Vinyl-Functionalized Silsesquioxanes and Germasilsesquioxanes

Article abstract of DOI:10.1002/ejic.201700465

We report herein an efficient procedure for the synthesis of new polyhedral oligomeric silsesquioxane (POSS) derivatives as multifunctional reagents. This study concerns the incompletely condensed silsesquioxanes and germasilsesquioxanes with vinyl-substituted silyl and germyl functional groups, which allow further modification. Furthermore, our experiments have been extended to the synthesis of a new subclass of completely condensed vinylgermasilsesquioxanes. These hybrid building blocks were obtained selectively within a few hours and isolated with excellent yields.

Full text of DOI:10.1002/ejic.201700465

A Journal of
Accepted Article
Title: Vinyl functionalized silsesquioxanes and germasilsesquioxanes
Authors: Magdalena Grzelak, Dawid Frąckowiak, and Bogdan
Marciniec
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700465
Link to VoR: http://dx.doi.org/10.1002/ejic.201700465

European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
Vinyl functionalized silsesquioxanes and germasilsesquioxanes
[
a]
[b]
[a,b]
Magdalena Grzelak, Dawid Frąckowiak, and Bogdan Marciniec*
Abstract: We report herein an efficient procedure for the synthesis
of new POSS derivatives, as a multifunctional reagents. This study
concerns the incompletely condensed silsesquioxanes and
germasilsesqiuoxanes with vinylsubstituted silyl and germyl
functional groups which allow to further modification. Furthermore,
our experiments have been extended to synthesis new subclass of
completely condensed vinylgermasilsesquioxanes. These hybrid
building blocks were obtained selectively within a few hours and
were isolated with excellent yields.
(TMS)-capped
heptaphenylsilsesquioxane.
compounds,
e.g.
trimethylsilylated
[
14]
Introduction
Polyhedral oligomeric silsesquioxanes (POSS) make a large
class of structurally well-defined inorganic-organic materials.
Thanks to their nanometric size and unusual three-dimensional
structure of the silicon-oxygen core they are suitable for the
introduction to the hybrid systems. A considerable number of
reactions has been proposed that allow straightforward
functionalization of POSS endowing them with well-defined
Figure 1. General structures of completely condensed silsesquioxanes (A,B),
and POSS silanols (C,D,E).
Recently, studies on the POSS chemistry have been extended
to include heterosilsesquioxanes, e.g. germasilsesquioxanes.
These compounds containing Ge-O-Si moiety in their structure
combine the features of the known silsesquioxanes and
[1]
physical, chemical and biological properties. Furthermore,
[
2]
silsesquioxanes are also used in composite materials, as
[
3]
[4]
hanging groups or dendrimeric cores for the synthesis of
hybrid integrated POSS-chromophores which can be used in
germasiloxanes, with improved parameters, e.g. higher
[5]
organic light emitting diodes (OLEDs).
Currently, the most widely described group of POSS are
[15]
refractive index.
First germasilsesquioxane has been
[16]
synthesized by Feher et al. while Roesky and co-workers have
described the synthesis of cubic germasilsesquioxane
containing four germanium atoms.
[
6]
completely condensed silsesquioxanes (Figure 1 A, B) with
a
[
7]
various organic substituents. Over the past few years, research
on incompletely condensed silsesquioxanes have been also
[17]
Other studies have
concerned theoretical calculations. Our group has synthesized
[18]
[8]
extended (Figure 1 C, D, E).
The number of reports regarding the modified incompletely
the
fully
condensed
vinylgermasilsesquioxanes
and
[19]
dimethylvinylgermoxysilsesquioxanes,
as well as double-
[
9]
condensed silsesquioxanes is scarce.
However, these
decker germasilsesquioxane and examined their reactivity in
compounds exhibit distinct physicochemical properties and
[20]
olefin cross-metathesis. So far, there has been no reports on
[
10]
different reactivity. Only a few examples have been reported in
literature on modification of POSS silanols in reactions with
chlorosilanes that lead to the formation of incompletely
condensed silsesquioxane derivatives. Lorenz et al. have
provided only one example of complete substitution of the
the synthesis of incompletely condensed POSS with germanium
atoms.
This study was undertaken to design vinylsubstituted
silsesquioxane and germasilsesquioxane derivatives and to
provide an efficient procedure for their synthesis. The
trisilanolcyclohexyl
chlorodimethylvinylsilane. Other examples are based on the
substitution of one or two groups in trisilanol POSS,
POSS
-OH
groups
with
condensation
reactions
of
chloroalkylvinyl-
and
[
11]
chloroarylvinylsilanes and germanes with POSS silanols allowed
us to obtain various types of incompletely condensed POSS with
vinylsubstituted Si and Ge atoms. Introduction of vinylmetalloid
moieties make them a good multifunctional templates for further
modifications e.g. as polydentate ligands for the metal
complexes and cross linking agents for composite materials.
