Highly stereoselective synthesis of arylene-silylene-vinylene polymers

Article abstract of DOI:10.1002/adsc.200404350

Stereoregular trans-arylene-silylene-vinylene polymers of M_W = 13100-34800 and PDI = 1.6-2.9 of the general formulas CH₂=CH-[- SiMe₂C₆H₄SiMe₂CH=CH-]-(16, 17, 18) and CH₂=CH-[-(R)

Full text of DOI:10.1002/adsc.200404350

FULL PAPERS
Highly Stereoselective Synthesis of Arylene-Silylene-Vinylene
Polymers
Mariusz Majchrzak, Bogdan Marciniec,* Yujiro Itami
Department of Organometallic Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6,
60-780 Poznan, Poland
Tel: (þ48)-61-8291-366, Fax: (þ48)-61-8291-508, e-mail: marcinb@amu.edu.pl
Received: November 17, 2004; Accepted: April 15, 2005
Dedicated to Professor Julian Chojnowski on the occasion of his 70th birthday in recognition of his significant
contribution to organosilicon polymer chemistry.
Abstract: Stereoregular trans-arylene-silylene-vinyl- of bis(vinyldimethylsilyl)arenes (10, 12 and 14) with
ene polymers of Mw ¼13100–34800 and PDI¼1.6– 1,4-divinylbenzene (9) catalyzed by [RuH(Cl)(CO)
¼
ꢀ ꢀ
2.9 of the general formulas CH2 CH [ SiMe2C6H4- (PCy3)2] (7). Such highly stereoregular products can-
SiMe2CH CH ] (16, 17, 18) and CH2 CH [ (R) not be synthesized via ADMET polycondensation
¼
ꢀ ꢀ
¼
ꢀ ꢀ
¼
¼
ꢀ ꢀ
ꢀ
ꢀ
CH CHC6H4CH CH ] (where R¼ Me2Si-p C6H4- or ring opening metathesis ROM or polyaddition of
ꢀ ꢀ
ꢀ
ꢀ
ꢀ
SiMe2
,
Me2Si-m C6H4SiMe2 and Me2SiC6H4- hydridosilanes to acetylenes.
ꢀ
C6H4SiMe2 ) (19, 20, 21) have been effectively syn-
thesized via silylative coupling (SC) homopolycon-
densation of bis(vinyldimethylsilyl)arenes (10, 12, Keywords: arylene-silylene-vinylene polymers; homo-
14) and cross-polycondensation of 4-(vinyldimethyl- geneous catalysis; polycondensation; ruthenium; sily-
silyl)styrene (11) as well as cross-copolycondensation lative coupling
Introduction
mopolymers, which include carbosilane and carbosilox-
ane units, can be synthesized using this methodology[9]
Polymers with silylene-bridged p-conjugated systems (Scheme 1).
have recently received a lot of attention because of their
As opposed to the aforesaid monomers, the vinyl de-
potential usefulness in opto-electronic functional mate- rivatives of silicon compounds are completely inert to
rials.[1–3] In particular arylene-silylene-vinylene poly- productive homometathesis due to steric and electronic
mers have been reported to show interesting photophys- effects of the silyl group stimulating non-productive
ical properties.[4] The introduction of silicon atoms into cleavage of metalla-cyclobutane intermediate contain-
p-conjugated systems seems to raise the LUMO of the ing two silyl groups attached to adjacent carbon
p-conjugated systems, and improves their solubility atoms.[10]
and processibility due to increased flexibility. Moreover,
However, in the presence of ruthenium complexes
ꢀ
ꢀ
the presence of Si-atoms reduces the barrier injection which contain or generate [Ru H] and [Ru Si] bonds,
and transportation processes, in comparison with those such compounds as divinylsilanes,[11,12] divinyldisilox-
of other polymers containing saturated spacer groups.[5] anes,[11,12] divinyldisilazane[13] and bis(vinylsilyl)al-
Polymers containing phenylene-silylene-vinylene kanes[14] undergo a silylative coupling (SC) polyconden-
units are usually synthesized by Pt- and Rh-catalyzed sation to linear products according to Scheme 2 (for a re-
hydrosilylation,[6] but the polymer-chain structures cent review, see[8]).
were present as a mixture of gem-, cis-1,2- and trans-
1,2-isomeric fragments.
Furthermore, we have also reported preliminary re-
sults for the synthesis of homopolymers containing phe-
One of the ways of the synthesis of unsaturated silicon
oligomers and polymers is acyclic diene metathesis
(ADMET) polymerization of silicon-containing dienes
such as dialkenylenes and siloxanes (with the exception
of divinyl derivatives), occurring smoothly in the pres-
ence of highly active metallacarbenes (M¼W, Mo,
Ru) (for recent reviews, see[7,8]). These unsaturated ho- Scheme 1.
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DOI: 10.1002/adsc.200404350
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Mariusz Majchrzak et al.
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under different conditions (temperature, ratio of sub-
strates, substituted at silicon, etc.).
For the synthesis of homopolymers having the ary-
lene-silylene-vinylene unit we have made several cata-
lytic tests of the following model reaction – the silylative
homo-coupling process of vinylphenyldimethylsilane
(whose structure is similar to the fragments of chains
of the desired polymers) catalyzed by five- and six-coor-
dinated ruthenium catalysts, according to the Scheme 4.
Many ruthenium complexes have been tested in the si-
lylative-coupling reaction. The basic assumption of the
Scheme 2.
nylene-silylene-vinylene and copolymers consisting of synthetic procedure requires the absence of gem-prod-
phenylene-silylene-vinylene-phenylene-vinylene frag- uct. The results are presented in Table 1, along with
ments with well-defined structures[17] which are of grow- those reported earlier on silylative coupling occurring
ing interest due to their efficient photo- and electrolumi- in the presence of different catalysts and under different
nescence properties.[4,16]
conditions.
