One-pot synthesis and structural characterization of poly(alkoxysilane)s catalyzed by silver-gold complexes

Article abstract of DOI:10.1166/jnn.2013.6942

Combinative one-pot Si-Si/Si-O dehydrocoupling of hydrosilanes with alcohols (1:1.5 mole ratio), mediated by a mixture of AgNO₃-AuCl ₃ (100/1 mole ratio) rapidly produced poly(alkoxysilane)s in reasonably high yield. The addition of small amount of gold complex to the reaction mixture effectively accelerated the coupling reaction compared to the reaction rate with AgNO₃ alone. The hydrosilanes include p-X-C ₆H₄SiH₃ (X = H, CH₃, OCH ₃, F), PhCH₂SiH₃, and (PhSiH₂) ₂. The alcohols include MeOH, EtOH, iPrOH, PhOH, and CF ₃(CF₂)₂CH₂OH. The weight average molecular weight and polydispersity of the poly(alkoxysilane)s were in the range of 1,600～8,000 Dalton and 1.4～3.5, respectively. The dehydrocoupling reactions of phenylsilane with ethanol (1:3 mole ratio) in the presence of the Ag-Au complexes gave only triethoxyphenylsilane. Copyright

Full text of DOI:10.1166/jnn.2013.6942

Copyright © 2013 American Scientific Publishers
All rights reserved
Printed in the United States of America
Journal of
Nanoscience and Nanotechnology
Vol. 13, 702–705, 2013
One-Pot Synthesis and Structural Characterization of
Poly(alkoxysilane)s Catalyzed by Silver-Gold Complexes
1
2
3
4
Hyeonsook Cheong , Sung-Hee Roh , Myong-Shik Cho , Myoung-Hee Kim ,
5ꢀ∗
6
6
7
8
Hee-Gweon Woo , Kap-Seung Yang , Bo-Hye Kim , Jin Jun , and Honglae Sohn
1Department of Biotechnology, Chosun University, Gwangju 501-759, Korea
2
Department of Chemical and Biochemical Engineering, Chosun University, Gwangju 501-759, Korea
3
Gwangju Regional Food and Drug Administration, Gwangju 500-480, Korea
Department of Chemistry, University of Wisconsin, Madison 53706-1396, USA
Alan G. MacDiarmid Energy Research Institute (AMERI), Nanotechnology Research Center (NTRC),
4
5
and Department of Chemistry, Chonnam National University, Gwangju 500-757, Korea
Department of Polymer and Fiber System Engineering and Alan G. MacDiarmid Energy Research
6
Institute (AMERI), Chonnam National University, Gwangju 500-757, Korea
7
Department of Optometry and Optic Science, Dongshin University, Naju 520-714, Korea
8
Department of Chemistry, Chosun University, Gwangju 501-759, Korea
Combinative one-pot Si–Si/Si–O dehydrocoupling of hydrosilanes with alcohols (1:1.5 mole ratio),
mediated by a mixture of AgNO –AuCl (100/1 mole ratio) rapidly produced poly(alkoxysilane)s
3
3
in reasonably high yield. The addition of small amount of gold complex to the reaction mixture
effectively accelerated the coupling reaction compared to the reaction rate with AgNO alone. The
3
Delivered by Publishing Technology to: Chalmers Tekniska Hogskola (Chalmers University of Technology)
hydrosilanes include p-X-C H SiH (X = H, CH , OCH , F), PhCH SiH , and (PhSiH ꢀ . The alco-
6
4
3
3
3
2
3
2 2
IP: 117.253.164.33 On: Fri, 29 Jan 2016 14:11:57
i
hols include MeOH, EtOH, PrOH, PhOH, and CF (CF ꢀ CH OH. The weight average molecular
3
2
2
2
Copyright: American Scientific Publishers
weight and polydispersity of the poly(alkoxysilane)s were in the range of 1,600∼8,000 Dalton and
1
.4∼3.5, respectively. The dehydrocoupling reactions of phenylsilane with ethanol (1:3 mole ratio)
in the presence of the Ag–Au complexes gave only triethoxyphenylsilane.
Keywords: Hydrosilanes, Alcohols, Si–O Dehydrocoupling, Silver Nitrate, Gold(III) Chloride,
Catalyst, Cocatalyst, Poly(alkoxysilane), Nanoparticle, Mixed catalyst.