Furthermore, our experiments have been extended to synthesis
[
10,12]
and
then the formation of complexes, e.g. with tetrahedrally
[
13]
coordinated tin atom. There are also reports on trimethylsilyl
[
[
a]
b]
Department of Organometallic Chemistry, Faculty of Chemistry,
Adam Mickiewicz University in Poznań, Umultowska 89b, 61-614
Poznań, Poland,
E-mail: Bogdan.marciniec@amu.edu.pl
http://www.metalorg.amu.edu.pl/
of
a
new
subclass
of
completely
condensed
vinylgermasilsesquioxanes.
Center for Advanced Technologies, Adam Mickiewicz University in
Poznań, Umultowska 89c, 61-614 Poznań, Poland
Results and Discussion
The first stage of our studies was to develop efficient synthetic
methods for the preparation of chlorovinylgermanes which in
contrast to silicon analogues are not commercially available.
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
Chloroarylvinyl-
and
chloroalkylvinylgermanes
can
be
Following the procedure adopted before, we used the same
reaction conditions for condensation and we obtained
trivinylfunctional silsesquioxanes and germasilsesquioxanes (5-
synthesized by transmetalation of chlorogermanes with
organotin reagents in the presence of radical initiator.
[
19-21]
These
reactions were carried out under inert gas atmosphere (Ar),
using a vacuum-gas line and a standard Schlenk techniques due
to the sensitivity of the reagents. The next step was
condensation of POSS silanols and the respective
chlorovinylometalloids. Our introductory experiments showed
that it was necessary to use dilute THF solutions of reagents to
avoid side reactions. At the initial stage of the process the
reaction mixture was cooled in an ice bath. Then,
chlorometalloid was added, and the cooling bath was left to
warm up to room temperature. The progress of the condensation
reaction (disappearance of the signals from stretching vibrations
of the -OH in POSS silanols) was analyzed by FT-IR. At the end
the crude product was isolated from the reaction mixture and
purified.
9)
(iBu/Ph/C
(Scheme 3).
from
trisilanol(isobutyl/phenyl/isooctyl)
POSS
8
H17_3OH POSS) and the same vinylmetalloids
Scheme
3.
Synthesis
of
trivinylyfunctional
silsesquioxane
and
Synthesis of incompletely condensed silsesquioxanes and
germasilsesquioxanes
germasilesquioxane derivatives.
We
converted
the
commercially
available
dichlorodimethylgermane to chlorodimethylvinylgermane via
ABCN-mediated transmetallation with tributylvinylstannane
Taking into consideration the positive results of the previous
syntheses, we decided to expand the range of obtained
compounds to the derivatives containing four vinyl groups. The
tetravinylfunctional derivatives (10-11) were prepared in the
same way as trifunctional POSS (Scheme 4).
(
Scheme 1). Chlorodimethylvinylgermane (1) was isolated by
trap-to trap distillation of the reaction mixture in 77% yield (purity
ca. 98%). The next step of the synthesis of the open caged
POSS was a typical condensation reaction of commercially
available POSS di- and trisilanols with chloroarylvinyl- and
chloroalkylvinylmetalloids in the presence of triethylamine as a
base (Scheme 2).
Scheme 4. Synthesis of tetravinylyfunctional silsesquioxane and
Scheme 1. Synthesis of chlorodimethylvinygermane.
germasilesquioxane derivatives.
In each case the product was isolated and purified in an
analogous manner (by evaporation of the solvent from the
reaction mixture and then extraction from water-toluene mixture).
Then, toluene extracts were dried over magnesium sulfate,
filtered off and evaporated to dryness. Results of our
experiments are collected in Table 1.
Scheme
germasilesquioxane derivatives.
2.
Synthesis
of
divinylyfunctional
silsesquioxane
and
Table 1. Condensation of POSS silanols with monochlorovinylmetalloids
Reaction
time [h]
Isolated
yield [%]
POSS silanol
R
2
E(Cl)CH=CH
2
Product
[a]
For the synthesis of divinylfunctional POSS we used
iBuPOSS_2OH
Me
2
Si(Cl)CH=CH
2
2
3
4
2
2.5
4
92
91
91
disilanolisobutyl
POSS
(iBuPOSS_2OH)
and
chlorodimethylvinylsilane,
chlorodiphenylvinylsilane
and iBuPOSS_2OH
2
Me Ge(Cl)CH=CH2
chlorodimethylvinylgermane respectively to obtain the final
products 2-4 (Scheme 2).
iBuPOSS_2OH
2 2
Ph Si(Cl)CH=CH
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
Scheme 5. Synthesis of dichloro(alkyl/aryl)lvinygermanes.
iBuPOSS_3OH
iBuPOSS_3OH
PhPOSS_3OH
PhPOSS_3OH
Me
Me
Me
Me
Me
Me
2
2
2
2
2
2
Si(Cl)CH=CH
Ge(Cl)CH=CH
Si(Cl)CH=CH
Ge(Cl)CH=CH
Si(Cl)CH=CH
Ge(Cl)CH=CH
Si(Cl)CH=CH
2
5
2.5
3
90
91
93
90
92
90
91
2
2
2
6
Equimolar reaction of disilanolisobutyl POSS (iBuPOSS_2OH)
and dichloromethylvinylgermane (12), dichloroethylvinylgermane
2
7
3
(
13) or dichlorophenylvinylgermane (14) led to formation of
8
3
completely condensed germasilsesquioxanes (15-17) with front-
ended germyl moiety in silicon-oxygen core.