Under suitable conditions, the mechanism of silylative
The catalysis of the initial hexacovalent ruthenium
coupling reaction of monovinylsilanes is well-establish- complexes (2, 3, 4, 5 and 8) was less effective than in
ed (for reviews, see[7,8,15] and involves a cleavage of the the presence of pentacoordinated (6 and 7) species,
¼ ꢀ
carbon-silicon ( C Si) bond of the vinylsilane and the i.e., coordinatively unsaturated. Obviously, the catalytic
¼ ꢀ
carbon-hydrogen ( C H) bond of the olefin (e.g., styr- activities of complexes 6 and 7 are very similar but when
ene) or a second vinylsilane molecule (in the silylative the silyl-ruthenium complex (6) is used a significant
homo-coupling) as shown in Scheme 3, for the stereose- amount of gem-product was also observed.
lective synthesis of trans-product.
In this case, we selected more active catalysts from this
The aim of this work was to apply silylative coupling group – dimeric ruthenium (1) and two ruthenium phos-
(SC) polycondensation as a new synthetic route to pre- phine complexes (6, 7) – and used them in preliminary
pare regio- and stereoselectively trans-polymeric mate- catalytic tests in order to choose the best conditions
rials, poly(arylene-silylene-vinylene)s.
for selective synthesis of a well-defined trans-polymer.
The results are presented in Table 2.
While the catalyst 6 gave a mixture of trans-1,2-iso-
meric fragments and 1,1-isomeric fragments the cata-
lysts 1 and 7 gave only trans-isomeric derivatives. There-
Results and Discussion
Although different ruthenium complexes have been fore, we used the [RuH(Cl)(CO)(PCy3)2] complex 7 as a
used for the silylative coupling reaction of various ole- catalyst for a long-time reaction occurring according to
fins, their reactivity and selectivity have not been direct- Scheme 5, to obtain polymers with rather high average
ly compared, since the reactions have been performed molecular weight and low polydispersity index.
The structures of the obtained polymers were charac-
terized and determined by 1H, 13C and 29Si NMR as well
as IR and Raman spectroscopy. The absence of frag-
ments with a quaternary carbon atom was also revealed
by DEPT spectroscopic analysis. The 13C NMR and
DEPT spectra are shown in Figs. 1 and 2, respectively.
Similarly, in order to synthesize a homopolymer con-
sisting of arylene-silylene-vinylene-phenylene-vinylene
Scheme 3. Mechanism of silylative coupling reaction of vinyl-
silanes catalyzed by ruthenium complexes.
Scheme 4. Model reaction of silylative coupling of vinylphe-
nyldimethylsilane.
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Stereoselective Synthesis of Arylene-Silylene-Vinylene Polymers
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Table 1. Effect of catalyst on the conversion of vinylphenyldimethylsilane and chemo-selectivity process.
Catalyst
Conversion of VinSiMe2Ph [%][a]
Yield of products[b] [%]
[trans-] : [gem-]
ꢀ
{[Ru(m Cl)2(CO)3]}2
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
53
74
36
16
11
85
85
13
512
72
36
16
10
78
85
13
2
2
–
–
1
7
–
–
[RuH(Cl)(CO)(PPh3)3]
[RuH(Cl)(CO)2(PPh3)2]
[RuH(OAc)(CO)(PPh3)2]
[RuH(OAc)(PPh3)3]
[Ru(SiMe3)(Cl)(CO)(PPh3)2]
[RuH(Cl)(CO)(PCy3)2]
[RuH(OAc)(CO)(PCy3)2]
[a]
Conversion calculated from GC.
Calculated from GC and identified by use GC-MS and NMR methods.
– Not observed.
[b]
Reaction conditions: [VinSi]:[Ru]¼100: 1, in toluene (1 M), under Ar, 18 h, 1108C.
Table 2. Catalytic tests for polycondensation of 1,4-bis(vinyldimethylsilyl)benzene (10).
Catalyst
Conversion of monomer [%][a]
Ratio of products [%][b]
Selectivity [%][c]
[1,2-]/[1,1-]
Dimer
Trimer
Oligomers
1
6
7
86
92
97
23
17
12
22
21
16
55
62
72
>99
75 25
>99
0
0
[a]
Conversion calculated from GC.
[b]
[c]
Identified by use GC-MS and GPC.
1
Calculated from H NMR.
Reaction conditions: [monomer]:[cat.]¼100: 1, in toluene (1 M), 24 h, 1108C, under Ar.
Scheme 5. General scheme of silylative coupling (SC) poly-
condensation of bis(vinyldimethylsilyl)arenes (10, 12, 14) in
the presence of complex 7.
Figure 1. 13C NMR spectrum of homopolymer 16 in CDCl3.
units, various ruthenium complexes have been tested for nylsilyl and styryl) using the very effective and active
the silylative cross-coupling reaction. The catalytic ruthenium complex 7 as a catalyst, see Scheme 6.
screenings have been carried out in the model catalytic
The structure of its main chain was a result of a ꢁhead-
to-tailꢂ polycondensation reaction. The next issue of our
process of vinyldimethylphenylsilane with styrene.[20]
The regio- and stereoregular trans-homopolymer 15 interest was the synthesis of unsaturated organosilicon
was effectively prepared by polycondensation of 11 copolymers. Like in the case of establishing the reaction
(monomer which consists of two functional groups: vi- conditions for the synthesis of homopolymers, we car-
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Scheme 7. Model reaction of silylative cross-coupling of vi-
nylsilanes with 1,4-divinylbenzene (9).
Figure 2. DEPT spectrum of homopolymer 16.
Complex 7 catalyzes chemoselectively this coupling
reaction to obtain exclusively trans-stereoproducts.