1
. INTRODUCTION
prepared by Wurtz reductive coupling of dichlorosilanes
using sodium metal in refluxing hydrocarbon solvents such
as toluene. The introduction of useful high functional-
Polysilanes [–Si(R)X–]n (R = alkyl, aryl; X = alkyl,
alkenyl, alkynyl, aryl, hydrogen, chloride), a representa-
tive main group inorganic polymer along with polysilox-
anes, with unusual photoelectronic properties have recently
attracted great interests because of their powerful appli-
cations in microlithography, in silicon ceramics, as pho-
toconducting polymers, photoinitiator, as 3rd order NLO
materials, and precursor functional polymers. The unique
properties of polysilanes originated from the extensive
delocalization (like ꢀ-bonding electron conjugation) of
ꢁ
and depend on the type of the substituents attached to
the polymer backbone, the polymer conformation, and
the polymer molecular weight. Polysilanes are generally
5
ity onto the polymer chain is quite limited due to the
6
harsh reduction conditions used in the coupling reaction.
Some recentadvances has been made in functionalizing
polysilanes prepared by Wurtz coupling, particularly for
1
2
7
–10
phenyl-substituted polysilanes.
Transition-metal cat-
3
alyzed dehydrocoupling of polysilanes provides excel-
lent methodologies for the synthesis of polymers with
4
1
1
defined structure and functionality. The backbone Si
H
functional group of polysilanes can be transformed to
other useful functional groups by simple chemical reac-
-bonding electrons along the silicon polymer backbone
1
2ꢂ13
tions. Waymouth and co-workers
recently reported a
free-radical synthetic methodology for selectively substi-
tuting the backbone Si H bonds of polyphenylsilane.
Free radical chlorination of polyphenylsilane [–Si(H)Ph–]n
with CCl4 at room temperature for a day afforded
5
∗
Author to whom correspondence should be addressed.
7
02
J. Nanosci. Nanotechnol. 2013, Vol. 13, No. 1
1533-4880/2013/13/702/004
doi:10.1166/jnn.2013.6942

Cheong et al.
One-Pot Synthesis and Structural Characterization of Poly(alkoxysilane)s Catalyzed by Silver-Gold Complexes
poly(chlorophenylsilane) [–Si(Cl)Ph–] , which was sub-
F, CH , OCH ꢃ compounds were obtained by the reac-
3 3
n
sequently reacted with nucleophiles to produce a new
tion p-X-C H MgBr with Si(OEt) , respectively, in THF.
6 4 4
polysilane [–Si(X)Ph–] (X = Me, OMe). A wide range
The p-X-C H SiH reagents were then prepared in
6 4 3
n
of catalysts have been reported for Si–O dehydrocou-
60∼70% yield by reduction of the p-X-C H Si(OEt) with
6
4
3
1
4ꢂ15
pling of OH-containing compounds with silanes.
These
LiAlH in diethyl ether at ambient temperature.
4
catalysts include acids, bases, and both homogeneous
and heterogeneous transition metal catalysts. Bedard and
Corey16 carried out a survey of the dehydrocoupling of
a range of organosilanes and alcohols under the influ-
2
.2. Synthesis of Poly(alkoxysilane)s Using
AgNO –AuCl
3
3
n
ence of Cp TiCl /2 BuLi. The transition metal complexes
2.2.1. General Procedure for the Reaction of PhSiH3
and EtOH ([Si]:[EtOH] = 1:1.5) Catalyzed by
AgNO –AuCl
2
2
of Group VIII (Ni, Co, Rh, Pd, Ir, Pt, etc.) have been
extensively employed for the catalytic dehydrocoupling of
hydrosilanes with various nucleophilic reagents.17–21 In the
presence of Raney nickel and Pd/C catalysts, the dehy-
drocoupling of triallylsilane with excess alcohol produced
3
3
To a Schlenk flask containing AgNO (5.1 mg, 0.03 mmol)
and AuCl (0.91 mg, 0.003 mmol) was syringed phenylsi-
3
3
2
2
lane (0.18 g, 1.66 mmol) and ethanol (0.11 g, 2.43 mmol)
at room temperature. The reaction mixture immediately
turned brown with vigorous gas evolution while stirring.
