Highly stereoselective synthesis of novel trans-thiophenylene-silylene- vinylene-arylene molecular and macromolecular compounds

Article abstract of DOI:10.1016/j.jorganchem.2011.01.020

Novel stereoregular molecular compounds 8-13 containing thiophenylene-silylene-vinylene-phenylene units have been synthesised via highly effective silylative coupling of styrene and 1,4-divinylbenzene (7) with respective vinylsilylthiophenes (3, 4) and bis(vinylsilyl)thiophenes (5, 6) catalyzed by RuHClCO(PCy₃)₂. Respective copolymers (14, 15) were produced via silylative copolycondensation of 5 and 6 with 7. All products were isolated and characterised by NMR, MS, HRMS and two of them 10 and 11 by X-ray method. Catalytic study as well as stoichiometric reactions of Ru-H (1) with 2-(vinylsilyl)thiophene (3) and Ru-Si (16) with styrene confirmed the mechanism of the silylative coupling olefins with vinylsilicon compounds.

Full text of DOI:10.1016/j.jorganchem.2011.01.020

Journal of Organometallic Chemistry 696 (2011) 1456e1464
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Highly stereoselective synthesis of novel trans-thiophenylene-silylene-vinylene-
arylene molecular and macromolecular compounds
*
Monika Ludwiczak, Mariusz Majchrzak, Bogdan Marciniec , Maciej Kubicki
ꢀ
Faculty of Chemistry, Adam Mickiewicz University, 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:
Novel stereoregular molecular compounds 8e13 containing thiophenylene-silylene-vinylene-phenylene
units have been synthesised via highly effective silylative coupling of styrene and 1,4-divinylbenzene (7)
with respective vinylsilylthiophenes (3, 4) and bis(vinylsilyl)thiophenes (5, 6) catalyzed by RuHClCO
(PCy3)2. Respective copolymers (14, 15) were produced via silylative copolycondensation of 5 and 6
with 7. All products were isolated and characterised by NMR, MS, HRMS and two of them 10 and 11 by
X-ray method. Catalytic study as well as stoichiometric reactions of RueH (1) with 2-(vinylsilyl)thio-
phene (3) and RueSi (16) with styrene confirmed the mechanism of the silylative coupling olefins with
vinylsilicon compounds.
Received 6 December 2010
Received in revised form
12 January 2011
Accepted 17 January 2011
Keywords:
trans-Conjugated polymers
Thiophene
Homogeneous catalysis
Silylative coupling
Silicon
Ó 2011 Elsevier B.V. All rights reserved.
Ruthenium
1. Introduction
polymer using the chain flexibility owing to silicon atoms. Organo-
silicon polymers, dendrimers and hyperbranched polymers con-
Polymeric materials consisting of sulphur-containing heterocy-
cles have not been studied intensively as units in poly(p-phenyl-
enevinylene) PPV. Poly(thienylene-vinylene) is reported to show
only very weak red electroluminescence (EL) properties [1]. This
type of polymer is really difficult to prepare by precursor routes. In
view of their possible applications in electronics, optoelectronics
and as non-linear optical materials [2], conjugated polymers have
attracted a lot of attention recently. At present, their commercial
applications include mainly production of charge dissipations films
[3], light-emitting diodes (LED) [4] and electrochromic displays [5].
Conductive polymers are also used as volatile organic gas sensors
[6]. Polythiophenes, which are one of the most important conju-
gated polymer families, have been investigated in terms of spec-
troscopic and photophysical behaviour by the so-called oligomer
approach [7]. Additionally, the study of the properties of poly(thio-
phene)s appears tobe of the greatimportance in this field [2b, 7e17].
The possibility of synthesis of varied functionalized conjugated
oligomers and polymers based on thiophene residues, especially
those carrying heteroatoms (phosphorus or silicon) in the side chain
or main chain [15,18,19], has considerably increased in recent years.
It is achievable to enhance the solubility and processability of the
sisting of silylene-thiophene fragments and saturated carbon bridge
(eCH2eCH2e) between two silicon atoms have been synthesized via
hydrosilylation process catalyzed by Pt catalysts, which gave poly-
meric materials with high polydispersity index (3.71e4.18) and low
molecular weight. Moreover, the final product included the colloidal
metal [20]. Wang studied the synthesis of unsaturated silicon-
thiophene derivatives of oligomers from (p-(dimethylsilyl)phenyl)
acetylene via the above mentioned reaction. The products were
mostly cross-linked polymers and did not dissolve in organic
solvents [21].
The optional and unique as well as convenient and effective way
to get this type of unsaturated organosilicon polymers is silyla-
tive coupling polycondensation (SCP) reaction of vinylsilanes in the
presence of transition metal complexes (e.g. ruthenium and
rhodium) containing or generating metalehydrogen ([M]eH) and
metal-silicon ([M]eSi) bonds. The silylative coupling reaction of
monovinyl-silanes proceeds through cleavage of the ]CeSi bond of
the vinylsubstituted silicon compounds and the activation of the ]
CeH bond of the second vinylsilane molecules [22] (see Scheme 1).
The mechanism of this reaction involving b-silyl elimination and
insertion of a C]C double bond into the resulting [M]eSi bond has
been proved by insertion of ethylene and vinylsilane into [M]eSi
(where M ¼ Ru, Rh, Ir, Co) bonds as well as by a series of elaborate
mass spectroscopic studies with deuterated styrene and vinyl-
silanes [23].
* Corresponding author. Tel.: þ48 61 82191 509; fax: þ48 61 8291 508.
E-mail address: bogdan.marciniec@amu.edu.pl (B. Marciniec).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.01.020

M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
1457
H
H
H
SiR3
H
complete conversion of substrates and selective formation of cross-
coupling products (8, 9), Scheme 3.
[M]-H, [M]-Si
- H C=CH
R'
R'
R'
R'
+
+
+
SiR3
H
R3Si
H
H
The results obtained are collected in Table 1.
H
SiR3
H
M = Ru, Rh, Ir, Co
A very similar reactivity was observed when vinyl derivatives
5 and 6 were used as reaction partners, see Scheme 4.
The coupling reactions were examined in the presence of the
mononuclear, five-coordinate ruthenium (II) complex 1 checked in
the previous system. In each case the reaction led to efficient and
selective formation of E-isomer of 10 and 11. The results obtained
were collected in Table 2.
A 10% excess of styrene was used to achieve quantitatively or in
high yield disubstituted bis(silyl)thiophenes. Very efficient and
selective functionalisation was observed.
Scheme 1. General scheme of silylative coupling (SC) reaction.
The evidence for the non-metallacarbene mechanism of mon-
ovinylsilane transformation has been reported [23, 26b], but it can
be generalized for dimerization of divinyl-substituted silanes [24a,
24b, 25] siloxane [24a, 24b, 25a], silazanes [25b] and bis(vinylsilyl)
alkanes [25c] leading subsequently to competitive linear oligo-
merization [24].
An analogous system of 1,4-divinylbenzene (7) with 3 or 4 in
toluene was obtained using 1 as a catalyst, see Scheme 5.
The above mentioned reactions of 7 (DVB) with 3 and 4 per-
formed under the same conditions as above (Tables 1 and 2) lead to
not so high conversions of substrates and evolution of ethylene but
with good stereo-selectivity. 1H NMR investigation of the reaction
mixtures after 48 h of the reactions course indicated formation
of functionalized products 12 and 13. The results obtained are
collected in Tables 3 and 4.