C
8
H
17POSS_3OH
2
9
2.5
4
PhPOSS_4OH
PhPOSS_4OH
10
11
Ph
2
2
4
[
9
POSS silanol] : [chlorometalloid] = 1 : 2 (products 2, 3, 4), 1 : 3 (products 5-
), 1 : 4 (products 10, 11), THF, 0-25°C, 2-4 h, reactions carried out in an
open system [a] progress of the reaction was followed by IR spectroscopy
The HRMS and NMR spectral analysis of the compounds
1
29
showed their high purity. The H and Si NMR spectra of (5)
showed us pretty clean example of
trifunctionalvinylsilsesquioxane (Figure 2).
a
Scheme 6. Synthesis of completely condensed germasilsesquioxanes.
Products 15-17 were purified in a similar fashion as the
incompletely condensed sil- and germasilsesquioxanes and
were obtained in high yields (91-95%) (Table 2).
Table 2. Condensation of iBuPOSS_2OH silanol with dichlorovinylgermanes
R
2
E(Cl)CH=CH
2
Reaction
time [h]
Isolated
yield [%]
POSS silanol
Product
[a]
iBuPOSS_2OH
iBuPOSS_2OH
iBuPOSS_2OH
Me
2
Ge(Cl)CH=CH
Ge(Cl)CH=CH
Ge(Cl)CH=CH
2
2
15
16
17
6
6
8
95
92
91
Et
2
2
Ph
2
[
2
POSS silanol] : [dichlorometalloid] = 1 : 1 (products 15, 16, 17), THF, 0-
5°C, 6-8 h, reactions carried out in an open system [a] progress of the
reaction was followed by IR spectroscopy
1
29
Figure 2. Example of the H NMR and Si NMR spectrum of 5 (after isolation)
in CDCl at 25 °C.
3
As mentioned above, the reaction progress was followed by FT-
IR spectroscopy by sampling of the reaction mixture. We
observed disappearance of the characteristic band of -OH in
-1
Synthesis of completely condensed germasilsesquioxanes
The outcome of our earlier studies enabled us to work out
effective syntheses of di-, tri- and tetrafunctional derivatives and
encouraged us to extend the range of our studies. The absence
of literature reports on capping reaction of disilanolisobutyl
POSS with dichlorogermanes prompted us to synthesise a new
subclass of germasilsesquioxanes. Firstly, we successfully
synthesized selected dichloro(alkyl/aryl)vinylgermanes from the
commercially available trichlorogermanes (Scheme 5).
POSS silanol 3000cm during the course of reaction. The
reaction was run over for 2-4 h (2-11) and for 6-8 h (15, 16, 17).
We discovered that after such a short time the conversion of
substrates was complete in 100%. The IR spectra of reaction
mixtures of 15–17 after complete conversion of POSS silanols
and disilanolisobutyl POSS are shown in Figure 3. The reason
for longer condensation time of silanol POSS with
chlorogermanes is the poorer reactivity of the former in
substitution reactions.
All POSS derivatives (2-11 and 15-17) were obtained in
1
13
29
excellent yields and were fully characterized by H, C and Si
NMR as well as HRMS mass spectrometry. These compounds
are air-stable white powders and gels, which are easy to handle
and can be prepared on a multigram scale. Furthermore, the
solubility of obtained compounds in common organic solvents
was good.
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
Dichloromethylvinylgermane (12): A glass Schlenk reactor equipped
with Rotaflo® stopcock and filled with argon was charged with
tributylvinylstannane (7.5 mL, 25.7 mmol), trichloromethylgermane (2.93
mL, 25.7 mmol) and ABCN (0.3 g, 1.2 mmol). The whole mixture was
frozen in liquid nitrogen bath and subjected to freeze-pump-thaw cycling.
After the mixture warmed up to room temperature, it was heated on an oil
o
bath for the 48 h, at 130 C. Then the reaction mixture was cooled down
to room temperature and transferred to 25 mL round bottom flask.