After disappearance of the gas evolution the reaction mix-
ture was allowed to stir continuously. The reaction medium
became viscous. After 48 h, the catalyst was deactivated
by exposure to the air for a few minute. The mixture was
passed through a silica gel column (28–200 mesh, 20 ×
trialkoxysilane. Si–Si dehydrocoupling of hydrosilanes
with late transition metal catalysts produced a mixture of
oligomers along with a significant amount of dispropor-
2
3
tionation by-products. Poly(alkoxysilane)s can be used
as precursors for preparing interesting polysilane-siloxane
2
4
hybrids by sol–gel methods. Here we report a mild and
effective one-pot synthetic procedure for the introduction
i
of alkoxy groups (OMe, OEt, O Pr, OCH (CF ꢃ CF ꢃ onto
2
2
2
3
2
cm) using 200 ml diethyl ether as an eluent. Removal
the polysilane backbone with AgNO –AuCl mixed cata-
3
3
2
5
of the volatiles in vacuo yielded a pale yellow tacky prod-
uct. The tacky product was washed well with dry n-hexane
(10 ml×3) and dried in vacuo to give 0.23 g of off-white
lyst, which could transform to mainly Ag(0) nanoparticles
along with possibly small portion of Ag–Au bimetal-
2
6
lic alloy nanoparticles during the reaction, to give
Delivered by Publishing Technology to: Chalmers Tekniska Hogskola (Chalmers University of Technology)
brittle powder which was soluble in most organic solvents.
poly(alkoxysilane)s. Gold complexes are known to catalyze
IP: 117.253.164.33 On: Fri, 29 Jan 2016 14:11:57
2
7
Off-White powder, yield 86%. M = 1800, M = 1060.
many reactions.
Copyright: American Scientific Publishers
w
n
IR (KBr pellet): 3060, 2977, 2925, 2850, 1894, 1721, 1597,
1
3
1
435, 1390, 1295, 1134, 1070, 738. H-NMR (CDCl ,
3
2. EXPERIMENTAL DETAILS
00 MHz): ꢄ 0.79–1.04 (br, OCH2CH3), 3.46–3.70
(br, OCH2CH3), 7.08–7.20 (br, Ph).
2
.1. General Procedures and Materials
All reactions and manipulations were carried out under
prepurified nitrogen atmosphere using Schlenk techniques.
Dry, oxygen-free solvents were employed throughout. All
glasswares were flamed-dried before use. Infrared spectra
were obtained using a Nicolet 520 FT-IR or a Perkin-Elmer
2
.2.2. Reaction of PhSiH and MeOH
3
(
[Si]:[MeOH] = 1:1.5) Catalyzed by
AgNO –AuCl
3
3
Off-White powder, yield 79%. M = 6000, M = 3830.
w
n
1
600 Series FT-IR spectrometer. Electronic spectra were
IR (KBr pellet): 3079, 3052, 2890, 1725, 1130, 1070,
1
acquired using an IBM 9420 UV-vis spectrophotometer.
Proton NMR spectra were recorded on a Varian Gemini
998, 736, 699. H-NMR (CDCl , 300 MHz): ꢄ 3.00–3.33
(br, OCH3), 7.16–7.77 (br, Ph).
3
3
00 spectrophotometer using CDCl /CHCl as a refer-
3 3
ence at 7.24 ppm downfield from Me Si (TMS) standard.
4
2.2.3. Reaction of PhSiH and PhOH
3
GPC was performed on a Waters Millipore GPC liquid
chromatograph. The calibrant (monodisperse polystyrene)
and the sample were dissolved in THF and separately
eluted from an Ultrastyragel GPC column series (sequence
([Si]:[PhOH] = 1:1.5) Catalyzed by AgNO –AuCl
3
3
Off-White powder, yield 86%. M = 5380, M = 1540. IR
w
n
1
(KBr pellet): 3060, 1982, 1641, 1499, 1137, 928, 697. H-
3
4
5
ꢀ
5
00, 10 , 10 , 10 A columns). Molecular weights were
NMR (CDCl , 300 MHz): ꢄ 6.20–7.80 (br, Ph).
3
extrapolated from the calibration curve derived from the
polystyrene standard. Data analyses were carried out
using a Waters Data Module 570. AgNO3 and AuCl3
2
.2.4. Reaction of PhSiH and CF CF CF CH OH
3 3 2 2 2
(
purchased from Sigma-Aldrich) were used as received.