All tables demonstrate good or very high yields of correspond-
ing products obtained via silylative coupling reaction. The proce-
dures applied for isolation of products from the reaction mixture
are very simple and useful. Each molecular compound (8e13) was
isolated (the crude product obtained was purified by column
chromatography (silica gel/hexane), in practically quantitative yield
(80e99%)), and fully characterised spectroscopically, which
allowed to confirm expected structures.
Moreover, the synthesis of homo- and copolymers containing
phenylene-silylene-vinylene and copolymers consisting of phenyl-
ene-silylene-vinylene-phenylene-vinylene units with well-defined
structures [26] has been successfully performed, Scheme 2.
In 2008 we reported the stereoselective synthesis of poly(sily-
lene-thiophene)s and their basic photophysical properties [27].
Therefore, in this paper we would like to describe efficient
selective procedures for synthesis of novel stereoregular thiophene
(and bithiophene)-silylene-vinylene molecular compounds as well
as suitable copolymers with the trans-silylene-vinylene-phen-
ylene-silylene bridged structures via the respective reaction of
bis(vinyldimethylsilyl)thiophene or bithiophene derivatives with
1,4-divinylbenzene.
2. Results and discussion
2.1. Synthesis of substrates
All substrate monomers: 2-(vinyldimethylsilyl)thiophene (3), 5-
(vinyldimethylsilyl)-2,20-bithiophene (4), 2,5-bis(vinyldimethylsilyl)
thiophene (5) and 5,50-bis(vinyldimethylsilyl)-2,20-bithiophene (6)
were obtained in ‘one pot’ by the well known Grignard’s reaction of
commercially available compounds. Treatment of mono- or dibro-
mothiophene derivatives with magnesium in THF generated ‘in situ’
the so-called ‘Grignard reagent’, which in the presence of 10% excess
of chlorodimethylvinylsilane at a suitable temperature (from 5 ꢀC to
35 ꢀC, which was controlled all the time), under an argon atmosphere
afforded the desirable compounds with good yields (83e93%). All the
above mentioned silyl-compounds (3e6) are air- and moisture-
stable, liquids (at room temperature) and were fully characterised by
accessible methods.
2.3. X-ray study
The structures of 10 and 11 were confirmed by crystallographic
method analysis. Molecular compounds 10 and 11 proved to be
solid ones and gave crystals amenable to X-ray crystal structure
determination. To the best of our knowledge, this is the first
structural characterisation of thionyl-silyl-substituted aromatic
compounds containing heteroaryl group.
In 10 the planes of the terminal phenyl rings are almost
perpendicular to the central thiophene ring; the dihedral angles are
74.1(2)ꢀ and 85.8(2)ꢀ. The double bond is in trans disposition, the
appropriate torsion angles are Si6eC9eC10eC11 ꢁ176.4(5)ꢀ and
Si18eC21eC22eC23 ꢁ175.3(4)ꢀ. The molecular dimensions are
typical, see Fig. 1.
2.2. Reactivity of vinylsilylthiophene derivatives in the presence of
ruthenium-hydride complex
In 11, the planes of central thiophene rings are inclined by 25.7
(2)ꢀ, and the terminal phenyl rings are also significantly twisted, by
54.06(8)ꢀ and 76.4596ꢀ, which leads to the almost perpendicular
disposition of the phenyl rings (75.22(7)ꢀ). The double bonds are
also in the trans disposition, the SieC]CeC dihedral angles are
176.87(15) and ꢁ178.74(16)ꢀ, see Fig. 2.
While the mixture ofequimolaramounts of2-(vinyldimethylsilyl)
thiophene (3) or 5-(vinyldimethylsilyl)-2,20-bithiophene (4) and
styrene was treated in toluene with 16-electron ruthenium-hydride
catalyst [RuHCl(CO)(PCy3)2] (1) (2e0.5 mol% in relation to vinyl
group of vinylsilane), slow evolution of ethene was observed.
Monitoring of the reaction progress via GC shows regular conversion
of both substrates. Proton NMR analysis of the reaction mixture
performed after 6 and 24 h of the reaction course, indicated nearly
In both structures there are practically no specific, directional
intermolecular interactions (one can list some weak CeH/S
contacts), so the packing is probably determined by the van der
Waals interactions and close packing requirements. The crystal data
are collected in Table 5, please see supporting materials.
Me
Si
Me
Me
Me
Si
Me
Me
Si
Me
[Ru-H]
Me
Si
Me
[Ru-H]
Me
Si
Me
Si
r
+
m
m
r
Me
S
- n H2C=CH2
n
S
x
x
- H2C=CH2
r = 0, 1; m = 1, 2
trans-organosilicon polymer
x = 1 (3), x = 2 (4)
8, 9
Scheme 2. SCP mono- or bis(vinyldimethylsilyl)arenes in the presence of ruthenium
complex.
Scheme 3. SC of dimethylvinylsilylthiophene derivatives with styrene.

1458
M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
Table 1
Table 2
Silylative coupling of dimethylvinylsilylthiophene derivatives with styrene.
Silylative coupling of bis(dimethylvinylsilyl)thiophenes with styrene.
Vinylsilane
Molar ratio [ViSi]: Time Conversion of Yield
Vinylsilane
Molar ratio
[ViSi]:[Styrene]: (h)
[RuH]
Time Conversion
Yield (%)b
[Styrene]:[RuH]
(h)
vinylsilane (%)a (%)b
>99 (99)c
of vinylsilane
A
B (10 v 11)
(%)a
1:1:0.015
1:1:0.010
3
3
6
3
6
18
3
6
3
>99
87
95
70
88
94
85
98
57
94
99
30
47
79
86
13
36
59
73
Me
Si
Me
87
95
70
88
94
85
3
97
20 77
1:2.1:0.015
6
3
>99
>99
e
>99 (92)c
Me
Si
Me
Me
Si
Me
S
1:1:0.005
1:2.1:0.010
1:2.1:0.005
20 80
S
S
6
e
>99
3
99
9
3
90
97
99
6
>99
1:1:0.020
1:1:0.015
98 (95)c
57
94
99
30
47
79
86
13
36
59
73
12
3
e
63 33
48 52
35 65
24 76
6
18
3
6
96
>99
Me
Si
Me
Me
Si
Me
Me
Si
Me
1:2.1:0.015
1:2.1:0.010
12
18
24
3
1:1:0.010
1:1:0.005
6
1
99 (96)c
S
S
2
18
24
3
6
18
24
91
51 40
46 53
39 60
32 68
6
>99
12
18
Reaction conditions: T ¼ 83e85 ꢀC, toluene (1 M solution).
a
Conversion of silane was calculated from GC chromatogram (decane, 5% the total
Reaction conditions: T ¼ 83e85 ꢀC, toluene (1 M solution).
volume).
a
b
c
Conversion of silane was calculated from GC chromatogram (decane, 5% the
Yield was calculated from GC chromatogram (decane, 5% the total volume)
total volume).
Isolated yield; argon; selectivity of the reaction >99% isomer trans-(1H NMR
b
c
Yield was calculated from GC chromatogram (decane, 5% the total volume)
calculation).
Isolated yield; argon; selectivity of the reaction ¼ 100% isomer trans-(1H NMR
calculation).
styrene. The progress was controlled by GCMS and NMR methods.
1H NMR examination confirmed the formation of the [RueH]
complex e trace amount (signal e dt, at ꢁ5.82 ppm) providing
a convenient test for insertion of the olefin into RueSiMe2(C4H3S)
bond and next b-H transfer with elimination of 2-silylthionylstyr-
ene, according to Scheme 8.