Careful trap-to-trap distillation gave 3.28
g
(70% yield) of
1
dichloromethylvinylgermane. H NMR (CDCl
3
, δ, ppm): 6.43 (dd, 1H),
1
3
6
.25 (dd, 1H), 6.09 (dd, 1H), 1.25 (s, 3H). C NMR (CDCl
3
, δ, ppm):
135.43, 134.64, 8.94; MS: m/z (rel. intensity): 186 (17), 171 (100), 167
(39), 159 (31)
Figure 3. Example of the IR spectra of a reaction mixtures of 15 and 16 (after
Dichlorophenylvinylgermane (14): A 25 mL high-pressure Rotaflo
6
h) and 17 (after 8 h) compared to disilanolisobutyl POSS.
Schlenk vessel connected to gas and vacuum line was filled with ABCN
(0.152 g, 0.62 mmol), tributylvinylstannane (4.56 mL, 15.62 mmol) and
trichlorophenylgermane (2.51 mL, 4 g, 15.62 mmol). The whole mixture
was frozen in liquid nitrogen bath and subjected to freeze-pump-thaw
cycling. After the mixture warmed up to room temperature, it was heated
Conclusions
o
on an oil bath for the 24 h at 140 C. The reaction mixture was cooled
down to room temperature and transferred to 25 mL round bottom flask.
We prepared novel incompletely condensed silsesquioxanes
and germasilsesquioxanes and completely condensed
germasilsesquioxanes with vinylsubstituted metalloid groups that
could be used for further functionalization. We reveal simple and
efficient way of their synthesis and isolation with high purity. The
study presented is an important element in the search for new
materials and efficient methods of their syntheses.
Physicochemical properties of incompletely condensed
silsesquioxanes that result from their open framework make
them attractive potential ligand systems and unique cross linking
agents.
Fractional
distillation
gave
1.55
g
(40%
yield)
SnCl).
3
, δ, ppm): 7.79 – 7.32 (m, 7H), 6.53 (dd, 1H), 6.36 (dd,
of
dichlorophenylvinylgermane (contaminated with ca. 5% of Bu
3
1
H NMR (CDCl
13
1H), 6.18 (dd, 1H). C NMR (CDCl
3
, δ, ppm): 136.94, 134.52, 133.24,
132.58, 132.55, 131.96, 131.55, 129.62, 129.16, 128.89; MS: m/z (rel.
intensity): 248 (7), 221 (14), 186 (16), 109 (28), 104 (100), 77 (35), 51
42)
(
Synthesis of POSS compounds
Difunctional compounds
8
iBu Si
8
O11[OSiMe
2 2
(CH=CH )]
2
(2):
A two-necked, 250 mL flask
equipped with a magnetic stirring bar, reflux condenser and connected to
gas and vacuum line was charged under argon with disilanolisobutyl
POSS (2 g, 2.24 mmol), tetrahydrofuran (80 mL), and triethylamine (1.25
mL, 8.96 mmol). The reaction mixture was cooled in an ice bath and then,
chloro(dimethyl)vinylsilane (0.62 mL, 4.49 mmol) was added dropwise
and the cooling bath left to warm up to room temperature. The molar ratio
of the reactants was as follows: [silanol POSS] : [chlorovinylmetalloid] =
Experimental Section
Methods and Materials: The chemicals were obtained from the
following sources: toluene, tetrahydrofuran, magnesium sulfate (MgSO
from Chempur and P.O.Ch. Gliwice, triethylamine,
chloro(dimethyl)vinylsilane, chloroform-d (CDCl ), tributylchlorostannane,
vinylmagnesium bromide, ABCN (1,1'-Azobis(cyclohexanecarbonitrile)
from Sigma Aldrich, chloro(diphenyl)vinylsilane, trichloromethylgermane
4
)
1
: 2. Progress of the reaction was followed by IR spectroscopy. After
that, tetrahydrofuran was evaporated from the filtrate on rotary
evaporator. Crude product was purified by extraction in toluene-water
3
system, dried over anhydrous MgSO
4
, filtered off. The excess of solvent
was evaporated under vacuum. The product was thoroughly dried giving
from
ABCR,
dichlorodimethylgermane,
form Gelest,
trichloroethylgermane,
disilanolisobutyl POSS,
1
waxy solid (2.19 g, 92%). H NMR (300 MHz, CDCl
3
) δ 6.23 – 6.08 (m,
trichlorophenylgermane
2
0
1
2
6
H), 5.93 (dd, 2H), 5.74 (dd, 2H), 1.92 – 1.77 (m, 8H), 0.96 (m, 48H),
trisilanolisobutyl POSS, trisilanolphenyl POSS, trisilanolisooctyl POSS,
tetrasilanolphenyl POSS from Hybrid Plastics. Tributylvinylstannane was
prepared according to the procedure given in literature.
Liquid substrates were purified by ‘bulb-to-bulb’ distillation and degassed.
All the syntheses of chloro(alkyl/aryl)vinylgermananes were carried out
under an inert argon atmosphere. Tetrahydrofuran was dried over
sodium benzophenone ketyl and freshly distilled prior to use.
