), 13C (75 MHz) spectra were recorded by using a
Varian XL 300 MHz spectrometer with samples in a solution of
CDCl3 or C6D6; chemical shifts are reported in ppm with reference
to the residue portion solvent (CH3Cl) peak for 1H and 13C. Analyt-
ical GC analyses were performed by using a Varian Star 400CX with
a DB-5 fused-silica capillary column (30 ml, 0.15 mm) and ther-
mal-conductivity detector (TCD). Mass spectra of the substrates
and products were obtained by GC–MS analysis (VarianSaturn
2100T, equipped with a BD-5 capillary column (30 m) and an
ion-trap detector). Elemental analyses were carried out by using
a VarioEL III system. Thin-layer chromatography (TLC) was carried
out by using plates coated with 250 mm-thick silica gel (Aldrich
and Merck), and the column chromatography was performed by
using silica gel 60 (70–230 mesh; Fluka). Toluene was dried by dis-
tillation using sodium and hexane from sodium hydride. Liquid
substrates were also dried and degassed by using bulb-to-bulb dis-
tillation. All of the reactions were carried out under a dry argon
atmosphere. The chemicals were obtained from the following
sources: toluene, dodecane and hexane were purchased from Flu-
ka; ethyl acetate from POCH; CDCl3 and C6D6 from Dr. Glaser,
A.G. Basel. The organosilicon compounds were purchased from
ABCR or Aldrich. The ruthenium complexes [Ru(CO)ClH(PCy3)2]
and [Ru(CO)ClH(PPh3)3] were prepared according to literature
[12]. Dichlorovinylborane was synthesized from trichloroborane
and tributylvinyltin. 2-vinyl-1,3,2-dioxaborinane and 2-vinyl-
1,3,2-dioxaborolane were synthesized according to literature pro-
cedures with some modifications [13,14].
Complex Ru(CO)ClH(PCy3)2 (25 mg, 0.034 mmol), toluene
(3.4 mL), 2-vinyl-1,3,2-dioxaborinane (0.76 g, 6.8 mmol) and
methylphenyldivinylsilane (0.29 g, 1.7 mmol) were placed in a
glass ampoule under argon atmosphere at 25 °C for 24 h. The con-
version of silane was 63% (GC). The crude product was isolated
using silica gel column (hexane/ethyl acetate = 4/1 as eluent).
0.160 g (0.620 mmol) of the product (1a) were obtained with 37%
isolated yield.
1H NMR (300 MHz, C6D6, d, ppm): 0.68 (s, 3H, SiCH3), 1.11 (t, 2H,
OCH2CH2), 3.46 (q, 4H, OCH2CH2), 5.9 (dd, 1H, J (H,H) = 3.8, 19.7 Hz,
Ph(Me)SiCH@CHH), 6.15 (dd, 1H, J (H,H) = 3.9, 14.7 Hz, Ph(Me)-
SiCH@CHH), 6.45 (d, 1H, J (H,H) = 5.8 Hz, HHC@CB(Si)), 6.78 (dd,
1H, J (H,H) = 14.5, 20.1 Hz, Ph(Me)SiCH@CH2), 7.07 (d, 1H, J
(H,H) = 5.8 Hz, HHC@CB(Si)), 7.73 (t, 2H, C6H6), 7.27 (m, 3H,
C6H6) ppm; 13C NMR (75 MHz, C6D6 d, ppm): ꢀ3.5 (SiCH3) 27.4
(OCH2CH2), 61.7 (OCH2CH2), 128.4 (C6H5), 128.9 (C6H5), 131.0
(C6H5) 133.4 (C6H5), 135.2 (Ph(Me)SiCH@CH2), 137.9 (Ph(Me)-
SiCH@CH2), 145.8 (CH2@CB(Si)) ppm; MS (EI) [m/z (%)]: 258(M+,
2), 243(100), 215(26). 201(18), 181(21), 163(51), 147(27),
121(70), 105(50), 87(30), 53(45), Elemental Anal. Calc. for
C14H19BO2Si: C, 65.12; H, 7.42. Found: C, 64.88; H 7.63%.