Careful analysis of GCMS chromatogram and spectrum revealed
the formation of 8 after 24 h and free triphenylphosphine as a result
of decoordination from complex 16 (see Figs. 3 and 4 in the
supporting material). Analysis of full MS(EI) spectrum gave us clear
proof that the catalytic process occurs according to the silylative
coupling reaction. Only one product shows a very high chemo-
selectivity of reaction.
When DVB was used as a substrate, the coupling reaction
required longer time (48 h). DVB is less reactive than styrene in SC
reaction but could be very active in radical polymerization partic-
ularly in high concentration solution and temperature. Further-
more, vinylsilyl part at thiophene derivatives is definitely less
reactive than at typical alkyl- or aryl- substituted silanes. Con-
ceivably, this fact comes from a strongly drawn out heterocyclic
fragment of the substrate.
2.4. Proposed of silylative coupling mechanism and stoichiometric
studies
As we have reported earlier, ruthenium-hydride complexes
effectively catalyse silylative coupling of olefins with vinylsilicon
compounds (for review see ref. 22b). This reaction proceeds
according to the non-metalacarbene mechanism involving inser-
tion of vinylsilylthiophene into [RueH] bond ((a) / (b) / (c))
followed by evolution of ethylene (b-Si transfer) to get [RueSi]
intermediate (d). The insertion of styrene (also 1,4-divinylbenzene)
into [RueSi] bond ((d) / (e) / (f)) leads to complex (f). The final
2.5. Synthesis of polymeric materials
A preliminary study allowed us to optimise highly stereo-
selective synthesis of well-defined trans-cooligomers. Application
of 1 as catalyst for silylative-coupling copolycondensation of 5 and
6 with 7 gave exclusively linear oligomers 14 and 15 containing
trans-vinylene bond between siliconecarbon atoms with medium
average molecular weight Mw ¼ 4313e6065 and low polydispersity
index PDI ¼ 1.31e1.41, see Scheme 9.
step of the product formation (b-H transfer) occurs via reductive
elimination of product regenerating complex (a), see Scheme 6.
In order to confirm this mechanism, we mixed a more stable
complex [RueH] with triphenylphosphine {RuHCl(CO)(PPh3)3} with
3 at 100e110 ꢀC for 22 h and new thionyl-silyl species Ru
(SiMe2C4H3S)Cl(CO)(PPh3)2 (16) wasprepared accordingto Scheme 7.
The NMR spectroscopic analysis evidently showed the typical
silyl-ruthenium catalysis structure. Afterwards, 16 was tested in
equimolar reaction in the presence of excess of fresh distilled
The new polymer products obtained were purified by precipi-
tation two times from alcohol at room temperature.
3. Conclusion
Novel stereoregular trans-thiophenylene-silylene-vinylene-ary-
lene molecular derivatives have been easily synthesized via
Me
A
Si
Me
S
x
x
Me
Si
Me
[Ru-H]
Me
Si
Me
+
S
x
S
- H2C=CH2
Me
Si
Me
x
S
3
x = 1 ( ), x = 2 (
4
)
7
B (12 or 13)
Scheme 4. SC of bis(dimethylvinylsilyl)thiophene derivatives with styrene.
Scheme 5. SC of dimethylvinylsilylthiophene derivatives with 7.

M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
1459
Table 3
Silylative coupling of 2-dimethylvinylsilylthiophenes with 7.
Molar ratio [ViSi]:[DVB]:[RuH]
Sol. con. (M)/temperature (ꢀC)
Time (h)
Conversion (%)a
ViSi
Selectivity (%)b
A
DVB
B (12)
2:1:0.030
1 M/100 ꢀC
3
3
6
24
48
3
24
3
8
55
44
60
>99
8
e
0.5 M/100 ꢀC
30
42
83
99
21
98
24
79
99
30
45
15
1
21
2
24
13
2
e
20
75
99
e
2:1:0.020
1 M/100 ꢀC
0.5/100 ꢀC
42
>99
26
87
e
24
48
>99
72
98
a
Conversions of substrates were calculated from GC chromatogram (decane, 5% the total volume).
b
Selectivity of the reaction >99% isomer trans-(GCeMS and 1H NMR calculations); argon.
silylative coupling of 2-vinyldimethylsilylthiophene (3) and 5-
chromatography (GPC) analysis was performed using an Agilent
HPLC system equipped with UV absorbance detector and RI detector
(analysis conditions: mobile phase e CH2Cl2; flow rate e 0.80 mL/
vinyldimethylsilyl-2,20-bithiophene (4) with styrene and 1,4-
divinylbenzene (7) to yield respective new products 8e13. The
structures of 10 and 11 were solved by X-ray crystal structure
method. The compounds 2,5-bis(vinyldimethylsilyl)thiophene (5)
and 5,50-bis(vinyldimethylsilyl)-2,20-bithiophene (6) react effectively
with styrene to yield respective compounds 12 and 13. Compounds 5
and 6 undergo silylative coupling copolycondensation with 7 (DVB)
to get exclusively linear oligomers 14 and 15 of low molecular weight
and low polydispersity index 1.31e1.41. Catalytic results and stoi-
chiometric reactions of ruthenium-hydride (2) with 3 and ruthe-
nium-silyl (16) complex with styrene confirm a general catalytic
scheme of the silylative coupling of olefins with vinylsilanes.
min; temperature e 20 ꢀC; injection volume e 17
mL). The number-
average molecular weight (Mn), weight-average molecular weight
(Mw) and polydispersity index (PDI) were determined by poly-
styrene standard calibration curve. Thin-layer chromatography
(TLC) was made on plates coated with 250
mm thick silica gel
(Aldrich and Merck), and column chromatography was conducted
with silica gel 60 (70e230 mesh, Fluka).
4.2. Materials
The chemicals were obtained from the following sources:
toluene, diethyl ether, THF, pentane and hexane, were purchased
from Fluka, CDCl3, from Dr Glaser A.G. Basel, styrene, 2,5-dibro-
mothiophene, 5,50-dibromo-2,20-bithiophene from Avocado, 2-
bromothiophene, 5-bromo-2,20-bithiophene, magnesium sulphate,
calcium hydride (CaH2), sodium hydride (NaH),1,2-dibromoethane,
ethanol, methanol, from Aldrich and chlorodimethylvinylsilane
from Gelest. Tetrahydrofuran (THF), toluene and diethyl ether were
distilled from sodium and hexane from calcium hydride under
argon. The above mentioned solvents were stored over molecular
sieves type 4 Å. All liquid substrates were also dried and degassed
by bulb-to-bulb distillation. All the syntheses of monomers, poly-
meric materials and catalytic tests were carried out under an inert
argon atmosphere. The ruthenium complexes RuHCl(CO)(PCy3)2 (1)
and RuHCl(CO)(PPh3)3 (2) were prepared according to the literature
procedure [28,29].
4. Experimental
4.1. Instruments
1H NMR (300 MHz), 13C NMR (75 MHz) and 29Si NMR (60 MHz)
and DEPT spectra were recorded on a Varian XL 300 MHz spec-
trometer in CDCl3 solution. Chemical shifts are reported in d (ppm)
with reference to the residue solvent (CD3Cl) peak for 1H, 13C and to
TMS for 29Si. Analytical gas chromatographic (GC) analyses were
performed on a Varian Star 3400CX with a DB-5 fused silica capillary
column (30 m ꢂ 0.15 mm) and TCD. Mass spectra of the monomers
and products were obtained by GCMS analysis (Varian Saturn 2100T,
equipped with a BD-5 capillary column (30 m)) and an ion trap
detector. High-resolution mass spectroscopic (HRMS) analyses were
performed on an AMD-402 mass spectrometer. Gel permeation
Table 4
Silylative coupling of 5-dimethylvinylsilylbithiophene with 7.