Thus, copolymers 19, 20, and 21 were synthesized by co-
polycondensation via silylative-cross-coupling reaction
of bis(vinyldimethylsilyl)arene derivative monomers
(10, 12 and 14) with DVB (9) under the conditions pre-
sented in Scheme 8.
In the above reaction conditions we have never ob-
served uncontrolled radical polymerization of 1,4-di-
vinylbenzene.
The chemical structures of the products were verified
by methods described in the experimental section. The
analytical data allowed us to propose linear and trans-
(stereo)regular structures of the polymeric materials ob-
tained with perfect consecutive arylene-silylene-vinyl-
Scheme 6. Scheme of silylative cross-coupling (SC) polycon-
densation of 4-(vinyldimethylsilyl)styrene (11) in the pres-
ence of catalyst 7.
ried out preliminary catalytic tests using chosen rutheni- ene or arylene-silylene-vinylene-phenylene-vinylene
um complexes, according to the Scheme 7: linkages. The results of spectroscopic analyses of all
The results are presented in Table 3. It has been found products obtained in the presence of this catalyst exclud-
that only one catalyst, complex 7, is the best for the prep- ed the occurrence of quaternary carbons
[( SiMe2)2C CH2)] in the polymerꢂs main chains. Ex-
ꢀ
¼
aration of well-defined copolymers.
Table 3. Effect of catalyst on the conversion of DVB (9), vinylsilanes and chemoselectivity of the process.
Vinylsilane
Catalyst
Conversion of DVB [%][a]
Conversion of VinSi [%][a]
Yield of products [%][b]
homo-
mono-
di-
VinSiMe2Ph
2
6
7
2
6
7
84
92
97
80
86
95
71
69
91
66
68
88
4
8
–
2
5
–
34
54
12
33
46
14
50
38
85
47
40
81
VinSiMe2C12H9
[a]
Conversion calculated from GC.
Calculated from GC and identified by use GCMS and NMR methods.
– Not observed.
[b]
Reaction conditions: [VinSi]:[DVB]:[Ru]¼200: 100: 1, in toluene (0.5 M), under Ar, 18 h, 808C.
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Stereoselective Synthesis of Arylene-Silylene-Vinylene Polymers
FULL PAPERS
izing similar structures). The typical GPC traces of ex-
emplary products 15, 19, 20, 21 are presented in Figure 5.
The calculated polydispersity (PDI) of the polymers
was in the range between 1.6 and 2.9 (see Table 4).
The thermal stability of the polymers was ascertained
on the basis of thermogravimetric analysis (TGA), see
Table 4. As follows from the TGA thermal analysis pro-
files (Fig. 6), the polymers started to lose weight near
1008C for 17, 1988C for 16 and very similarly for 18,
1158C for 19, 2408C for 20 and 2658C for 15 and 21,
and the maximum decomposition rate was between
4148C and 5998C in the TGAexperiment (Figure 6).
The final residue yields were in the range 53–77% at
9008C.
Although the overall trends are very similar, early-
stage decomposition profiles differ, depending on the
arene structure: that with biphenylene fragment 21 is
more stable than those with phenylene units. The Td10
(temperature showing 10% weight loss) can be conven-
Scheme 8. General scheme of silylative cross-coupling (SC)
copolycondensation of bis(vinyldimethylsilyl)arenes (10, 12,
14) with 1,4-divinylbenzene (9) in the presence of catalyst 7.
amples of proton spectra of homopolymer 16 and co- iently employed to quantify the difference (Figure 6).
polymer 21, which prove the purity of the structures of The results are summarized in Table 4. The parameter
the final products (Fig. 3 and Fig. 4) are shown below.
Td10 revealed the difference of about 278C between
For all homopolymers 16, 17 and 18 we have identi- the two types of polymers. This indicated that polymer
fied single signals (adequately: 6.82, 6.84 and 15 is more stable than copolymers 19 and 12, but similar
6.88 ppm) corresponding with homo-coupling frag- to copolymer 21. The photophysical properties of these
ꢀ
¼
ꢀ
ments ( SiCH CHSi ).
polymeric materials have been understudied.
However, for copolymers 19, 20 and 21, the 1H NMR
spectra showed us two characteristic, double signals
ꢀ ꢀ
¼
ꢀ
ꢀ ꢀ
¼
ꢀ
( Si CH CH C<and Si CH CH C>) with cou-
pling constant JH,H from 19.0 Hz to 19.2 Hz, typical for Conclusion
the trans isomer only.
The yields and molecular weights of the final products The first stereoregular trans-arylene-silylene-vinylene
are listed in Table 4. The yields (after isolation) of poly- polymers (Mw ¼13100–34800 and PDI¼1.6–2.9) can
mers are between 78 and 92%.
be effectively synthesized via silylative coupling (SC)
The molecular weights of 15, 16 and 19 are higher than catalyzed by [RuH(Cl)(CO)(PCy3)2] (7):
those of the previously reported polymers[17] (character-
Figure 3. 1H NMR spectrum of homopolymer 16 in CDCl3.
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Mariusz Majchrzak et al.
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Figure 4. 1H NMR spectrum of copolymer 21 in CDCl3.
Table 4. The results of silylative coupling polycondensation reaction and thermal properties of silicon-containing arylene-sily-
lene-vinylene polymers.
[b]
Polymer
Yield [%][a]
Mw ꢁ104 [b]
Mw/Mn
n[c]
Td10 [8C][d]
Wt loss [%][e]
15
16
17
18
19
20
21
88
89
85
92
89
78
94
1.84
1.63
1.64
3.48
1.76
1.31
2.46
2.1
1.6
1.7
2.5
2.0
2.2
2.9
55
47
44
47
28
18
21
491
447
433
486
464
473
478
53
53
77
57
61
55
62
[a]
Yield after isolation.