Methanol, ethanol, isopropyl alcohol, phenol and 1, 2,
-heptafluorobuthanol (Aldrich) were dried according to
([Si]:[CF3CF2CF2CH2OH] = 1:1.5) catalyzed by
AgNO –AuCl .
3
3
3
Off-White powder, yield 76%. Mw = 3060, M =
n
2
8
the literature procedure. The p-X-C H Si(OEt) (X = H,
1050. IR (KBr pellet): 3079, 3010, 1959, 1824, 1592,
6
4
3
J. Nanosci. Nanotechnol. 13, 702–705, 2013
703

One-Pot Synthesis and Structural Characterization of Poly(alkoxysilane)s Catalyzed by Silver-Gold Complexes
Cheong et al.
Table I. GPC characterization of hydrosilane and alcohol using
poly(alkoxysilane)s at room temperature in 65∼91%
a
AgNO –AuCl catalyst.
3
3
yields after workup and column chromatography.
b
Mol wt.
3.2. UV Absorption Spectrum of
Silane:Alcohol (mole ratio)
Yield
Mw
Mn
M /M
w
n
Poly(ethoxyphenylsilane)
PhSiH :EtOH (1:0.5)
84
86
90
79
80
86
76
91
82
60
65
2720
1800
-
1810
1060
-
1.5
1.7
-
3
PhSiH :EtOH (1:1.5)
3
The UV absorption spectrum of polyphenylsilane contains
PhSiH :EtOH (1:3)
3
−1
−1
a weak transition at 297 nm (ꢅSi–Si = 2062 cm M ꢃ.
Substitution of the Si–H group with a Si–OEt group
resulted in a red shift of 45 nm and an increase in the
extinction coefficient. The differences in the ꢆmax for the
PhSiH :MeOH (1:1.5)
6900
5000
5380
3060
4070
7900
1950
1670
3830
2940
1540
1050
2260
2920
1300
1190
1.8
1.7
3.5
2.9
1.8
2.7
1.5
1.4
3
PhSiH :iPrOH (1:1.5)
3
PhSiH :PhOH (1:1.5)
3
PhSiH :CF (CF ꢃ CH OH (1:1.5)
3
3
2
2
2
(
(
PhSiH ꢃ :EtOH (1:2)
2 2
–
H and –OEt substituents are likely a result of an elec-
PhSiH ꢃ :MeOH (1:2)
2
2
tronic perturbation of the silicon backbone by the ethoxy
substituent. The lonepair electrons on the oxygen sub-
stituent might be expected to perturb the electronic struc-
ture of the polymer backbone by destabilizing the HOMO
more than the LUMO, leading to a decrease of the tran-
sition energy. For other poly(alkoxyphenylsilane)s similar
red shifts were observed. For poly(phenoxyphenylsilane) a
larger red shift (55 nm) was observed.
PhCH SiH :EtOH (1:1.5)
2
3
PhCH SiH :MeOH (1:1.5)
2
3
Notes: Stirred at ambient temperature in neat until the reaction mixture became
a
b
rigid. [Ag/Au]/[Si] = /0.02. Measured with GPC (vs. polystyrene) in THF.
1
1
3
7
434, 1230, 1129, 1060, 910, 732, 699. H-NMR (CDCl ,
00 MHz): ꢄ 3.41–4.13 (br, CF3CF2CF2CH2OH), 6.81–
.74 (br, Ph).
3
1
H-NMR spectra of the polymers prepared from
the Si–Si/Si–O dehydrocoupling reaction of hydrosilanes
2
.2.5. Reaction of PhSiH SiH Ph and EtOH
2
2
(
(
PhSiH , PhCH SiH , PhSiH SiH Ph) and alcohols ROH
3 2 3 2 2
i
R = Et, Pr) using AgNO –AuCl catalyst showed no
([Si]:[EtOH] = 1:2) catalyzed by AgNO –AuCl .