Molar Ratio [ViSi]:[DVB]:[RuH]
2:1:0.040
Sol. con. (M)/temperature (ꢀC)
Time (h)
Conversion (%)a
ViSi
Selectivity (%)b
A
DVB
B (13)
0.5 M/100 ꢀC
3
3
5
3
e
6
15
44
80
7
16
49
>99
8
15
44
35
7
e
24
48
3
trace
62
e
2:1:0.030
2:1:0.020
0.5 M/100 ꢀC
0.5 M/100 ꢀC
6
14
32
49
1
17
60
87
6
14
53
43
e
e
24
48
3
5
27
e
6
24
48
17
30
39
21
66
70
17
54
62
e
3
8
a
Conversions of substrates were calculated from GC chromatogram (decane, 5% the total volume).
b
Selectivity of the reaction >99% isomer trans-(GCeMS and 1H NMR calculations); argon.

1460
M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
Me
Me
Si
[Ru]
(a)
H
Si
n
n
S
S
Ph
Me
Me
H
[Ru]
Me
H
Si
f
( )
(b)
Si
n
S
n
[Ru]
S
Me
Me
Me
Ph
Me
Me
Si
n
Fig. 1. A perspective view of 10 with labelling scheme. Ellipsoids are drawn at the 50%
probability level, hydrogen atoms are shown as spheres of arbitrary radii.
[Ru] Si
Me
S
[Ru]
e
( )
n
S
Me
(c)
Ph
Me
[Ru] Si
4.3. Syntheses of organosilicon and organic compounds
n
S
Ph
Me
2-(Vinyldimethylsilyl)thiophene (3): In a two-neck flask equipped
with magnetic stirrer, under Argon atmosphere, a suspension of Mg
(0.6 g, 24.7 mmol, whose surface was activated by the use of 1,2-
dibromoethane, 0.2 mL) and chlorodimethylvinylsilane (3.1 mL,
22.7 mmol) in 6 mL of THF was prepared. A solution of 2-bromo-
thiophene (3.37 g, 20.6 mmol) in 14 mL of THF was added dropwise
to the suspension and the reaction mixture was refluxed. Progress
of the reaction was controlled by GC analysis. Then, the mixture
was cooled to room temperature, excess of organic solvent was
evaporated and the product was isolated by extraction with
hexane/water solvents. The organic layer was separated, dried
under magnesium sulphate and filtered. Then, the solvent was
evaporated, and the residue was separated with silica gel column
(hexane, Rf ¼ 0.45) to afford (3) as a colourless liquid. Yield: 2.9 g
(84%).
(d)
n = 1, 2
Scheme 6. Proposed SC of mechanism of vinylsilylthiophene derivatives with styrene.
5-bromo-2,20-bithiophene (1 g, 4.1 mmol) in 2.5 mL of THF was
added dropwise to the suspension and the reaction mixture was
refluxed. The reaction progress was controlled by GC analysis. Then,
the mixture was cooled to room temperature, excess of organic
solvent was evaporated and the product was isolated by extraction
with hexane/water solvents. The organic layer was separated, dried
under magnesium sulphate and filtered. Then, the solvent was
evaporated, and the residue was separated with silica gel column
(hexane, Rf ¼ 0.33) to afford (4) as a green liquid. Yield: 0.87 g (83%).
1H NMR (CDCl3,
¼
d
(ppm)): 0.42 (s, 6H, eCH3), 5.83 (dd, 1H,
3.8, 20.0 Hz, eHC]CH2), 6.09 (dd, 1H, JHH 3.8,
1H NMR(CDCl3,
d
(ppm)):0.43(s, 6H, eCH3), 5.81(dd,1H, JHH ¼ 3.8,
JHH
¼
14.6 Hz, eHC]CH2), 6.34 (dd, 1H, JHH ¼ 14.6, 20.0 Hz, eHC]CH2),
7.02 (dd, 1H, JHH ¼ 3.7, 5.0 Hz, eSCH]CHeCH]Ce from eC4H3S),
7.16 (d, 1H, JHH ¼ 3.3 Hz, eSeC]CHeCH]Ce from eC4H2Se), 7.20
(d, 1H, JHH ¼ 3.7 Hz, eSCH]CHeCH]Ce from eC4H3S), 7.21 (d, 1H,
JHH ¼ 5.0 Hz, eSCH]CHeCH]Ce from eC4H3S), 7.24 (d, 1H,
JHH ¼ 3.6 Hz, eSeC]CHeCH]Ce from eC4H2Se). 13C NMR (CDCl3,
20.0 Hz, eHC]CH2), 6.08 (dd,1H, JHH ¼ 3.7,14.7 Hz, eHC]CH2), 6.32
(dd,1H, JHH ¼ 14.6, 20.4 Hz, eHC]CH2), 7.22 (dd,1H, JHH ¼ 3.3, 4.7 Hz,
eSCH]CHeCH]Ce from eC4H3S), 7.30 (d,1H, JHH ¼ 3.3 Hz, eSCH]
CHeCH]Ce from eC4H3S), 7.64 (d, 1H, JHH ¼ 4.7 Hz, eSCH]
CHeCH]Ce from eC4H3S). 13C NMR (CDCl3,
d
(ppm)): ꢁ1.6 (eCH3),
128.1 (]CHe from eC4H3S), 130.8 (eCH]CHeSe from eC4H3S),
133.0 (eHC]CH2), 134.6 (eCH]CeS from eC4H3S), 137.5 (eHC]
d
(ppm)): ꢁ1.7 (eCH3), 123.8 (eSeC]CHe from eC4H3S), 124.4
CH2), 137.7 (SieC<). 29Si NMR (CDCl3,
d
(ppm)): ꢁ11,43. MS (EI): m/z
(eSeC]CHe from eC4H3S), 125.0 (eSeC]CHeCH]CeSi
from eC4H2Se), 127.7 (]CHe from eC4H3S), 133.2 (eHC]CH2),
135.4 (eSeC]CHeCH]CeSi from eC4H2Se), 137.1 (eSeC]
CHeCH]CeSie from eC4H2Se), 137.2 (eSeC]CHeCH]CeSie
from eC4H2Se), 137.3 (eHC]CH2), 142.8 (SieC<). 29Si NMR (CDCl3,
(rel. intensity e %): 168 (40), 153 (100), 141 (27), 138 (3), 127 (19), 115
(3),101 (8), 85 (12). HRMS (m/z) Calcd. for C8H12SSi: 168.04290, found
168.04278.
5-(Vinyldimethylsilyl)-2,20-thiophene (4): In a two-neck flask
equipped with magnetic stirrer, under Argon atmosphere,
a suspension of Mg (0.14 g, 5.7 mmol, whose surface was activated
by 1,2-dibromoethane, 0.2 mL) and chlorodimethylvinylsilane
(0.67 mL, 4.9 mmol) in 6 mL of THF was prepared. A solution of
d
(ppm)): ꢁ11.49. MS (EI): m/z (rel. intensity e %): 250ꢃþ (80), 235
(100), 223 (15), 209 (38), 183 (10), 160 (14), 133 (12), 115 (15), 89
(17), 75 (18). HRMS (m/z) Calcd. for C12H14S2Si: 250.03062, found
250.03025.