3.2.2. (1E)–1-(methylphenylvinylsilyl)-2-(10,30,20-dioxaborinan-20-yl)
ethene (1b)
Complex Ru(CO)ClH(PCy3)2 (25 mg, 0.034 mmol), toluene
(3.0 mL), 2-vinyl-1,3,2-dioxaborinane(0.19 g, 1.7 mmol) and meth-
ylphenyldivinylsilane (0.29 g, 1.7 mmol) were placed in a glass am-
poule under argon atmosphere at 80 °C for 48 h. The conversion of
silane was 100% (GC).The crude product was isolated using silica
gel column (hexane/ethyl acetate = 4/1 as eluent). 0.105 g
(0.408 mmol) of the product (1b) were obtained with 24% isolated
yield.
3.2. Representative procedure for synthesis by silylative coupling
reactions
In a typical test, the ruthenium catalyst [Ru(CO)ClH(PCy3)2)] or
[Ru(CO)ClH(PPh3)3] (2 mol%) was dissolved in toluene and placed
in a glass ampoule under argon. The reagents and dodecane as
internal standard (5% by volume all components) used in appropri-
ate molar ratios (see Tables 1 and 2) were added. The reaction was
conducted in an opened or closed system (when 2-vinyl-1,3,2-
dioxaborolane was used as substrate). Subsequently, the ampoule
was heated at 25–80 °C and maintained at this temperature for
24 h. The progress of the reaction was monitored by GC and GC–
MS. The conversion of reagents, chemoselectivity of the reactions
and yields of products were calculated by using the internal stan-
dard method. After the reaction, the crude product was purified by
1H NMR (300 MHz, C6D6, d, ppm): 0.61 (s, 3H, SiCH3), 1.15 (m,
2H, OCH2CH2), 3.42 (t, 4H, OCH2CH2), 5.84 (dd, 1H, J (H,H) = 3.8,
19.7 Hz, Ph(Me)SiCH@CHH), 6.11 (dd, 1H, J (H,H) = 3.8, 14.5 Hz,
Ph(Me)SiCH@CHH), 6.18 (d, 1H, J (H,H) = 19.5 Hz, SiHC@CHB),
6.66 (dd, 1H, J (H,H) = 14.5, 20.1 Hz, Ph(Me)SiCH@CH2), 7.11 (d,
1H, J (H,H) = 19.5 Hz, SiHC@CB), 7.21 (m, 3H, C6H6), 7.63 (m, 2H,
C6H6), ppm; 13C NMR (75 MHz, C6D6 d, ppm): ꢀ3.4 (SiCH3) 27.5
(OCH2CH2), 61.3 (OCH2CH2), 128.5 (C6H5), 130.2 (C6H5), 131.3
(C6H5) 133.8 (C6H5), 135.2 (Ph(Me)SiCH@CH2), 138.4 (Ph(Me)-
SiCH@CH2), 143.3 (SiCH@CHB) ppm; MS (EI) [m/z (%)]: 258(M+,
2), 243(100), 215(26). 201(18), 181(21), 163(51), 147(27),

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J. Walkowiak et al. / Journal of Organometallic Chemistry 695 (2010) 1287–1292
Table 1
Silylative coupling of 2-vinyl-1,3,2-dioxaborinane with divinylsubstituted organosilicon compounds.