Mw and PDI were determined by GPC using polystyrene standards.
Calculated from GPC and compared H NMR.
Temperature of 10% weight loss.
[b]
[c]
[d]
[e]
1
Weight loss in the range 25–9008C under N2.
Figure 5. GPC chromatograms of polymers 15, 19, 20, 21 in
THF.
Figure 6. TGAthermal analysis profiles for homopolymers
and copolymers.
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Stereoselective Synthesis of Arylene-Silylene-Vinylene Polymers
FULL PAPERS
(8) were prepared on the basis of the procedure described in
the above-cited literature. Pure 1,4-divinylbenzene, DVB (9)
was synthesized by the Ni-catalyzed coupling reaction[19] be-
tween vinyl bromide and 1,4-bis(bromomagnesium)benzene.
Monomeric 1,4-bis(vinyldimethylsilyl)benzene (10) was pre-
pared according to a literature procedure.[17a]
. homopolycondensation of bis(vinyldimethylsilyl)ar-
enes (10, 12 and 14),
. cross-polycondensation of 4-(vinyldimethylsilyl)styr-
ene (11),
. cross-copolycondensation of bis(vinyldimethylsilyl)-
arenes (10, 12 and 14) with 1,4-divinylbenzene (9).
The structures of the polymers were characterized and
1
determined by H, 13C and 29Si NMR as well as FTIR
Syntheses of Organosilicon Monomers
spectroscopy. The absence of fragments with quaternary
4-(Vinyldimethylsilyl)styrene (11): Asolution of 4-bromostyr-
ene (6.1 g, 33.3 mmol) in 50 mL of THF was added slowly drop-
wise to a suspension of Mg (1.05 g, 43.2 mmol, whose surface
was activated by use of 1,2-dibromomethane, 50 mL) and vinyl-
dimethylchlorosilane (4.41 g, 36.6 mmol) in 20 mL of THF (the
mixture was lightly warmed, 20–308C). After the addition was
completed, the reaction mixture was heated at 408C for 1 hour
ꢀ
¼
carbon atoms [( SiMe2)2C CH2)] in the chains of each
polymer was also confirmed by DEPT spectroscopic
analysis.
The polymeric products cannot be synthesized via
ADMET polymerization process due to the stereoelec-
tronic effect of silyl groups in vinyl-silicon compounds,
therefore SC polycondensation opens a new synthetic and then it was cooled at room temperature, 1 mL of water was
added and the reaction mixture was filtered off. The organic
solvent was removed, and the residue was distilled under
reduced pressure (in the presence of 4-methoxyphenol) to
afford 11 as a colourless liquid; yield: 5.33 g (85%); bp
route to regio- and stereoregular arylene-silylene-vinyl-
ene type polymers.
1
66–678C/5 mmHg. H NMR (CDCl3): d¼0.34 (s, 6H, CH3),
Experimental Section
ꢀ
¼
5.23 (d, 1H, J¼10.8 Hz, >C CH CH2), 5.75 (dd, 1H,
¼
J¼3.9, 19.6 Hz, SiCH CH2), 5.76 (d, 1H, J¼16.9 Hz,
ꢀ
¼
¼
>C CH CH2), 6.05 (dd, 1H, J¼3.8, 14.9 Hz, SiCH CH2),
General Remarks
¼
6.28 (dd, 1H, J¼15, 19.5 Hz, SiCH CH2), 6.71 (dd, 1H,
ꢀ ¼
J¼10.8, 17.1 Hz, >C CH CH2), 7.4 [d, 1H, J¼3 Hz,
All syntheses of monomers, polymers and catalytic tests were
carried out under an inert argon atmosphere. 1H NMR
(300 MHz), 13C NMR (75 MHz), 29Si NMR (60 MHz) and
DEPT spectra were recorded on Varian XL 300 MHz spec-
trometer in CDCl3. Mass spectra of the monomers were ob-
tained by GC-MS analysis (Varian Saturn 2100T, equipped
with a BD-5 capillary column (30 m) and an ion trap detector.
High-resolution mass spectroscopic (HR-MS) analyses were
performed on an AMD-402 instrument. GC analyses were per-
formed on a Varian 3400 with a Megabore column (30 m) and
TCD. Infrared spectra (film) were recorded on an FT-IR Bruk-
er JFS-113v. Gel permeation chromatography (GPC) analysis
was carried out using a Gilson HPLC system equipped with
UVabsorbance detector and RI detector. The GPC was equip-
ped with a phenogel column 300ꢁ7.80 mm, 50, 500, 104 Š
(analysis condition: mobile phase: THF; flow rate: 0.7 mL/
min; temperature: ambient; injection volume: 20 mL). Mo-
lecular weight and dispersity indices were determined by poly-
styrene standard calibration. TGAanalysis was carried out un-
der nitrogen flow at heating rate of 108C minꢀ1 on a Setaram
Setsys 12 instrument with a model Setsoft version 154D data
analysis software program (the temperature range of analysis
was 25–11008C). The chemicals were obtained from the fol-
lowing sources: THF, toluene, methanol, methylene chloride,
1,2-dibromoethane, 4-methoxyphenol were purchased from
Fluka, CDCl3 from Dr Glaser A. G. Basel, chlorodimethylvi-
nylsilane and vinylphenyldimethylsilane from Gelest. All the
halogenated aryl derivatives and vinyl bromide were bought
¼
ꢀ
¼
H2C CH-(m C6H4)], 7.5 [d, 1H, J¼3 Hz, H2C CHSi-
(o C6H4)]; 13C NMR (CDCl3): d¼ ꢀ2.50 (CH3), 114.70
ꢀ
¼
ꢀ
¼
(H2C CH-C6H4 ),
126.08
134.59
(H2C CH-C6H4),
133.38
137.36
138.54
¼
ꢀ
ꢀ
¼
(SiCH CH2),
( C6H4 SiCH CH2),
¼
ꢀ
ꢀ
¼
(H2C CH C6H4 ),
138.41
(SiCH CH2),
(H2C C C<), 138.69 (>C SiCH CH2); 29Si NMR
(CDCl3): d¼ ꢀ10.22; HR-MS: m/z¼188.10223; calcd. for
C12H16Si: 188.10213.