2,5-bis(Vinyldimethylsilyl)thiophene (5):
A solution of 2,5-
dibromothiophene (6.45 g, 26.7 mmol) in 15 mL of THF was added
slowly dropwise to a suspension of Mg (1.62 g, 66.75 mmol, whose
surface was activated by 1,2-dibromoethane, 0.3 mL) and chlor-
odimethylvinylsilane (8.25 mL, 60.15 mmol) in 15 mL of THF (the
mixture was slightly warmed, 20e30 ꢀC). After the addition was
completed, the reaction mixture was refluxed. The reaction prog-
ress was controlled by GC analysis. Then the mixture was cooled to
Fig. 2. A perspective view of 11 with labelling scheme. Ellipsoids are drawn at the 50%
probability level, hydrogen atoms are shown as spheres of arbitrary radii.
Scheme 7. Stoichiometric reaction of [RueH] (2) with 3.

M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
1461
(CieCi, eC8H4S2e), 137.16 (Ci, 5-C4H2Se), 142.71 (eHC]CH2). 29Si
NMR (CDCl3,
d
(ppm)): ꢁ11.32. MS (EI): m/z (rel. intensity e %):
334ꢃþ (100), 319 (73), 307(17), 293 (22), 275 (5), 261 (10), 244 (25),
229 (16), 207 (8), 154 (6), 127 (9), 115 (14), 101 (10), 85 (23), 73 (14),
59 (26). HRMS (m/z) Calcd. for C16H22S2Si2: 334.07015, found
334.07012.
1,4-Divinylbenzene (DVB) (7): The synthesis of olefin consists of
two steps. We completed the two-stage synthesis of 1,4-divinyl-
benzene (7) using classical Wittig’s reaction (yield 85%, pure
>98.5% GC). In our recent studies we observed that this reaction
occurred even more efficiently when conducted in toluene (1 M
and 0.5 M solution) with lower catalyst loading (1 mol%), however,
it required longer time 48 h.
Scheme 8. Stoichiometric coupling reaction of [RueSi] (16) with styrene.
room temperature, excess of organic solvent was evaporated and
the product was extracted with hexane/water solvents. The organic
layer was separated, dried under magnesium sulphate and filtered.
Then the solvent was evaporated, and the residue was distilled
under reduced pressure to afford the crude product (5) as a col-
ourless liquid (collected fraction 66e70 ꢀC/0.6 mmHg). Yield: 6.26 g
(93%).
The first step, synthesis of methylenetriphenylphosphane:
1H NMR (CDCl3,
3.9, 20.1 Hz, eHC]CH2), 6.06 (dd, 2H, JHH
14.7 Hz, eHC]CH2), 6.31 (dd, 2H, JHH ¼ 19.5, 20.4 Hz, eHC]CH2),
7.35 (s, 2H, ]CHe from eC4H2Se). 13C NMR (CDCl3,
d
(ppm)): 0.41 (s, 12H, eCH3), 5.80 (dd, 2H,
3.9,
Et2O
Ar, r.t.-35oC
JHH
¼
¼
(Ph3PCH3)J
+
t-BuOK
(Ph3P=CH2) + KJ + t-BuOH
d
(ppm)): ꢁ1.45
(eCH3), 132.90 (eHC]CH2), 135.72 (]CHe from eC4H2Se), 137.50
(eHC]CH2), 147.97 (SieC<, from eC4H2Se). 29Si NMR (CDCl3,
Reaction mixture of methyltriphenylphosphane iodide (Ph3PCH3)
I (15 g, 37.1 mmol) and potassium butylate (4.37 g, 38.9 mmol) in
140 mL of diethyl ether was stirred at room temperature for 2 h and
then the mixture was heated at 35 ꢀC. After 12 h the reaction mixture
was cooled at room temperature and filtered with cannula. The
organic solvent was evaporated to afford methylenetriphenyl-
phosphane as yellow crystals (10.19 g, yield: 99%).
d
(ppm)): ꢁ11.82. MS (EI): m/z (rel. intensity e %): 252ꢃþ (24), 237
(100), 212 (50), 167 (16), 148 (24), 133 (9), 85 (73), 75 (18). HRMS
(m/z) Calcd. for C12H20SSi2: 252,08242, found 252.08239.
5,50-bis(Vinyldimethylsilyl)-2,20-bithiophene (6): A solution of
5,50-dibromo-2,20-bithiophene (5.83 g, 7.5 mmol) in 25 mL of THF
was added slowly dropwise to a suspension of Mg (0.45 g,
18.45 mmol, whose surface was activated by 1,2-dibromoethane,
0.15 mL) and chlorodimethylvinylsilane (2.33 mL, 16.95 mmol) in
8 mL of THF (the mixture was slightly warmed, 20e30 ꢀC). After the
The second step, synthesis of 1,4-divinylbenzene:
H
O
O
H
Et2O
Ar, 10-35oC
2.1 (Ph3P=CH2)
+
+ 2.1 (Ph3P=O)
addition was completed, the reaction mixture was heated at 40 ꢀC.
Progress of the reaction was controlled by GC analysis. Then the
mixture was cooled to room temperature, excess of organic solvent
was evaporated and the product was extracted with hexane/water
solvents. The organic layer was separated, dried under magnesium
sulphate and filtered. Then the solvent was evaporated, and the
residue was separated by silica gel chromatography, eluting with n-
hexane (Rf ¼ 0.46) (2.015 g, yield 90%) to afford the crude product
(6) as a greenish liquid.
Terephthalic aldehyde (2.22 g, 16.5 mmol) was added slowly to
a suspension of methylenetriphenylphosphane (10.19 g, 36.7 mmol)
in 100 mL diethyl ether at room temperature. The mixture colour
changed from yellow to green-blue-violet-bordeaux (deep-red).
After the addition was completed, the reaction mixture was heated
at 35 ꢀC for 2 h. Then, the synthetic air (20 mL) was injected into the
reaction mixture by syringe and cooled to 10 ꢀC, the mixture was
filtered with cannula, concentrated to 40 mL and filtered again. The
organic solvent was evaporated and the residue was distilled trap-
to-trap to afford the crude product (7) as a white solid (“flowing” at
30 ꢀC) (1.83 g, yield 85%, pure >98.5% GC).
1H NMR (CDCl3,
3.9, 20.4 Hz, eHC]CH2), 6.07 (dd, 2H, JHH
d
(ppm)): 0.40 (s, 12H, eCH3), 5.81 (dd, 2H,
3.9,
JHH
¼
¼
15.0 Hz, eHC]CH2), 6.29 (dd, 2H, JHH ¼ 14.7, 20.1 Hz, eHC]CH2),
7.17 (d, 2H, JHH ¼ 3.9 Hz, 3eC4H2Se), 7.28 (d, 2H, JHH ¼ 4.2 Hz, 4-
1H NMR (C6D6,
5.68 (d, 2H, JHH ¼ 17.4 Hz, eCH]CH2), 6.57 (dd, 2H, JHH ¼ 11.1,
18.0 Hz, eCH]CH2), 7.19 (s, 4H, eC6H4e). 13C NMR (C6D6,
(ppm)):
d
(ppm)): 5.25 (d, 2H, JHH ¼ 9 Hz, eCH]CH2),
C4H2Se). 13C NMR (CDCl3,
d
(ppm)): ꢁ1.72 (eCH3), 125.08 (]CHe,
d
3-C4H2Se), 133.22 (eHC]CH2), 135.42 (]CHe, 4-C4H2Se), 137.43
114.12 (eCH]CH2), 127.25 (eC6H4e), 137.36 (eCH]CH2), 137.96
(>CeCH]CH2). MS (EI): m/z (rel. intensity e %): 130 (Mþꢃ) (100),
115 (39),103 (10), 89 (5), 77 (12), 63 (15), 51 (20). HRMS (m/z) Calcd.
for C12H20SSi2: 130.07825, found 130.07838.