13
.57 (m, 16H), 0.23 (s, 4H), 0.19 (s, 8H). C NMR (75 MHz, CDCl
3
) δ
39.37, 131.91, 26.13, 26.06, 26.01, 25.94, 25.87, 25.79, 25.06, 24.06,
[
22]
29
3.73, 23.18, 22.65, 0.44, -0.03. Si NMR (79 MHz, CDCl
3
) δ -2.33, -
5.94, -65.99, -68.03. HRMS (m/z) calcd for C40 13Si10Na: 1081.39,
90
H O
found 1081.39.
iBu Si 11[OGeMe
same procedure and the following reagents: disilanolisobutyl POSS (1 g,
.12 mmol), tetrahydrofuran (40 mL), triethylamine (0.63 mL, 4.49 mmol)
and chloro(dimethyl)vinylgermane (0.29 mL, 2.35 mmol). Finally, a waxy
8
8
O
2 2 2
(CH=CH )] (3): Product (3) was prepared using the
1
Nuclear magnetic resonance (NMR) spectroscopy: H NMR (300, 400
1
13
29
MHz), C NMR (75, 101 MHz) and Si NMR (79 MHz) spectra were
recorded on a Varian XL 300 MHz spectrometer, Varian VNMR-S 400
1
solid was obtained (1.2 g, 91%). H NMR (300 MHz, CDCl
3
) δ 6.24 –
MHz spectrometer in CDCl
ppm) with reference to the residue solvent ( H NMR δ
NMR 77.36 ppm for CDCl ). The mass spectra of the
chlorovinylgermanes were obtained by GC-MS analysis (Varian Saturn
100T, equipped with a CP-SLI 6CB capillary column (30 m × 0.25 mm)
3
solution. Chemical shifts are reported in δ
6
4
1
.07 (m, 2H), 5.92 (dd, 2H), 5.74 (dd, 2H), 2.0 – 1.71 (m, 8H), 0.96 (m,
1
1
3
(
H
= 7.26 ppm,
C
13
8H), 0.58 (m, 16H), 0.19 (s, 12H). C NMR (75 MHz, CDCl
31.74, 25.95, 25.81, 24.08, 23.26, 23.20, 22.64, 22.59, 0.65. Si NMR
) δ -57.90, -66.65, -68.39. HRMS (m/z) calcd for
: 1150.30, found 1149.31.
11[OSiPh (CH=CH )] (4) Product (4) was prepared using the
same procedure and the following reagents: disilanolisobutyl POSS (1 g,
.12 mmol), tetrahydrofuran (40 mL), triethylamine (0.63 mL, 4.49 mmol)
and chloro(diphenyl)vinylsilane (0.5 mL, 2.24 mmol). Finally, a waxy solid
3
) δ 138.55,
δ
C
=
3
29
(79 MHz, CDCl
3
2
C
iBu
40 2 8
H90Ge O13Si
and an ion trap detector). Mass spectrometry analyses were performed
using a Synapt G2-S HDMS (Waters) and UltrafleXtreme (Bruker) mass
spectrometer equipped with the electrospray ion source and quadrupole-
time-of-flight mass analyzer.
8
Si
8
O
2
2 2
1
1
was obtained (1.34 g, 91%). H NMR (300 MHz, CDCl
3
) δ 7.60 –7.07 (m,
Synthesis of vinylchlorogermanes
2
–
0H), 6.53 – 6.33 (m, 2H), 6.24 – 6.02 (m, 2H), 5.92 – 5.62 (m, 2H), 1.87
13
1.57 (m, 8H), 0.95 – 0.68 (m, 48H), 0.58 – 0.34 (m, 16H). C NMR (75
) δ 135.69, 135.08, 134.97, 134.74, 130.25, 129.92, 129.56,
[
19]
Chlorodimethylvinylgermane (1)
and dichloroethylvinylgermane (13)
MHz, CDCl
3
28.08, 127.78, 127.59, 26.10, 25.95, 24.00. Si NMR (79 MHz, CDCl )
3
[
20] were prepared according to the procedures given in literature.
29
1
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
δ -6.29, -67.62, -67.79, -68.29. HRMS (m/z) calcd for C60
98
H O13Si10Na:
g, 0.935 mmol), tetrahydrofuran (60 mL), triethylamine (1.04 mL, 7.48
1329.46, found 1330.45.