3
3
3
3
appreciable Si H resonances. The IR spectra of all
the polymers exhibited a strong
Off-White powder, yield 91%. M = 4070, M = 2260.
w
n
v
band around 1000–
IR (KBr pellet): 3071, 3042, 2922, 2887, 1957, 1824,
1
(
Si–O
−
1
1
1100 cm , suggesting complete Si–O coupling to give
596, 1423, 1390, 1134, 1058, 956, 789, 735. H-NMR
Delivered by Publishing Technology to: Chalmers Tekniska Hogskola (Chalmers University of Technology)
poly(alkoxysilane)s. The weight average molecular weight
CDCl , 300 MHz): ꢄ 0.60–1.2 0I P( :b 1r ,1 O7 .C2 H5 32 C. 1 H6 34 ). ,3 33 . 2O 1 n– : Fri, 29 Jan 2016 14:11:57
3
Copyright: American S co i fe nt ht i ef icp Pr ou d bu l ci se hd e rp so lymers ranged from 1,600 to 8,000
3
.84 (br, OCH2CH3), 7.62–7.82 (br, Ph).
Dalton with the polydispersity (M /M ꢃ of 1.4∼3.5
w
n
range.
2
.2.6. Reaction of PhCH SiH and EtOH
2
3
The mole ratio of hydrosilane to alcohol significantly
affected the degree of alkoxy-substitution and the poly-
mer molecular weights in the dehydrocoupling reaction
of silane and alcohol with AgNO –AuCl catalyst. The
([Si]:[EtOH] = 1:1.5) catalyzed by AgNO –AuCl .
3
3
Off-White powder, yield 60%. M = 1950, M = /1300.
w n
IR (KBr pellet): 3076, 2926, 1870, 1736, 1603, 1493,
1
3
3
3
392, 1293, 1175, 1075, 959, 697. 1H-NMR (CDCl3,
00 MHz): ꢄ 0.98–1.11 (br, OCH2CH3), 1.94–2.13 (br,
reaction of phenylsilane and ethanol (1:0.5 mole ratio)
produced 40% (based on NMR analysis) partially substi-
tuted polymer in 84% yield. The dehydrocoupling reaction
of phenylsilane with ethanol produced a mixture of prod-
ucts such as triethoxyphenylsilane as major and uniden-
tified materials as minor. It has been reported that the
dehydrocoupling of hydrosilanes with late transition metal
catalysts produced a mixture of oligomers along with sig-
PhCH2Si), 3.53–3.71 (br, OCH CH ), 6.75–7.52 (br, Ph).
2
3
3
. RESULTS AND DISCUSSION
3
.1. Si–Si/S–O Dehydrocoupling of Hydrosilanes and
Alcohols Catalyzed by AgNO –AuCl
3
3
nificant amounts of redistribution products.2 AgNO trans-
3
3
The Si–Si/Si–O dehydrocoupling of hydrosilanes and alco-
hols with 2 mol% AgNO and 0.02 mol% AuCl yielded
formed to Ag(0) colloidal nanoparticles (size of 20∼30 nm)
3
3
Ph
[
Si]:[EtOH] = 1:1.5
Si
n
AgNO /AuCl
3
3
OEt
PhSiH + EtOH
3
o
2
5 C
[
Si]:[EtOH] = 1:3
PhSi (OEt) + unidentified material
3
7
04
J. Nanosci. Nanotechnol. 13, 702–705, 2013

Cheong et al.
One-Pot Synthesis and Structural Characterization of Poly(alkoxysilane)s Catalyzed by Silver-Gold Complexes
during the dehydrocoupling, confirmed by SEM analysis.
For the higher concentration of alcohol to hydrosilane the
larger size (30∼50 nm) of nanoparticles were observed.
References and Notes
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2
6
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2
9
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4
5
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. CONCLUSION
1
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(
65∼91%) by the Si–Si/Si–O dehydrocoupling reactions of
hydrosilanes with alcohols (1:1.5 mole ratio) in the pres-
ence of AgNO –AuCl (100:1 mole ratio) catalyst which
3
3
Delivered by Publishing Technology to: Chalmers Tekniska Hogskola (Chalmers University of Technology)
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ethanol (1:3 mole ratio) in the presence of the mixed
catalyst produced only triethoxyphenylsilane. Thus, the
ratio of hydrosilane to alcohol is very important to con-
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the dehydrocoupling of hydrosilane with alcohol. The
ratio also affects the size of metal nanoparticles, lead-
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2
Acknowledgment: This research was supported by
the International S&T Cooperation Program thru NRF
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H.S.C. is grateful to the Research Fund from Chosun
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2
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Received: 19 November 2011. Accepted: 29 May 2012.
J. Nanosci. Nanotechnol. 13, 702–705, 2013
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