4.4. A typical procedure for catalytic examinations
The oven dried 5 mL glass ampoule-reactor equipped with
a magnetic stirring bar was charged under argon with toluene
(amount depend of total concentration e 1 M, 0.5 M), vinylsilane
(0.595 mmol), decane (5% of total volume of reaction mixture -
internal standard) olefin (styrene or 1,4-divinylbenzene (DVB), the
amount depended on the [olefin]:[ViSi] ratio ¼ 1:1 for styrene and
Scheme 9. SCCP of bis(dimethylvinylsilyl)thiophenes with 7.

1462
M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
1:2.1 for DVB) and ruthenium-hydride complex RuHCl(CO)(PCy3)2
(1) (2 mol%, 1.5 mol%, 1 mol%, 0.5 mol%). The system was heated in
an oil bath at 80e100 ꢀC for 3e48 h. The reaction progress was
monitored by gas chromatography (GC), mass spectroscopic anal-
ysis (MS) and 1H NMR (NMR spectra were measured at room
temperature in CDCl3 solution).
2,5-bis{((E)-2-Phenylethenyldimethylsilyl)}thiophene (10): 1H NMR
(CDCl3,
(ppm)): 0.51 (s,12H, CH3), 6.61 (d, 2H, JHH ¼ 18.6 Hz, SieCH]
d
CHe), 7.01 (d, 2H, JHH ¼ 18.6 Hz, SieHC]CHe), 7.28e7.38 (m, 6H, 3,4-
C6H5), 7.43 (]CHe z C4H2S), 7.48 (d, 4H, JHH ¼ 7.8 Hz, 2-C6H5). 13
C
NMR (CDCl3,
d
(ppm)): ꢁ1.25 (eCH3), 126.48 (3-C6H5), 128.16
(4-C6H5), 128.41 (2-C6H5), 135.82 (SieHC]CHe), 137.87 (Ci from
C6H5), 144.26 (Ci from C4H2S), 145.25 (SieHC]CHe). 29Si NMR
(CDCl3,
d
(ppm)): ꢁ11.43. MS (EI): m/z (rel. intensity e %): 404 (Mþꢃ),
4.5. Isolation procedure of molecular compounds
389, 315, 301, 286, 219, 195, 161, 145, 105, 73. HRMS (m/z) Calcd. for
C24H28SSi2: 404.14502, found 404.14499. White powder, yield 92%.
All molecular compounds were isolated from the best catalytic
tests mixtures. After the reaction was completed, solvent was
evaporated. The final solution was separated with silica gel column
(hexane, Rf ¼ 0.30e0.55).
Me
Me
4.5.1. Analytical data of molecular compounds
{(E)-1-Phenyl-2-(dimethyl-2-thienylsilyl)}ethene (8): 1H NMR
S
Si
Me
Si
Me
(CDCl3,
d
(ppm)): 0.51 (s, 6H, eCH3), 6.60 (d, 1H, JHH ¼ 18.9 Hz,
SieCH]CHeC<), 7.00 (d, 1H, JHH ¼ 19.2 Hz, SieCH]CHeC<), 7.23
(dd, 1H, JHH ¼ 3.3, 4.7 Hz, SeCH]CHeCH]C, from eC4H3S),
7.30e7.38 (m, 3H, 3,4-C6H5), 7.34 (d, 1H, JHH ¼ 3.3 Hz, SeCH]
CHeCH]Ce from eC4H3S), 7.47 (d, 2H, JHH ¼ 8.2 Hz, 2-C6H5), 7.60
(d, 1H, JHH ¼ 4.7 Hz, eSeCH]CHeCH]Ce from eC4H3S). 13C NMR
5,50-bis{((E)-2-Phenylethenyldimethylsilyl)}-2,20-bithiophene
(11): 1H NMR (CDCl3,
(ppm)): 0.51 (s, 12H, eCH3), 6.59 (d, 2H,
d
JHH ¼ 19.2 Hz, SieHC]CHe), 7.01 (d, 2H, JHH ¼ 19.2 Hz, SieHC]
CHe), 7.20 (d, 2H, JHH ¼ 3.9 Hz, 3-C4H2Se), 7.28 (d, 2H, JHH ¼ 3.2 Hz,
4-C4H2Se), 7.31e7.38 (m, 6H, 3,4-C6H5), 7.48 (d, 4H, JHH ¼ 7.8 Hz,
(CDCl3,
d
(ppm)): ꢁ1.2 (eCH3), 126.5 (3-C6H5), 126.5 (SieHC]CHe),
128.1 (]CHeS from eC4H3S), 128.2 (4-C6H5), 128.4 (2-C6H5), 130.8
(eCH]CHeSe from eC4H3S), 134.7 (eCH]CeS from eC4H3S),
145.4 (SieHC]CHe), 137.9 (Ci from eC6H5), 137.9 (SieC<). 29Si
2-C6H5). 13C NMR (CDCl3,
d
(ppm)): ꢁ1.30 (eCH3), 125.13 (]CHe,
3-C4H2Se), 126.11 (3-C6H5), 126.50 (SieHC]CHe), 128.24 (4-C6H5),
128.42 (2-C6H5), 135.51 (]CHe, 4-C4H2Se), 137.68 (CieCi,
from eC8H4S2e),137.80 (Ci from eC6H5), 142.78 (Ci from 5-C4H2Se),
NMR (CDCl3,
d
(ppm)) ¼ ꢁ10.78. MS(EI) m/z (rel. intensity e %): 244
(Mþꢃ) (60), 229 e CH3 (59), 195 (16), 154 e styryl (24), 145 e CH3
and eC4H3S (100), 127 MeSiC4H3S (18), 101 (12), 91 (10), 75 (18).
HRMS (m/z) Calcd. for C12H14S2Si: 244.07420, found 244.07412.
White powder/solid, yield 99%.
145.59 (SieHC]CHe). 29Si NMR (CDCl3,
d
(ppm)): ꢁ10.67. MS (EI):
m/z (rel. intensity e %): 487 (Mþꢃ), 472, 457, 397, 382, 370, 327, 307,
282, 238, 207, 162, 147, 137, 115, 105, 73. HRMS (m/z) Calcd. for
C28H30S2Si2: 486.13275, found 486.13268. White powder, yield 96%.