¼ ꢀ
ꢀ
¼
1,3-Bis(vinyldimethylsilyl)benzene (12): Asolution of 1,3-
dibromobenzene (5 g, 21.2 mmol) in 45 mL of THF was added
slowly dropwise to a suspension of Mg (1.29 g, 53.0 mmol,
whose surface was activated by use of 1,2-dibromomethane,
100 mL) and vinyldimethylchlorosilane (5.62 g, 46.6 mmol) in
15 mL of THF (the mixture was slightly warmed). After the ad-
dition was completed, the reaction mixture was refluxed for 4
hours. Then the mixture was cooled to room temperature,
2 mL of water were added, and the whole was filtered. The or-
ganic solvent was evaporated, and the residue was distilled un-
der reduced pressure to afford 12 as a colourless liquid; yield:
4.23 g (81%); bp 66–688C/0.6 mmHg. 1H NMR (CDCl3): d¼
¼
0.39 (s, 12H, CH3), 5.80 (dd, 2H, J¼3.9, 20.1 Hz, SiCH CH2),
¼
6.10 (dd, 2H, J¼3.9, 15.0 Hz, SiCH CH2), 6.34 (dd, 2H, J¼
¼
14.7, 20.1 Hz, SiCH CH2), 7.38 (t, 1H, p-C6H4), 7.58 (d, 1H,
m-C6H4), 7.72 (s, 1H, SiC CH CSi); 13C NMR (CDCl3): d¼
ꢀ
ꢀ
¼
ꢀ2.74 (CH3), 127.02 (p-C6H4), 132.69 (SiCH CH2), 134.45
¼
(m-C6H4), 137.35 (o-C6H4), 137.88 (SiCH CH2), 139.02
(>C SiCH CH2); 29Si NMR (CDCl3): d¼ ꢀ10.70; HR-MS:
m/z¼246.12635; calcd. for C14H22Si2: 246.12600.
ꢀ
¼
ꢀ
from Aldrich. The dimeric complex {[Ru(m Cl)2(CO)3]}2 (1)
was purchased from Stream. CH2Cl2 was additionally passed
through a column with aluminium oxide. The ruthenium com-
plexes: [RuH(Cl)(CO)(PPh3)3][18b] (2), [RuH(Cl)(CO)2-
(PPh3)2][18c] (3), [RuH(OAc)(CO)(PPh3)2][18d] (4), [Ru-
H(OAc)(PPh3)3][18e] (5), [Ru(SiMe3)(Cl)(CO)(PPh3)2][18f] (6),
[RuH(Cl)(CO)(PCy3)2][18a] (7), [RuH(OAc)(CO)(PCy3)2][18c]
4-(Vinyldimethylsilyl)biphenyl (13): Anew compound:
this vinylsilane was prepared from vinyldimethylchlorosilane
and 4-bromobiphenyl according to the synthesis of 12 and ob-
tained by distillation under reduced pressure as a liquid; yield:
95%; bp 79–828C/5 mmHg. 1H NMR (CDCl3): d¼0.39 (s, 6H,
¼
CH3), 5.80 (dd, 1H, JH,H ¼3.9, 20.1 Hz, SiCH CH2), 6.09 (dd,
Adv. Synth. Catal. 2005, 347, 1285–1294
asc.wiley-vch.de
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1291

Mariusz Majchrzak et al.
FULL PAPERS
¼
1H, JH,H ¼3.9, 20.1 Hz, SiCH CH2), 6.34 (dd, 1H, JH,H ¼14.4,
(0.0078 mmol) and toluene (1.56 mL, 0.5M) were placed in a
5-mL mini-reactor. The reaction mixture was stirred and heat-
ed at 808C under an argon flow for 6–7 days. The isolated
yields were between 78 and 94% depending on combination
of starting monomer and derivative of bis(vinyldimethylsily-
l)arenes.
¼
ꢀ
19.8 Hz, SiCH CH2), 7.38 (t, 4H, m-C6H4 C6H5), 7.47 (t, 1H,
C6H4 p-C6H5), 7.61 (d, 4H, o-C6H4 C6H5); 13C NMR
(CDCl3): d¼ ꢀ2.86 (CH3), 126.54 (m-C6H4), 127.10 (p-
ꢀ
ꢀ
ꢀ
¼
C6H5), 127.37 (o-C6H5), 128.77 (m-C6H5), 132.77 (SiCH CH2),
ꢀ
¼
134.43 (o-C6H4), 137.31 (>C C<), 141.05 (SiCH CH2),
141.79 (>C SiCH CH2); 29Si NMR (CDCl3): d¼ ꢀ11.35;
HR-MS: m/z¼238.11798; calcd. for C16H18Si: 238.11778.