(%)a
Si
T (°C)
Selectivity (a)/(b)/(c) (%)b
Isolated yield (%)
[cat]:
:[B]
Conversion of
Si
Si
2 ꢁ 10ꢀ2:1:3c
2 ꢁ 10ꢀ2:1:4
10ꢀ2:1:4
80
100
80
80d
80
80
80
60
25
80
89
100
67
100
57
100
100
83
20/28/52
2/21/77
15/31/54
4/25/71
9/15/76
2/12/74/12f
5/17/78
23/27/50
67/24/9
4/33/63
Me
Si
Ph
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4e
5 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:8
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
24(1b)g
70(1c)
63
100
37(1a)
55(2c)
Me
Si
Me
60
80
84
0
20/36/44
–
2 ꢁ 10ꢀ2:1:4
Ph
Si
Ph
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
100
100
83
86
7/15/78
2/28/70
Me
Me
Si
Si
Me
Me
Me Me
Si O Si
Me Me
2 ꢁ 10ꢀ2:1:3
10ꢀ2:1:4
80
80
80
80d
80
80
60
25
80
63
53
78
86
44
100
57
43
71
14/27/59
10/35/55
2/31/67
4/27/69
5/32/63
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4e
5 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
2 ꢁ 10ꢀ2:1:4
49(4c)
45(5c)
1/16/70/13f
17/28/55
38/28/36
0/30/70
OEt OEt
Si O Si
OEt OEt
Me
Si N Si
Me Me
2 ꢁ 10ꢀ2:1:4
80
90
0/92/8
H
Me
a
b
c
d
e
f
Determined by GC and GC–MS.
Determined by GC and 1H NMR.
t = 24 h, [Ru(CO)ClH(PCy3)2] unless otherwise stated.
t = 48 h.
[Ru(CO)ClH(PPh3)3].
Selectivity of a/b/c/d (%).
g
The numeration of the isolated products described in Section 3 is given in brackets.
Table 2
Silylative coupling of 2-vinyl-1,3,2-dioxaborolane with divinylsilicon compounds.

J. Walkowiak et al. / Journal of Organometallic Chemistry 695 (2010) 1287–1292
1291
121(70), 105(50), 87(30), 53(45); Elemental Anal. Calc. for
C14H19BO2Si: C, 65.12; H, 7.42. Found: C, 65.75; H 7.78%.
24 h. The conversion of 1,4-bis(dimethylvinylsilyl)benzene was
83% (GC).
MS (EI) [m/z (%)]: 399(M+-15, 100), 341(18), 281(15), 245(15),
207(20), 169(75), 141(35).
3.2.3. Bis[(E)-2-(10,30,20-dioxaborinan-20-yl)ethen-1-yl]methylphenylsilane
(1c)
3.2.7. [(E)-2-(10,30,20-Dioxaborinan-20-yl)ethen-1-
Complex Ru(CO)ClH(PCy3)2 (6.2 mg, 0.0085 mmol), toluene
(1.0 mL), 2-vinyl-1,3,2-dioxaborinane (0.3 g, 3.4 mmol) and
methylphenyldivinylsilane (0.075 g, 0.425 mmol) were placed in
a glass ampoule under argon atmosphere at 80 °C for 24 h. The
conversion of silane was 100% (GC).The crude product was isolated
using silica gel column (hexane/ethyl acetate = 4/1 as eluent).
0.10 g (0.3 mmol) of the product (1c) were obtained with 70% iso-
lated yield.
yl]tetramethylvinyldisiloxane (4b)and bis[(E)-2-(10,30,20-
dioxaborinan-20-yl)ethen-1-yl)]tetramethyldisiloxane (4c)
Compound (4c) was prepared from the appropriate starting
materials according to the above procedure for 2c. The conversion
of the tetramethyldivinyldisiloxane was 86%. The reaction afforded
(4c) (0.3 g, 0.83 mmol, isolated yield 49%).