Me
Si
S
Me
Me
Me
Si
S
S
Me
Si
{(E)-1-Phenyl-2-(dimethyl-5-(2,20-bithiophene)silyl)}ethene (9): 1H
NMR (CDCl3,
(ppm)): 0.51 (s, 6H, eCH3), 6.60 (d, 1H, JHH ¼ 19.1 Hz,
Me
d
SieCH]CHeC<), 7.00 (d, 1H, JHH ¼ 19.1 Hz, SieCH]CHeC<), 7.02
(dd, 1H, JHH ¼ 3.6, 5.0 Hz, SeCH]CHeCH]C, from eC4H3S), 7.20
(d, 1H, JHH ¼ 3.3 Hz, SeC]CHeCH]C, from eC4H2Se), 7.20
(d, 1H, JHH ¼ 3.6 Hz, SeCH]CHeCH]C, from eC4H3S), 7.22 (d, 1H,
JHH ¼ 5.0 Hz, SeCH]CHeCH]C, from eC4H3S), 7.28 (d, 1H,
JHH ¼ 3.0 Hz, SeC]CHeCH]C, from eC4H2Se), 7.30e7.38 (m, 3H,
1,4-bis{((E)-2-Ethenyldimethyl-2-thienylsilyl)}benzene (12): 1H
NMR (CDCl3,
d
(ppm)): 0.48 (s,12H, eCH3), 6.58 (d, 2H, JHH ¼ 18.9 Hz,
SieCH]CHeC<), 6.95 (d, 2H, JHH ¼ 19.2 Hz, SieCH]CHeC<), 7.22
(dd, 2H, JHH ¼ 3.3, 4.7 Hz, SeCH]CHeCH]C), 7.33 (d, 2H,
JHH ¼ 3.3 Hz, SeCH]CHeCH]C), 7.42 (s, 4H, eC6H4e), 7.64 (d, 2H,
3,4-C6H5), 7.5 (d, 2H, JHH ¼ 8.6 Hz, 2-C6H5). 13C NMR (CDCl3,
d (ppm)):
ꢁ1.3 (eCH3),123.8 (SeCH]CHeCH]C from eC4H3S),124.4 (SeCH]
CHeCH]C from eC4H3S), 125.0 (]CHe, 3-C4H2Se), 126.1 (3-C6H5),
126.5 (SieHC]CHeC<), 127.7 (SeCH]CHeCH]C from eC4H3S),
128.3 (4-C6H5), 128.5 (2-C6H5), 135.5 (]CHe, 4-C4H2Se), 137.2 (Ci
from eC4H3S), 137.6 (Ci, >CeC< from eC4H2Se), 137.8 (Ci
from eC6H5), 142.9 (Ci, >CeSi from eC4H2Se) 145.6 (SieHC]
JHH ¼ 4.7 Hz, SeCH]CHeCH]C). 13C NMR (CDCl3,
d
(ppm)): ꢁ1.2
(eCH3),126.8 (SieCH]CHeC<),128.1 (SeCH] from eC4H3S),128.7
(]CHe from eC6H4e), 130.9 (SeCH]CHeCH]C from eC4H3S),
134.7 (SeCH]CHeCH]C from eC4H3S), 137.8 (Ci from eC4H3S),
140.2 (Ci from eC6H4e), 144.9 (SieCH]CH<). 29Si NMR (CDCl3,
CHeCH<). 29Si NMR (CDCl3,
d
(ppm)): ꢁ10.84. HRMS (m/z) Calcd. for
d
(ppm)): ꢁ10.78. HRMS (m/z) Calcd. for C12H14S2Si: 410.10145,
found 410.10126. White powder, yield 95%.
C12H14S2Si: 326.06192, found 326.06175. White powder, yield 95%.
Me
S
S
Si
Me
Si
Me
Me
S
S
Me
Si
Me

M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
1463
1,4-bis{((E)-2-Ethenyldimethyl-5-(2,20-bithiophene)silyl)}benzene
(13): 1H NMR (CDCl3,
(ppm)): 0.51 (s, 12H, eCH3), 6.57 (d, 2H,
JHH ¼ 18.9 Hz, SieCH]CHeC<), 7.00 (d, 2H, JHH ¼ 19.1 Hz, SieCH]
CHeC<), 7.03 (dd, 2H, JHH ¼ 3.6, 5.0 Hz, SieC]CHeCH]Ce, from
C4H2S), 7.10 (d, 2H, JHH ¼ 3.0 Hz, eC]CHeCH]Ce, from C4H3S), 7.21
(d, 2H, JHH ¼ 3.6 Hz, SeCH]CHeCH]C, from C4H3S), 7.32 (d, 2H,
from copolymer), 5.80 (dd, 2H, JHH ¼ 3.6, 20.2 Hz, SieHC]CH2, from
terminal group), 5.96 (dd, 2H, JHH ¼ 3.6, 15.1 Hz, SieHC]CH2, from
terminal group), 6.16 (dd, 2H, JHH ¼ 14.7, 20.1 Hz, SieHC]CH2,
from terminal group), 6.56 (d, 1H, JHH ¼ 19.2 Hz, SieHC]CHeC<),
6.83 (s, 2H, SieHC]CHeSi homo-coupling traces), 6.96 (d, 1H,
JHH ¼ 18.9 Hz, SieHC]CHeC<), 7.18 (d, 2H, JHH ¼ 3.3 Hz, 3-C4H2Se),
7.27 (d, 2H, JHH ¼ 3.6 Hz, 4-C4H2Se), 7.42 (s, 4H, eC6H4e). 13C NMR
d
JHH
¼
5.0 Hz, CeCH]CHeCH]C, from C4H3S), 7.62 (s, 4H,
from eC6H4e), 7.64(d, 2H, JHH ¼ 4.7 Hz, CeCH]CH]Ce, from C4H2S).
(CDCl3,
d
(ppm)): ꢁ1.4 (eCH3 from copolymer), ꢁ1.5 (eCH3 from
13C NMR (CDCl3,
d
(ppm)): ꢁ1.29 (eCH3), 123.7 (]CHe from
terminal part), 126.8 (]CHe from eC6H4e), 132.7 (SieHC]CH2),
135.8 (]CHe from eC4H2Se), 135.9 (SieHC]CHeC<), 137.9 (Ci
from eC6H4e), 144.2 (SieHC]CH2), 144.2 (Ci from C4H2S), 145.2
ndash;C4H3S), 124.6 (]CHe from eC4H3S), 126.8 (SieHC]CHeC<),
125.3 (]CHe from eC4H3S), 128.7 (]CHe from eC6H4e), 135.7 (]
CHe, 4-C4H2Se), 136.9 (]CHe, 4-C4H2Se), 136.7 (Ci from eC4H3S),
137.6 (Ci, >CeC< from -C4H2Se), 140.2 (Ci from eC6H4e), 142.7
(Ci, >CeSi from eC4H2Se), 145.2 (SieHC]CHeCH<). 29Si NMR
(SieHC]CHeC<). 29Si NMR (CDCl3,
d
(ppm)) ¼ ꢁ10.82, ꢁ11.49.
Elem. Anal. Calcd. for (C22H24S2Si2)n: C 64.65, H 5.92; Found C 63.97,
H 5.90. GPC: Mw ¼ 6065 [g molꢁ1], Mn ¼ 4626 [g molꢁ1], PDI (M w/M
n) ¼ 1.31, n ¼ 11. The compound was isolated as white powder.
(CDCl3)
d
¼ ꢁ10.85. HRMS (m/z) Calcd. for C12H14S2Si: 486.13275,
found 486.13268. White powder, yield 80%.
4.7. Synthesis of rutheniumesilyl complex Ru(SiMe2C4H3S)Cl(CO)
(PPh3)2 (II) (16)
S
Me
S
S
The title compound was synthesized essentially in a manner
similar to that reported in ref. 23, with modifications applied to
improve meaningfully the yield of the reaction synthesis.