4,4’-Bis(vinyldimethylsilyl)biphenyl (14): Anew mono-
mer: this compound was prepared from vinyldimethylchlorosi-
lane and 4,4’-dibromobiphenyl according to the synthesis of 12
and obtained by distillation under reduced pressure as a white,
crystalline, stable solid; yield: 95%; bp 112–1158C/0.6 mmHg;
ꢀ
¼
Homopolycondensation Procedure of Monomer 11
Poly[p-phenylene-dimethylsilylene-(E)-vinylene] (15):
A
mixture of 0.24 g (1.27 mmol) of 11 and 9.3 mg (0.92ꢁ10ꢀ2
mmol) of complex 7 in 1.27 mL (1 M) of toluene was heated
at 808C under an argon flow for 7 days. After the reaction
was completed, the resulting polymer was isolated and purified
by repeated reprecipitation from methanol. Then the final pol-
ymeric material was filtered off and dried under vacuum at
room temperature to afford homopolymer 15 as a light yellow
powder; yield: 0.29 g (88%). 1H NMR (CDCl3): d¼0.34
(s, CH3, external), 0.43 (s, CH3, internal), 5.26 (d, J¼10.8 Hz,
1
mp 42.5–42.98C. H NMR (CDCl3): d¼0.41 (s, 12H, CH3),
¼
5.81 (dd, 2H, J¼3.6, 20.1 Hz, SiCH CH2), 6.10 (dd, 2H, J¼
¼
3.9, 14.7 Hz, SiCH CH2), 6.34 (dd, 2H, J¼14.4, 20.1 Hz,
SiCH CH2), 7.61 (s, 8H, o,m -C6H4 C6H4 ); 13C NMR
¼
ꢀ
ꢀ
ꢀ
ꢀ
(CDCl3): d¼ ꢀ2.76 (CH3), 126.46 (o-C6H4 C6H4 ), 132.57
¼
ꢀ
ꢀ
(SiCH CH2), 134.36 (m-C6H4 C6H4), 137.11 (>C C<),
141.79 (>C SiCH CH2), 149.49 (SiCH CH2); 29Si NMR
(CDCl3): d¼ ꢀ11.45; HR-MS: m/z¼322.15752; calcd. for
C20H26Si2: 322.15730.
ꢀ
¼
¼
ꢀ
¼
>C CH CH2, trace), 5.75 (dd, 1H, J¼3.9, 19.6 Hz,
¼
ꢀ
¼
SiCH CH2, trace), 5.79 (d, 1H, J¼17.4 Hz,>C CH CH2,
ꢀ ꢀ
ꢀ
¼
trace), 6.62(d, 1H, J¼19 Hz, >C HC CH Si ), 6.78 (dd,
ꢀ
¼
1H, J¼10.8, 17.5 Hz, >C CH CH2, trace), 6.93 (s, 1H,
ꢀ
¼
ꢀ ꢀ
Representative Procedures for Catalytic Reactions
J¼19 Hz, >C HC CH Si ), 7.44 (d, 2H, J¼7.8 Hz,
¼
ꢀ
¼
ꢀ
CH-o-C6H4 ), 7.53 (d, 2H, J¼7.8 Hz, CH-m-C6H4 );
13C NMR (CDCl3): d¼ ꢀ2.50 (CH3, external and internal),
Catalytic tests of silylative homo-coupling reactions: Catalyt-
ic screenings were essentially performed under argon using an
earlier prepared toluene solution (1 M) of a mixture of vinyl-
phenyldimethylsilane and 1 mol % of ruthenium catalysts at
1108C for 18 h.
Catalytic tests of silylative cross-coupling reactions: Cata-
lytic screenings were mainly performed under argon using an
earlier prepared toluene solution (0.5 M) of a 2:1 mixture of vi-
nylphenyldimethylsilane and 1,4-divinylbenzene with 1 mol %
of ruthenium catalysts at 808C for 18 h.
ꢀ
¼
¼
ꢀ
114.20 (>C HC CH2, trace), 125.92 ( CH-o-C6H4 ),
ꢀ
¼
¼
ꢀ
127.60 (>C HC CH2), 134.21 ( CH-m-C6H4 ), 138.7
ꢀ
¼
ꢀ ꢀ
ꢀ
¼
ꢀ
(>C HC CH Si ), 138.8 ( HC CH Si-C<), 145.32
( CH CH Si); 29Si NMR (CDCl3): d¼ ꢀ10.52; FTIR (film):
ꢀ
¼
ꢀ
n¼1261 (dsym, Si-Me), 1018 and 987 cmꢀ1 (gCꢀ
, trans-
H
¼
ꢀ
C6H4HC CHSi ); anal. calcd. for (C10H12Si)n: C 74.93,
H 7.55; found: C 73.23, H 7.31; TGA: Td10 ¼4918C; GPC:
Mw ¼18400, Mn ¼8760, Mw/Mn ¼2.1, n¼55
Procedure of catalytic tests for polycondensation of 1,4-
bis(vinyldimethylsilyl)benzene: Catalytic tests were per-
formed in the presence of argon using an earlier prepared tol-
uene solution (1 M) of a mixture of 1,4-bis(vinyldimethylsil-
lyl)benzene and 1 mol % of ruthenium catalysts at 1108C for
24 h.
Analytical Data of Homopolymers and Copolymers
Poly[dimethylsilylene-p-phenylene-dimethylsilylene-(E)-vi-
nylene] (16): 1H NMR (CDCl3): d¼0.25 (s, CH3, external), 0.34
ꢀ
¼
(s, CH3, internal), 5.75 (dd, 1H, J¼4, 24 Hz, Si CH CH2,
ꢀ
¼
trace), 6.04 (dd, 1H, J¼4, 14 Hz, Si CH CH2, trace), 6.30
ꢀ
¼
(dd, 1H, J¼14, 24 Hz, Si CH CH2, trace), 6.82 (s, 2H,
General Homopolycondensation Procedure
SiCH CHSi ), 7.50 (s, 8H, C6H4 ); 13C NMR (CDCl3):
d¼ ꢀ2.71 (CH3, internal), ꢀ2.6 (CH3, external), 132.26
ꢀ
¼
ꢀ
ꢀ
ꢀ
The syntheses were performed under argon using 7 as a cata-
lyst. Reagents and solvents were dried and deoxygenated. A
mixture of 10, 12 or 14 monomer (2.5 mmol), the ruthenium
complex 7 (0.025 mmol) and toluene (2.5 mL, 1 M) were
placed in a 5-mL mini-reactor. The reaction mixture was stirred
and heated at 1108C under an argon flow for 5–7 days. The iso-
lated yields were between 85 and 92% depending on the com-
bination of starting monomer and derivative of bis(vinyldime-
thylsilyl)arenes.