mmol) and chloro(diphenyl)vinylsilane (0.83 mL, 3.74 mmol). Finally, a
1
white precipitate was obtained (1.62 g, 91%). H NMR (300 MHz, CDCl
3
)
Trifunctional compounds: These compounds were prepared using an
analogous procedure and the following molar ratio of the reactants:
δ 7.57 – 7.28 (m, 17H), 7.24 – 6.67 (m, 28H), 6.47 – 6.31 (m, 4H), 6.16
13
(dd, 4H), 5.83 (dd, 4H). C NMR (75 MHz, CDCl
135.02, 134.73, 130.22, 129.18, 128.37, 128.06, 127.77, 125.44. Si
NMR (79 MHz, CDCl ) δ -14.59, -18.17, -68.28, -68.47, -73.43, -73.65, -
3
) δ 138.00, 136.65,
29
[
silanol POSS] : [chlorovinylmetalloid] = 1 : 3
iBu Si [OSiMe (CH=CH )] (5): Product (5) was prepared using the
same procedure and the following reagents: trisilanolisobutyl POSS (2 g,
.52 mmol), tetrahydrofuran (80 mL), triethylamine (2.11 mL, 15.16
mmol) and chloro(dimethyl)vinylsilane (1.05 mL, 7.58 mmol). Finally, a
7
O
7 9
2
2
3
3
77.67, -77.93, -78.16, -78.81. HRMS (m/z) calcd for C104
92
H O14Si12Na:
2
1923.36, found 1925.38.
1
waxy solid was obtained (2.38 g, 90%). H NMR (300 MHz, CDCl
3
) δ
Monofunctional vinylgermasilsesquioxanes
6
4
1
.14 (dd, 3H), 5.92 (dd, 3H), 5.74 (dd, 3H), 1.97 – 1.74 (m, 7H), 0.95 (d,
These compounds were prepared using analogous procedure and the
13
2H), 0.55 (d, 14H), 0.20 (s, 18H). C NMR (75 MHz, CDCl
31.91, 26.17, 26.01, 25.78, 25.12, 24.21, 24.10, 23.88, 0.50. Si NMR
) δ -2.69, -67.29, -67.82, -68.04. HRMS (m/z) calcd for
12Si10Na: 1065.40, found 1065.40.
[OGeMe (CH=CH )] (6): Product (6) was prepared using the
3
) δ 139.31,
following molar ratio of the reactants: [silanol POSS]
[chlorovinylmetalloid] = 1 : 1
:
2
9
(79 MHz, CDCl
3
8 8 2
iBu Si O13[GeMe(CH=CH )] (15): Product (15) was prepared using the
same procedure and the following reagents: disilanolisobutyl POSS (2 g,
2.24 mmol), tetrahydrofuran (100 mL), triethylamine (1.25 mL, 8.97
C
iBu
40 90
H O
7
Si
O
7 9
2
2 3
same procedure and the following reagents: trisilanolisobutyl POSS (2 g,
.52 mmol), tetrahydrofuran (80 mL), triethylamine (2.11 mL, 15.16
mmol) and chloro(dimethyl)vinylgermane (0.93 mL, 7.58 mmol). Finally, a
mmol) and dichloromethylvinylgermane (0.31 mL, 2.3 mmol). Finally, a
1
2
waxy solid was obtained (2.14 g, 95%). H NMR (400 MHz, CDCl
3
) δ
6.32 – 6.21 (m, 1H), 6.08 (dd, 1H), 5.88 (dd, 1H), 1.92 – 1.78 (m, 8H),
1
13
waxy solid was obtained (2.72 g, 91%). H NMR (400 MHz, CDCl
3
) δ
0.96 (m, 48H), 0.66 (s, 3H), 0.61 – 0.55 (m, 16H). C NMR (75 MHz,
6
0
.42 – 6.27 (m, 3H), 5.97 (dd, 3H), 5.73 (dd, 3H), 1.92 – 1.80 (m, 7H),
CDCl
22.72, 0.69. Si NMR (79 MHz, CDCl
(m/z) calcd for C35 Na: 1027.27, found 1027.27.
iBu Si 13[GeEt(CH=CH )] (16): Product (16) was prepared using the
same procedure and the following reagents: disilanolisobutyl POSS (2 g,
2.24 mmol l), tetrahydrofuran (100 mL), triethylamine (1.25 mL, 8.97
3
) δ 135.54, 133.47, 26.06, 26.00, 25.86, 24.58, 24.37, 24.14, 23.41,
13
29
.95 (d, 42H), 0.55 (m, 14H), 0.49 (s, 18H). C NMR (101 MHz, CDCl
3
)
3
) δ -65.82, -67.19, -69.21. HRMS
δ 139.57, 139.11, 131.45, 131.01, 26.28, 26.14, 25.85, 25.77, 24.34,
H78GeO13Si
8
29
2
6
4.06, 1.36, 1.00. Si NMR (79 MHz, CDCl
6.65, -67.44, -67.53, -68.28, -68.55. HRMS (m/z) calcd for
Na: 1203.24, found 1201.24.