Si
Me
Si
Me
S
Me
RuHCl(CO)(PPh3)3 (300 mg, 3.15 ꢂ 10ꢁ4 mol) was refluxed in
toluene (10 mL) forming a suspension. Afterwards, 2 (159 mg,
9.45 ꢂ 10ꢁ4 mol) was added to the mixture, and the final com-
mixture was refluxed for 22h to give a light yellow solution. The
excess of solvent was evaporated under reduced pressure, followed
by the addition of hexane and gave a yellow precipitate. Next, the
latter was filtered (‘canula’ system), washed with cold hexane
(3 ꢂ 15 mL) and dried in vacuum (0.18 g, 69% yield).
4.6. A general procedure for silylative coupling (SC)
copolycondensation
The syntheses were performed under argon using (1) as a cata-
lyst. Reagents and solvent were dried and deoxygenated. A mixture
of monomer 4 or 5 (1.5 mmol), DVB (1.5 mmol), complex 1
(0.015e0.075 mmol) and toluene (1.5e6 mL, 1e0.25 M) was placed
in a 5e10 mL glass mini-reactor equipped with a magnetic stirring
bar and condenser connected to a bubbler. The reaction mixture
was stirred and heated at 90e100 ꢀC under an argon flow for 72 h.
After the reaction was completed, the excess of solvent was evap-
orated under vacuum. The resulting polymer was dissolved in THF,
isolated and purified by repeated precipitation from methanol. The
final polymeric material was filtered off and dried under vacuum
for 10e15 min. The isolated yields were as follows: for 14 e 90% and
for 15 e 63% (depending on the combination of starting bis(silyl)
thiophene derivative monomer).
1H NMR (C6D6,
d (ppm)): 0.97 (s, 6H, eCH3), 7.03e7.11 (m, 18H,
-C6H5), 7.24 (dd, 1H, JHH ¼ 3.3, 4.7 Hz, from eC4H3S), 7.58 (d, 1H,
JHH ¼ 3.3 Hz, from eC4H3S), 7.68 (d, 1H, JHH ¼ 4.7 Hz, from eC4H3S).
31P NMR (C6D6,
d n (CO)).
(ppm)): 32.7 (s). IR (KBr, cmꢁ1) 1917 (
Elemental Analysis: calculated C 62.19, H 4.73; found C 62.11, H 4.70.
4.8. Procedure of stoichiometric reaction in NMR tube
In a typical NMR tube, 0.015 g (1.81 ꢂ 10ꢁ5 mol) of 16 (the tube
was deoxygenated), decane (internal standard) and 0.6 mL of C6D6
were placed under argon. Then, 2.82 mg (2.71 ꢂ 10ꢁ5 mol) of
styrene was added and the reaction mixture was heated at 35 ꢀC for
1 h, then up to 60 ꢀC. Progress of the catalytic process was moni-
tored by 1H NMR and MS at room temperature.
4.6.1. Analytical data of copolymers
Poly[dimethylsilylene-2,5-thienylene-dimethylsilylene-(E)-vinyl-
4.9. Procedure of GCMS test in glass reactor
ene-1,4-phenylene-(E)-vinylene] (14): 1H NMR (CDCl3,
d (ppm)): 0.40
(s, 12H, eCH3 from terminal part), 0.49 (s, 12H, eCH3 from copol-
ymer), 5.80 (dd, 2H, JHH ¼ 3.9, 20.1 Hz, SieHC]CH2, from ter-
minal group), 6.05 (dd, 2H, JHH ¼ 3.9, 14.7 Hz, SieHC]CH2,
from terminal group), 6.27 (dd, 2H, JHH ¼ 19.5, 20.4 Hz, SieHC]CH2,
from terminal group), 6.84 (s, 2H, SieHC]CHeSi, traces of homo-
coupling), 7.40 (s, 2H, ]CHe from eC4H2Se), 7.41 (s, 4H,
In a typical glass reactor (3 mL), 0.010 g (1.21 ꢂ 10ꢁ5 mol) of 16
(the tubewas deoxygenated), and 1 mL of toluene wereplaced under
argon. Then, 7
m
L (3.63 ꢂ 10ꢁ5 mol) of styrene was added and the
reaction mixture was heated at 60 ꢀC for 1 h and 24 h. Progress of the
catalytic process was monitored by GCeMS at room temperature.
from eC6H4e DVB). 13C NMR (CDCl3,
d
(ppm)): ꢁ1.1 (eCH3 from
4.10. X-ray structure determination
copolymer), ꢁ1.6 (eCH3 from terminal part), 126.7 (]CHe
from eC6H4-), 132.7 (SieHC]CH2), 135.8 (]CHe from -C4H2Se),
135.9 (SieHC]CHeC<),137.8 (Ci from eC6H4e),144.2 (SieHC]CH2),
144.2 (Ci from C4H2S), 144.7 (SieHC]CHeC<). 29Si NMR (CDCl3,
Diffraction data were collected at room temperature by the
u
-scan technique on an Oxford Diffraction SuperNova four-circle
diffractometer with Atlas CCD-detector, equipped with Nova
microfocus CuKa radiation source (
d
(ppm)): ꢁ11.10, ꢁ11.12. Elem. Anal. Calcd. for (C18H22SSi2)n: C 66.19,
l
¼ 1.5418 Å). The data were
H 6.79; Found C 65.97, H 6.75. GPC: Mw ¼ 4313 [g molꢁ1], Mn ¼ 3067
[g molꢁ1], PDI ðMw=MnÞ ¼ 1.406, n ¼ 8. The compound was isolated as
white powder.
corrected for Lorentz-polarization as well as for absorption effects
[30]. Accurate unitecell parameters were determined by the least-
squares fit of 4419 (10) and 19387 (11) reflections of highest inten-
sity, chosen from the whole experiment. The structures were solved
with SIR92 [31] and refined with the full-matrix least-squares
procedure on F2 by SHELXL97 [32]. Scattering factors incorporated
Poly[dimethylsilylene-5,50-(2,20-bithienylene)-dimethylsilylene-
(E)-vinylene-1,4-phenylene-(E)-vinylene] (15): 1H NMR (CDCl3,
d
(ppm)): 0.40 (s, 12H, eCH3 from terminal part), 0.48 (s, 12H, eCH3

1464
M. Ludwiczak et al. / Journal of Organometallic Chemistry 696 (2011) 1456e1464
in SHELXL97 were used. The function Sw(jFoj2-jFcj2)2 was
(c) B.C. Thomas, P. Schotlland, K. Zong, J.R. Reynolds, Chem. Mater. 12 (2000)
1563.
minimized, with wꢁ1 ¼ [
s
2(Fo)2 þ (A$P)2 þ B$P] (P ¼ [Max
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(Fo2, 0) þ 2F2c]/3). The final values of A and B are listed in Table 1. All
non-hydrogen atoms were refined anisotropically. The hydrogen
atoms in 10 were found in the difference Fourier maps and iso-
tropically refined, while in 11 they were placed geometrically, in
idealized positions, and refined as rigid groups with their Uiso’s as 1.2
or 1.5 (methyl) times Ueq of the appropriate carrier atom. Relevant
crystal data are listed in Table 1, together with refinement details.
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Acknowledgement
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This work is supported by a grant No. N204 26 55 38 from the
Ministry of Science and Higher Education (Poland).
Appendix A. Supplementary material
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CCDC numbers 795151 (10) and 795152 (11) contain the
supplementary crystallographic data for this paper. This data can be
obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif.
Appendix. Supplementary material
Supplementary data associated with this article including GCMS
spectra (Fig. 3 and Fig. 4) and summary of crystals data (Table 5).
Supplementary data related to this article can be found online at
doi:10.1016/j.jorganchem.2011.01.020.
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