ꢀ
¼
¼
ꢀ
ꢀ
(Si CH CH2), 132.87 (SiCH CH2), 133.20 ( C6H4 ), 139.32
(>C Si ), 150.22 ( SiCH CH Si); 29Si NMR (CDCl3): d¼
ꢀ ꢀ
ꢀ
¼
ꢀ
ꢀ11.78; FT-IR (film): n¼1250 (dSi-Me), 1008 cmꢀ1 (gCꢀH, trans-
¼
ꢀ
SiHC CHSi ); anal. calcd. for (C12H18Si2)n: C 65.98, H 8.31;
found: C 65.76, H 8.41; TGA: Td10 ¼4478C; GPC: Mw ¼
16300, Mn ¼10190, Mw/Mn ¼1.6, n¼47. The compound was
isolated as a white powder.
Poly[dimethylsilylene-m-phenylene-dimethylsilylene-
(E)-vinylene] (17): 1H NMR (CDCl3): d¼0.34 (s, CH3, exter-
nal), 0.35 (s, CH3, internal), 5.78 (dd, 1H, J¼4, 24 Hz,
¼
¼
SiCH CH2, trace), 6.06 (dd, 1H, J¼4, 14 Hz, SiCH CH2,
General Copolycondensation Procedure
¼
trace), 6.32 (dd, 1H, J¼14, 24 Hz, SiCH CH2, trace), 6.84 (s,
¼
ꢀ
ꢀ
The syntheses processes were carried out under argon, where 7
was used as a catalyst. Reagents and solvents were dried and
SiCH CHSi), 7.31–7.36 (m, m-C6H4 ), 7.50 (d, o-C6H4 ),
7.67 (s, SiC CH CSi); 13C NMR (CDCl3): d¼ ꢀ2.72 (CH3,
internal), ꢀ2.66 (CH3, internal), 127.03 (p-C6H4), 134.50
ꢀ
ꢀ
deoxygenated. Amixture of
10, 12 or 14 monomer
ꢀ ꢀ ꢀ ꢀ
ꢀ
(0.78 mmol) with 9 (0.78 mmol), the ruthenium complex 7
(m-C6H4), 137.50 (Si C CH C Si), 139.15 (>C Si-
1292
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2005, 347, 1285–1294

Stereoselective Synthesis of Arylene-Silylene-Vinylene Polymers
FULL PAPERS
HC CH ), 150.23 ( SiCH CHSi ); 29Si NMR (CDCl3): d¼
C6H4HC CHSi ); anal. calcd. for (C26H28Si2)n: C 78.72, H
7.11; found: C 77.98, H 7.05; TGA: Td10 ¼4788C; GPC: Mw ¼
24600, Mn ¼8480, Mw/Mn ¼2.9, n¼21. The compound was iso-
lated as a white powder.
¼
ꢀ
ꢀ
¼
ꢀ
¼
ꢀ
ꢀ11.49; FT-IR (film): n¼1260 (dsym, Si-Me), 1009 cmꢀ1 (gCꢀ
,
H
ꢀ
¼
trans SiHC CHSi); anal. calcd. for (C12H18Si2)n: C 65.98, H
8.31; found: C 65.76, H 8.21; TGA: Td10 ¼4338C; GPC: Mw ¼
16400, Mn ¼9650, Mw/Mn ¼1.7, n¼44. The compound was iso-
lated as a white powder.
The progress of the synthesis reactions of homopolymers
and copolymers, in the initial stage, was monitored by GC-
1
MS and H NMR. The isomer structures were confirmed by
Poly[dimethylsilylene-p-biphenylene-dimethylsilylene-
1
DEPTanalysis. The polymeric materials were isolated accord-
ing to the work-up of procedure 15. The polymers were soluble
in some organic solvents, such as chloroform, CH2Cl2 and THF,
but insoluble in benzene, toluene and alcohols, that is why the
polymers were readily separated from the reaction mixture by
reprecipitation from alcohols.
(E)-vinylene] (18): H NMR (CDCl3): d¼0.38 (s, CH3, inter-
¼
ꢀ
ꢀ
ꢀ
nal), 6.88 (s, 2H, SiHC CHSi), 7.60 (s, 8H, C6H4 C6H4 );
13C NMR (CDCl3): d¼ ꢀ2.70 (CH3, internal), 126.45 (o-
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
C6H4 C6H4 ), 134.29 (m-C6H4 C6H4 ), 137.31 (>C C<),
141.53 (>C SiHC CH ), 150.22 ( SiCH CHSi); 29Si NMR
(CDCl3): d¼ ꢀ11.43; FT-IR (film): n¼1262 (dsym, Si-Me),
ꢀ
¼
ꢀ
ꢀ
¼
990 cmꢀ1 (gCꢀ
,
H
trans-SiHC CHSi ); anal. calcd. for
¼
ꢀ
(C18H22Si2)n: C 73.40, H 7.53; found: C 73.15, H 7.39; TGA:
Td10 ¼4868C; GPC: Mw ¼34800, Mn ¼13290, Mw/Mn ¼2.5,
n¼47. The compound was isolated as a white powder.
Poly[dimethylsilylene-p-phenylene-dimethylsilylene-(E)-
Acknowledgements
This work was supported by Grant No. 3T09A 145 26 from the
State Committee for Scientific Research (Poland).