(4c) 1H NMR (300 MHz, C6D6, d, ppm): 0.17 (s, 12H, SiCH3), 1.10
(m, 4H, OCH2CH2), 3.40 (t, 8H, OCH2CH2), 6.21 (d, 1H,
(H,H) = 19.8 Hz, SiHC@CHB), 6.93 (d, 1H, (H,H) = 19.8 Hz
1H NMR (300 MHz, C6D6, d, ppm): 0.64 (s, 3H, SiCH3), 1.13 (m,
J
4H, OCH2CH2), 3.46 (t, 8H, OCH2CH2), 6.07 (d, 1H,
J
J
SiHC@CB) ppm; 13C NMR (75 MHz, C6D6 d, ppm): 0.2 (Si(CH3)2)
26.3 (OCH2CH2), 61.1 (OCH2CH2), 149.7 (BCH@CHSi) ppm; MS (EI)
[m/z (%)]: 339(M+-15, 37), 281(51), 253(30). 243(100), 215(69),
185(8), 173(19), 143(17), 73(7), 59(4); Elemental Anal. Calc. for
C14H28B2O5Si2: C, 47.48; H, 7.97. Found: C, 47.11; H, 7.57%.
(4b) MS (EI) [m/z (%)]: 255(M+-15, 49), 230(18), 227(100),
169(28), 173(49), 85(37) 73(21).
(H,H) = 19.5 Hz, SiHC@CHB), 6.72 (d, 1H, (H,H) = 19.6 Hz
J
SiHC@CB), 7.24 (m, 3H, C6H6), 7.59 (m, 2H, C6H6) ppm; 13C NMR
(75 MHz, C6D6 d, ppm): ꢀ3.4 (Si(CH3)2) 27.8 (OCH2CH2), 61.0
(OCH2CH2), 128.7 (C6H5), 131.2 (C6H5), 132.0 (C6H5) 133.8 (C6H5),
135.3 (Ph(Me)SiCH@CH), 144.3 (SiCH@CHB) ppm; MS (EI) [m/z
(%)]: 258(M+, 2), 243(100), 215(26), 201(18), 181(21), 163(51),
147(27), 121(70), 105(50), 87(30), 53(45); Elemental Anal. Calc.
for C17H24B2O4Si: C, 59.69; H, 7.07. Found: C 59.37; H 7.00%.
3.2.8. Bis[(E)-2-(10,30,20-dioxaborinan-20-yl)ethen-1-y)]tetraethoxydis
iloxane (5c)
3.2.4. 1-Dimethylvinylsilyl-1-(10,30,20-dioxaborinan-20-yl)ethene (2a)
and (E)-1-dimethylvinylsilyl-2-(10,30,20-dioxaborinan-20-yl)ethene
(2b)
Complex Ru(CO)ClH(PCy3)2 (25 mg, 0.034 mmol), toluene
(3.4 mL), 2-vinyl-1,3,2-dioxaborinane (0.76 g, 6.8 mmol) and
dimethyldivinylsilane (0.19 g, 1.7 mmol) were placed in a glass
ampoule under argon atmosphere at 60 °C for 24 h. The conversion
of dimethyldivinylsilane was 84% (GC).
Compound (5c) was prepared from the appropriate starting
materials according to the above procedure for (2c). The conver-
sion of the tetraethoxydivinyldisiloxane was 71%. The crude prod-
uct was isolated using silica gel column modified with HMDS
(hexane/ethyl acetate = 4/1 as eluent). The reaction afforded (5c)
(0.37 g, 0.77 mmol, isolated yield 45%).
1H NMR (300 MHz, C6D6, d, ppm): 1.10 (m, 4H, BOCH2CH2), 1.22
(t, 12H, J (H,H) = 6.8 Hz, SiOCH2CH3), 3.36 (t, 8H, BOCH2CH2), 3.87
(q, 8H, J (H,H) = 6.8 Hz, SiOCH2CH3) 6.11 (d, 1H, J (H,H) = 19.9 Hz,
SiHC@CHB), 6.78 (d, 1H, J (H,H) = 20.1 Hz, SiHC@CB) ppm; 13C
NMR (75 MHz, C6D6 d, ppm): 18.8 (SiOCH2CH3) 26.5 (BOCH2CH2),
57.8 (SiOCH2CH3), 61.5 (BOCH2CH2), 151.2 (BCH@CHSi) ppm; MS
(EI) [m/z (%)]: 474(M+, 4), 445 (16), 416 (11), 392(4), 308(100),
293 (92), 225(34), 159(7), 133(7), 85(36), 73(38), 59(45); Elemen-
tal Anal. Calc. for C18H36B2O9Si2: C, 45.58; H, 7.65. Found: C, 45.41;
H, 7.46%.