[OSiMe (CH=CH )] (7): Product (7) was prepared using the
same procedure and the following reagents: trisilanolphenyl POSS (2 g,
.14 mmol), tetrahydrofuran (120 mL), triethylamine (1.8 mL, 12.88
mmol) and chloro(dimethyl)vinylsilane (0.89 mL, 6.44 mmol). Finally, a
3
) δ -58.00, -63.76, -64.83, -
8
8
O
2
40 3 7
C H90Ge O12Si
Ph
7
Si
O
7 9
2
2
3
mmol) and dichloroethylvinylgermane (0.27 mL, 2.29 mmol). Finally, a
1
waxy solid was obtained (2.12 g, 92%). H NMR (300 MHz, CDCl
3
) δ
2
6.27 – 6.13 (m, 1H), 6.08 (dd, 1H), 5.89 (dd, 1H), 1.95 – 1.72 (m, 8H),
13
1.23 – 1.08 (m, 5H), 0.97 – 0.93 (m, 48H), 0.56 (m, 16H). C NMR (75
MHz, CDCl ) δ 134.15, 133.91, 25.96, 25.84, 24.58, 24.40, 24.09, 23.37,
22.70, 10.86, 7.05. Si NMR (79 MHz, CDCl
69.24. HRMS (m/z) calcd for C36 : 1018.30, found 1019.32.
iBu Si 13[GePh(CH=CH )] (17): Product (17) was prepared using the
1
white solid was obtained (2.38 g, 93%). H NMR (300 MHz, CDCl
3
) δ
3
29
7
1
1
.60 – 7.02 (m, 35H), 6.22 (dd, 3H), 5.98 (dd, 3H), 5.83 (dd, 3H), 0.31 (s,
3
) δ -66.00, -67.20, -69.20, -
13
5H), 0.15 (s, 3H). C NMR (75 MHz, CDCl
3
) δ 134.17, 132.88, 132.55,
31.27, 130.22, 127.60, 0.54. Si NMR (79 MHz, CDCl ) δ -0.15, -77.39,
12Si10Na: 1205.18, found
H80GeO13Si
8
29
3
8
8
O
2
-
77.78, -78.14. HRMS (m/z) calcd for C54
62
H O
same procedure and the following reagents: disilanolisobutyl POSS (2 g,
2.24 mmol), tetrahydrofuran (100 mL), triethylamine (1.25 mL, 8.97
1205.18.
Ph
7
Si
7
O
9
[OGeMe
2
(CH=CH
2
)]
3
(8): Product (8) was prepared using the
mmol) and dichlorophenylvinylgermane (0.42 mL, 2.35 mmol). Finally, a
1
same procedure and the following reagents: trisilanolphenyl POSS (2.5
g, 2.68 mmol), tetrahydrofuran (140 mL), triethylamine (2.24 mL, 16.1
mmol) and chloro(dimethyl)vinylgermane (0.99 mL, 8.05 mmol). Finally, a
waxy solid was obtained (2.19 g, 91%). H NMR (300 MHz, CDCl
3
) δ
7.63 (d, 2H), 7.43 (t, 3H), 6.36 (dd, 1H), 6.15 (dd, 1H), 5.91 (dd, 1H),
13
1.93 – 1.74 (m, 8H), 0.93 (m, 48H), 0.63 – 0.51 (m, 16H). C NMR (75
MHz, CDCl ) δ 135.54, 133.47, 26.06, 26.00, 25.86, 24.58, 24.37, 24.14,
23.41, 22.72, 0.69. Si NMR (79 MHz, CDCl
1
waxy solid was obtained (3.19 g, 90%). H NMR (400 MHz, CDCl
3
) δ
)), 0.72 – 0.07 (m,
) δ 138.93, 138.81, 138.60,
34.66, 134.47, 134.37, 134.29, 131.52, 131.38, 131.27, 130.21, 130.11,
3
29
7
1
1
1
.92– 7.04 (m, 35H(-Ph)), 6.41 – 5.22 (m, 9H(-CH=CH
8H(-CH
2
3
) δ -65.49, -67.18, -69.00, -
8
69.09. HRMS (m/z) calcd for C40H80GeO13Si Na: 1089.29, found 1089.30.
13
3
). C NMR (101 MHz, CDCl
3
29
29.79, 129.70, 127.91, 127.70, 127.53, 127.43, 1.41, 1.18, 0.76. Si
) δ -72.71, -72.86, -75.96, -76.10, -79.83, -79.94.
HRMS (m/z) calcd for C54 Na: 1343.02, found 1341.02.
Si [OSiMe (CH=CH (9): Product (9) was prepared using
the same procedure and the following reagents: trisilanolisooctyl POSS
1 g, 0.84 mmol), tetrahydrofuran (40 mL), triethylamine (0.71 mL, 5.1
mmol) and chloro(dimethyl)vinylsilane (0.35 mL, 2.53 mmol). Finally, a
NMR (79 MHz, CDCl
3
H62Ge
3
O12Si
7
Acknowledgements
(
C
8
H
17
)
7
O
7 9
2
2 3
)]
(
We gratefully acknowledge financial support from the National
Science Centre (Poland) (Project UMO-2011/02/A/ST5/00472).