1
vinylene-p-phenylene-(E)-vinylene] (19): H NMR (CDCl3):
d¼0.33 (s, 12H, CH3, external), 0.41 (s, 12H, CH3, internal),
¼
5.75 (dd, J¼4, 24 Hz, SiCH CH2, trace), 6.04 (dd, J¼4,
ꢀ
¼
15 Hz, Si CH CH2, trace), 6.27(dd, J¼15, 20 Hz,
References
ꢀ
¼
ꢀ
>C HC CH Si-, trace), 6.56 (d, 1H, J¼19 Hz,
ꢀ
¼
ꢀ ꢀ
>C CH CH Si ),
6.92
(d,
1H,
ꢀ
J¼19 Hz,
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ꢀ
¼
ꢀ ꢀ
ꢀ
>C HC CH Si ), 7.36 (s, 4H, C6H4 ), 7.56 (s, 4H,
13
ꢀ ꢀ
ꢀ ꢀ
Si C6H4 Si ); C NMR (CDCl3): d¼ ꢀ2.9 (CH3, external),
ꢀ
¼
ꢀ2.60 (CH3, internal), 114.10 (>C HC CH2, trace), 126.69
ꢀ
ꢀ
ꢀ
¼
ꢀ
ꢀ
¼
( C6H4 ), 127.16 (>C HC CH Si), 132.89 ( Si-HC CH2),
ꢀ
ꢀ
¼
ꢀ ꢀ
133.26 (Si-C6H4 Si), 137.91 (>C HC CH Si ), 139.41
( HC CH Si-C<), 144.78 ( CH CH Si ); 29Si NMR
(CDCl3): d¼ ꢀ10.35; FT-IR (film): n¼1248 (dsym, Si-Me),
ꢀ
¼
ꢀ
ꢀ
¼
ꢀ ꢀ
985 cmꢀ1 (gCꢀH, trans-C6H4HC CHSi ); anal. calcd. for
(C20H24Si2)n: C 74.93, H 7.55; Found: C 74.31, H 7.38; TGA:
Td10 ¼4648C; GPC: Mw ¼17600, Mn ¼8800, Mw/Mn ¼2.0, n¼
28. The compound was isolated as a light yellow powder.
Poly[dimethylsilylene-m-phenylene-dimethylsilylene-
(E)-vinylene-p-phenylene-(E)-vinylene] (20): 1H NMR
(CDCl3): d¼0.33 (s, 12H, CH3, external), 0.43 (s, CH3, inter-
¼
ꢀ
ꢀ
¼
ꢀ
nal), 6.60 (d, 1H, J¼19.2 Hz,>C HC CH Si), 6.93 (d, 1H,
ꢀ
¼
ꢀ ꢀ
ꢀ
ꢀ
J¼19.2 Hz,>C HC CH Si ), 7.21 (s, 4H, C6H4 ), 7.36–
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
7.39 (m, m-C6H4 ), 7.60 (d, o C6H4 ), 7.77 (s, SiC CH CSi);
13C NMR (CDCl3): d¼ ꢀ2.88 (CH3, external), ꢀ2.52 (CH3,
ꢀ
ꢀ
ꢀ
internal), 126.73 ( C6H4 ), 127.24 (m-C6H4 ), 127.46
ꢀ
¼
ꢀ
ꢀ
(>C HC CH Si),
134.79
(o-C6H4 ),
137.72
ꢀ
¼
ꢀ ꢀ
ꢀ
ꢀ
ꢀ
(>C HC CH Si ), 138.04 (SiC CH CSi ), 139.24
( HC CH Si-C<), 144.82 ( CH CH Si ); 29Si NMR
(CDCl3): d¼ ꢀ10.09; FT-IR (film): n¼1250 (dsym, Si-Me),
ꢀ
¼
ꢀ
ꢀ
¼
ꢀ ꢀ
988 cmꢀ1 (gCꢀH, trans-C6H4HC CHSi ); anal. calcd. for
(C20H24Si2)n: C 74.93, H 7.55; found: C 74.33, H 7.37; TGA:
Td10 ¼4738C. GPC: Mw ¼13100, Mn ¼5960, Mw/Mn ¼2.2,
n¼18. The compound was isolated as a light brown powder.
Poly[dimethylsilylene-p-biphenylene-dimethylsilylene-
(E)-vinylene-p-phenylene-(E)-vinylene] (21): 1H NMR
(CDCl3): d¼0.47 (s, 12H, CH3, internal), 6.62 (d, 1H, J¼
¼
ꢀ
ꢀ
¼
ꢀ
19.2 Hz,>C HC CH Si), 6.96 (d, 1H, J¼19.2 Hz,>
ꢀ
¼
ꢀ ꢀ
ꢀ
ꢀ
C HC CH Si ), 7.43 (s, 4H, C6H4 ), 7.59–7.67 (m,
C6H4 C6H4 ); 13C NMR (CDCl3): d¼ ꢀ2.35 (CH3, internal),
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
126.50 (m C6H4 C6H4 ), 126.65 ( C6H4 ), 127.14 (>
ꢀ
¼
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
C HC CH Si), 134.32 (o C6H4 C6H4 ), 137.31 (>C C<),
ꢀ
¼
ꢀ
ꢀ
¼
ꢀ
137.84 (>C HC CH Si), 141.61 ( HC CH Si-C<),
144.74 ( CH CH Si ); 29Si NMR (CDCl3): d¼ ꢀ10.02; FT-
ꢀ
¼
ꢀ ꢀ
IR (film): n¼1259 (dsym
, , trans-
Si-Me), 992 cmꢀ1 (gCꢀ
H
Adv. Synth. Catal. 2005, 347, 1285–1294
asc.wiley-vch.de
ꢀ 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1293

Mariusz Majchrzak et al.
FULL PAPERS
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Adv. Synth. Catal. 2005, 347, 1285–1294