(2a) MS (EI) [m/z (%)]: 196(49), 168(50) 138(62), 129(100),
119(32), 110(18) 89(32), 66 (50), 53(48).
(2b) MS (EI) [m/z (%)]: 181(M+-15, 100), 153(76), 139(62),
101(85) 85(38), 155(35) 59(56).
3.2.5. Bis[(E)-2-(10,30,20-dioxaborinan-20-yl)ethen-1-yl]dimethylsilane
(2c)
Complex Ru(CO)ClH(PCy3)2 (25 mg, 0.034 mmol), toluene
(3.4 mL), 2-vinyl-1,3,2-dioxaborinane (0.76 g, 6.8 mmol) and dim-
ethyldivinylsilane (0.19 g, 1.7 mmol) were placed in a glass ampule
under an argon atmosphere at 80 °C for 24 h. The conversion of
dimethyldivinylsilane was 100% (GC). The crude product was iso-
lated using silica gel column (hexane/ethyl acetate = 4/1 as eluent).
0.26 g (0.94 mmol) of the product (2c) were obtained with 55% iso-
lated yield.
3.2.9. [(E)-2-(10,30,20-Dioxaborinan-20-yl)ethen-1-yl]tetramethylvinyl-
disilazane (6b) and bis[(E)-2-(10,30,20-dioxaborinan-20-yl)ethen-1-yl]
tetramethyldisilazane (6c)
The mixture of compound (6b) and (6c) (6b/6c = 98/2) was pre-
pared from the appropriate starting materials according to the
above procedure for (2c). The conversion of tetramethyldivinyldisi-
lazane was 90%.
1H NMR (300 MHz, C6D6, d, ppm): 0.64 (s, 3H, SiCH3), 1.13 (m,
4H, OCH2CH2), 3.46 (t, 8H, OCH2CH2), 6.07 (d, 1H,
J
(H.H) = 19.5 Hz, SiHC@CHB), 6.72 (d, 1H, (H,H) = 19.6 Hz
J
(6b) MS (EI) [m/z (%)]: 254 (M+-15, 100), 226(66), 184(72),
172(28), 154(37), 130(19) 100(18), 73(12), 59(21).
(6c) MS (EI) [m/z (%)]: 313(M+-30, 7), 298(11), 255(59),
227(100), 217(100), 189(68), 169(78), 149(23), 133(38), 99(13),
75(21), 59(45).
SiHC@CB), 7.24 (m, 3H, C6H6), 7.59 (m, 2H, C6H6) ppm; 13C NMR
(75 MHz, C6D6 d, ppm):-3,4 (Si(CH3)2) 27.5 (OCH2CH2), 61.3
(OCH2CH2), 128.5 (C6H5), 130.2 (C6H5), 131.3 (C6H5) 133.8 (C6H5),
135.2 (Ph(Me)SiCH@CH2), 138.4 (Ph(Me)SiCH@CH2), 143.3
(SiCH@CHB) ppm; MS (EI) [m/z (%)]: 342(M+, 10), 291(28),
267(8), 241(12), 207(32), 179(31), 147(63), 121(89), 105(29),
91(100), 77(12), 67(33)
3.2.10. 1-(Methylphenylvinylsilyl)-1-(10,30,20-dioxaborolan-20-yl)ethene
(7a)
Elemental Anal. Calc. for C12H22B2O4Si: C, 57.41; H, 7.92. Found:
C, 57.57; H 7.90%.