1
viscous oil was obtained (1.12 g, 92%). H NMR (300 MHz, CDCl
3
) δ
6
0
3
.24 – 6.05 (m, 3H), 5.91 (dd, 3H), 5.74 (dd, 3H), 1.36 – 0.44 (m, 119H),
13
.17 (s, 18H). C NMR (75 MHz, CDCl
1.33, 30.42, 26.45, 25.81, 25.44, 25.36, 0.60. Si NMR (79 MHz,
-2.85, -67.51, -67.86, -68.24. HRMS (m/z) calcd for
12Si10N: 1457.84, found 1458.84.
3
) δ 139.35, 131.94, 55.16, 54.75,
Keywords: silsesquioxane • germasilsesquioxane • POSS •
29
incompletely condensed silsesquioxane • heterosilsesquioxane
3
CDCl ) δ
C H O
68 146
[1]
K. Tanaka, Y. Chujo, J. Mater. Chem. 2012, 22, 1733.
Tetrafunctional compounds
These compounds were prepared using analogous procedure and the
[2]
a) G. Kickelbick, Prog.Polym. Sci. 2002, 28, 83; b) C. Jiang, W. Yang,
L. Li, Y. Hou, X. Zhao, H. Liu, Eur. J. Inorg. Chem. 2015, 3835–3842.
following molar ratio of the reactants: [silanol POSS]
chlorovinylmetalloid] = 1 : 4
Ph Si 10[OGeMe (CH=CH
:
[3]
a) V. Ervithayasuporn, J. Abe, X. Wang, T. Matsushima, H. Murata, Y.
[
Kawakami, Tetrahedron, 2010, 66, 9348-9355; b) T. Zhang, J. Wang, M.
8
8
O
2
2
)]
4
(10): Product (10) was prepared using
Zhou, L. Ma, G. Yin, G. Chen, Q. Li, Tetrahedron, 2014, 70, 2478-2486.
a) J. D. Froehlich, R. Young, T. Nakamura, Y. Ohmori, S. Li, A.
Mochizuki, Chem. Mater. 2007, 19, 4991-4997; b) W. Yang, Y. Gan, X.
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the same procedure and the following reagents: tetrasilanolphenyl POSS
2 g, 1.87 mmol), tetrahydrofuran (120 mL), triethylamine (2.08 mL, 14.96
mmol) and chloro(dimethyl)vinylgermane (0.92 mL, 7.48 mmol). Finally, a
[
4]
5]
(
1
white precipitate was obtained (2.68 g, 90%). H NMR (300 MHz, CDCl
3
)
[
a) H. Xu, R. Chen, Q. Sun, W. Lai, Q. Su , W. Huang, X. Liu, Chem.
Soc. Rev., 2014, 43, 3259-3302; b) D. Sun,Z. Ren, M. R. Bryce, S.
Yan J. Mater. Chem. C, 2015, 3, 9496-9508.
δ 7.63 – 7.13 (m, 40H), 6.48 – 6.32 (m, 4H), 5.99 (dd, 4H), 5.78 (dd, 4H),
1
3
0
1
7
1
.59 (s, 24H). C NMR (75 MHz, CDCl
3
) δ 138.83, 134.29, 131.34,
30.29, 127.86, 127.58, 1.32. Si NMR (79 MHz, CDCl ) δ -72.96, -
Na: 1611.01, found
29
3
[
6]
a) C. Hartmann-Thompson, Applications of Polyhedral Oligomeric
Silsesquioxanes, Springer, Dordrecht Heidelberg London New York,
2011; b) S. M. Ramirez, Y. J. Diaz, R. Campos, R. L. Stone, T. S.
Haddad, J. M. Mabry, J. Am. Chem. Soc. 2011, 133, 20084–20087.
6.53, -78.57. HRMS (m/z) calcd for C64
4 8
H76Ge O14Si
607.01.
8 8 2 2 4
Ph Si O10[OSiPh (CH=CH )] (11): Product (11) was prepared using the
same procedure and the following reagents: tetrasilanolphenyl POSS (1
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
FULL PAPER
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European Journal of Inorganic Chemistry
10.1002/ejic.201700465
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Text for Table of Contents
Key Topic*
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
((Insert TOC Graphic here: max.
width: 5.5 cm; max. height: 5.0 cm;
NOTE: the final letter height should
not be less than 2 mm.))
*one or two words that highlight the emphasis of the paper or the field of the study
Layout 2:
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O
FG
FG
Silsesquioxanes,
germasilsesquioxanes*
O
FG
FG
O
O
FG
FG
O
FG
O
O
FG
FG
FG
FG
O
O
O
O
Magdalena Grzelak, Dawid Frąckowiak,
Bogdan Marciniec
FG = ER
2
CH=CH
2
or ERCH=CH
2
E = Si, Ge R = alkil, aryl
Page No. – Page No.
A new group of incompletely condensed silsesquioxanes and
germasilsesqiuoxanes and completely condensed germasilsesquioxanes with
vinylsubstituted metalloid functional groups were synthesized.
Synthesis of incompletely condensed
silsesquioxanes and
germasilsesquioxanes
*one or two words that highlight the emphasis of the paper or the field of the study
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