Complex Ru(CO)ClH(PCy3)2 (15 mg, 0.021 mmol), toluene
(2.2 mL), 2-vinyl-1,3,2-dioxaborolane (0.43 g, 4.4 mmol) and
methylphenyldivinylsilane (0.18 g, 1.1 mmol) were placed and
sealed in a glass ampoule under argon atmosphere at 25 °C for
24 h. The conversion of methylphenyldivinylsilane was 61% (GC).
The crude product was isolated using silica gel column (hexane/
ethyl acetate = 4/1 as eluent). 0.11 g (0.45 mmol) of the product
(7a) were obtained with 41% isolated yield.
3.2.6. 1,4-Bis{[(E)-2-(10,30,20-dioxaborinan-20-yl)ethen-1-yl]dimethylsilyl}
benzene (3c)
Complex Ru(CO)ClH(PCy3)2 (10 mg, 0.014 mmol), toluene
(3.4 mL), 2-vinyl-1,3,2-dioxaborinane (0.31 g, 2.8 mmol) and
bis(1,4-dimethylvinylsilyl)benzene (0.29 g, 0.69 mmol) were
placed in a glass ampoule under argon atmosphere at 100 °C for

1292
J. Walkowiak et al. / Journal of Organometallic Chemistry 695 (2010) 1287–1292
1H NMR (300 MHz, C6D6, d, ppm): 0.65 (s, 3H, SiCH3), 3.48 (s, 4H,
(9b)MS (EI) [m/z (%)]: 241(M+-15, 100), 187(48), 155(75),
73(22), 45(20).
CH2), 5.83 (dd, 1H, J (H,H) = 3,8, 20.2 Hz, Ph(Me)SiCH@CHH), 6.12
(dd, 1H, J (H,H) = 3.8, 14.4 Hz, Ph(Me)SiCH@CHH), 6.23 (d, 1H, J
(H,H) = 5.2 Hz HHC@CB(Si)), 6.59 (dd, 1H, J (H,H) = 14.7, 20.2 Hz
Ph(Me)SiCH@CH2), 6.9 (d, 1H, J (H,H) = 5.2 Hz HHC@CB(Si). 7.32
(m, 3H, C6H6), 7.63 (t, 2H, C6H6) ppm; 13C NMR (75 MHz, C6D6 d,
ppm): ꢀ3.89 (SiCH3), 65.6 (OCH2), 128.9 (C6H5), 129.4(C6H5),
131.0 (C6H5) 134.0 (Ph(Me)SiCH@CH2), 135.1 (C6H5), 137.7
(Ph(Me)SiCH@CH2), 148.7 (CH2@B(Si)) ppm; MS (EI) [m/z (%)]:
229(M+-15, 72), 201(42), 147(47), 121(100), 77(24), 53(40); Ele-
mental Anal. Calc. for C13H17BO2Si: C, 63.95; H, 7.02. Found: C,
64.08; H, 7.22%.
3.2.15. Bis[(E)-2-(1,3,2-dioxaborolan-2-yl)ethenyl]tetramethyldisiloxane
(9c)
Compound (9c) was prepared from the appropriate starting
materials according to the above procedure for (7c). The conver-
sion of the tetramethyldivinyldisiloxane was 93%. The reaction
afforded (9c) (0.33 g, 1 mmol, isolated yield 59%).
1H NMR (300 MHz, C6D6, d, ppm): 0.15 (s, 12H, SiCH3), 3.60 (s,
8H, CH2), 6.15 (d, 2H, J (H,H) = 19.5 Hz, SiHC@CHB), 6.86 (d, 2H, J
(H,H) = 19.3 Hz SiHC@CB) ppm; 13C NMR (75 MHz, C6D6 d, ppm):
0.2 (Si(CH3)2), 62.9 (CH2), 147.6 (BCH@CHSi) ppm; MS (EI) [m/z
(%)]: 311(M+-15, 50), 267(25), 229(100), 175(45), 143(40),
73(18), 45(10); Elemental Anal. Calc. for C12H24B2O5Si2: C, 44.20;
H, 7.42. Found C, 44.82; H, 7.70%.
3.2.11. Bis[(E)-2-(10,30,20-dioxaborolan-20-yl)ethen-1-yl]phenylmethyl
silane (7c)
Ru(CO)ClH(PCy3)2 complex (15 mg, 0.021 mmol), toluene
(2.2 mL), 2-vinyl-1,3,2-dioxaborolane (0.43 g, 4.4 mmol) and
methylphenyldivinylsilane (0.18 g, 1.1 mmol) were placed and
sealed in a glass ampoule under argon atmosphere at 80 °C for
24 h. The conversion of methylphenyldivinylsilane was 77% (GC).
The crude product was isolated using silica gel column (hexane/
ethyl = 4/1 as eluent). 0.16 g (0.52 mmol) of the product (7c) were
obtained with 47% isolated yield.
3.2.16. [(E)-2-(10,30,20-Dioxaborolan-20-yl)ethen-1-yl]tetramethyl
vinyldisilazne (10b) and bis[(E)-2-(10,30,20-dioxaborolan-20-yl)ethen-
1-yl]tetramethyldisilazane (10c)
The mixture of compounds (10b) and (10c) ((10b)/(10c) = 94/6)
was prepared from the appropriate starting materials according to
the above procedure for (7c).
1H NMR (300 MHz, C6D6, d, ppm): 0.60 (s, 3H, SiCH3), 3.53 (s, 8H,
OCH2), 6.12 (d, 2H, J (H,H) = 19.9 Hz, SiHC@CHB), 6.65 (d, 2H, J
(H,H) = 20.0 Hz, SiHC@CHB), 7.29 (m, 3H, C6H6), 7.61 (m, 2H,
C6H6) ppm; 13C NMR (75 MHz, C6D6 d, ppm): ꢀ3.6 (Si(CH3)2) 65.3
(OCH2), 128.7 (m C6H5), 130.3 (p C6H5), 131.2 (C6H5) 133.8 (o
C6H5), 145.6 (SiCH@CHB) ppm; Elemental Anal. Calc. for
C15H20B2O4Si: C, 57.37 H, 6.42. Found: C, 57.00; H, 6.52%.
(10b) MS (EI) [m/z (%)]: 240(M+-15, 27), 203(74), 187(26),
155(100), 131(30), 85(47), 59(45).
(10c) MS (EI) [m/z (%)]: 311(M++1, 46), 267(19), 229(100),
175(36), 143(35), 73(12), 45(14).
Acknowledgement
This work was supported by the Ministry of Science and Higher
Education (Poland) (N N204265538).
3.2.12. 1-Dimethylvinylsilyl-1-(10,30,20-dioxaborolanyl-20-yl)ethene
(8a) and (E)-1-dimethylvinylsilyl-2-(10,30,20-dioxaborolan-20-yl)ethene
(8b)
References
Complex Ru(CO)ClH(PCy3)2 (15 mg, 0.021 mmol), toluene
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ethyldivinylsilane (0.12 g, 1.1 mmol) were placed and sealed in a
glass ampoule under argon atmosphere at 60 °C for 24 h. The con-
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(8a) MS (EI) [m/z (%)]:167(M+-15, 12), 153(5), 138(100),
123(25), 114(63), 89(59), 66(82), 54(70), 45(80).
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Compound (8c) was prepared from the appropriate starting
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methylvinyldisiloxane (9b)
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appropriate starting materials according to the above procedure
for (7a). The conversion of the dimethyldivinylsilane was 36%.
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101(19), 85(25), 45(9).
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