Preparation and identification of dendritic carbosilanes containing allyloxy groups derived from 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (Me(CH2=CH)SiO)4 and 1,2-bis(triallyloxysilyl)ethane ((CH2=CHCH2O)3SiCH2)2

Article abstract of DOI:10.1016/S0022-328X(98)00794-3

Synthesis and characterization of dendritic macromolecules using 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (Me(CH₂=CH)SiO)₄ and 1,2-bis(triallyloxysilyl)ethane ((CH₂=CHCH₂O)₃SiCH₂)₂ as core molecules and allylalcohol/dichloromethylsilane as a building block have been described. The dendrimers containing dichloromethylsilyl-groups (GS-1P~GS-4P and GH-1P~GH-3P) were produced by the hydrosilation process of double bonds in vinyl and allyloxy-groups in the GS-n and GH-n type dendrimers with dichloromethylsilane in the presence of a platinum catalyst (Pt/C). The GH-n and GS-n type dendrimers containing allyloxysilyl-groups were prepared by the reaction of GH-nP and GS-nP type dendrimers containing Si-Cl bonds and allylalcohol in the presence of TMED at room temperature. The purification of the prepared GH-n and GS-n type dendrimers used simple column chromatography. The yields of the prepared dendrimers have been obtained almost quantitatively. The analyses of the ¹H- and ¹³C-NMR, MALDI mass spectra, and elemental analysis made it possible to obtain the pure and unified dendrimers. In additive manner, the molar absorbities of each generation of GH-n and GS-n type dendrimers show increasing character by the increasing number of double bonds.

Full text of DOI:10.1016/S0022-328X(98)00794-3

Journal of Organometallic Chemistry 570 (1998) 9–22
Preparation and identification of dendritic carbosilanes containing
allyloxy groups derived from
2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane
(Me(CH2ꢀCH)SiO)4 and 1,2-bis(triallyloxysilyl)ethane
((CH2ꢀCHCH2O)3SiCH2)2
Chungkyun Kim *, Younsook Jeong, Inkyung Jung
Department of Chemistry, Dong-A Uni6ersity, Pusan 604-714, South Korea
Received 17 March 1998
Abstract
Synthesis and characterization of dendritic macromolecules using 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane
(Me(CH2ꢀCH)SiO)4 and 1,2-bis(triallyloxysilyl)ethane ((CH2ꢀCHCH2O)3SiCH2)2 as core molecules and allylalcohol/
dichloromethylsilane as a building block have been described. The dendrimers containing dichloromethylsilyl-groups (GS-1Pꢀ
GS-4P and GH-1PꢀGH-3P) were produced by the hydrosilation process of double bonds in vinyl and allyloxy-groups in the
GS-n and GH-n type dendrimers with dichloromethylsilane in the presence of a platinum catalyst (Pt/C). The GH-n and GS-n type
dendrimers containing allyloxysilyl-groups were prepared by the reaction of GH-nP and GS-nP type dendrimers containing Si–Cl
bonds and allylalcohol in the presence of TMED at room temperature. The purification of the prepared GH-n and GS-n type
dendrimers used simple column chromatography. The yields of the prepared dendrimers have been obtained almost quantitatively.
1
The analyses of the H- and 13C-NMR, MALDI mass spectra, and elemental analysis made it possible to obtain the pure and
unified dendrimers. In additive manner, the molar absorbities of each generation of GH-n and GS-n type dendrimers show
increasing character by the increasing number of double bonds. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Allyoxy groups; Dendritic macromolecules; Hydrosilation
1. Introduction
a unified form, a spherical molecular shape, periph-
eral functional groups, etc. [2]. According to litera-
ture, dendrimers with organic skeleton were first
studied, and later, transition metal-containing den-
dritic molecules and silicon-induced dendrimers such
as carbosilane and siloxane have come to the fore [3].
The dendrimers with transition metal complex, such
as ruthenium [4], osmium [5], platinum [6], palladium
[7], iron [8], cobalt [9], gold [10], and copper [11] have
been realized. The dendrimers including silicon metal
may be classified into three main categories, such as
Dendritic macromolecules are prepared by using
repetitive synthetic cycles, which are expected to be a
particularly promising structural concept for new ma-
terials [1]. They exhibit interesting properties, such as
* Corresponding author. Fax: +82 51 2007259; e-mail: ck-
kim@seunghak.donga.ac.kr
0022-328X/98/$ - see front matter © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00794-3

10
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
siloxane (Si–O) [12], carbosilane (Si–C) [13] and polysi-
lane (Si–Si) [14] backbone. The synthetic procedure of
carbosilane dendrimers derived from an alternating hy-
drosilation and alkenylation sequence has been first
given by van der Made, who used chlorosilane as a core
molecule and a Grignard reagent or lithiumorganyl as
generating material [15].
groups with dichloromethylsilane in the presence of a
platinum catalyst, and the complete formation of allyl
ether bonds (–MeSi(OCH2CHꢀCH2)2) on silicon atoms
by the reaction of the chlorosilyl-groups with allylalco-
hol as shown in Schemes 2 and 4. The GS-1P molecule
containing eight growing branches of Si–Cl bonds was
produced by the reaction of 4 equiv. of dichloromethyl-
silane and 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotet-
rasiloxane at room temperature in the presence of a
platinum catalyst. The solvent for hydrosilation must
be dried. If a polar solvent such as THF is used in the
system, it must not be put for a long time because it
will be polymerized in this condition. By our experi-
ence, GS-1P generation can be prepared without a
solvent and other GS-nP generations (n=2–4) formed
in THF or toluene at reflux temperature. GS-1P
molecule is easily converted into GS-1 via alcoholysis
with allyl alcohol in the presence of TMED. The com-
plete reaction of GS-1P to GS-1 and so on was confi-
rmed by NMR spectroscopy. The yields of the two
products in the system were revealed quantitatively by
NMR spectroscopy. The other chlorosilyl-containing
GS-nP (n=2–4) type dendrimers were produced by the
same hydrosilation process of the allyloxy-groups in
GS-n-1 generation with dichloromethylsilane in the
presence of a platinum catalyst (Pt/C, 10% platinum
content). The prepared GS-nP generations were re-
vealed without side products by the NMR spectro-
scopic view. The chlorosilylated generations contained
Cl2MeSi–groups (GS-nP) were converted into the cor-
responding dendritic carbosilanes by the treatment with
allylalcohol in the mixed medium of toluene and
TMED. The hyperbranched dendrimers based on
2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane
(GS-0) as a core molecule with OCH2CHꢀCH2 end
groups as a building block, progressed to GS-4 genera-
tion (Scheme 3), have been synthesized by utilizing the
two alternatives of hydrosilation-alcoholysis sequences.
The formation of GS-5P by the reaction of GS-4 and
HSiMeCl2 did not lead to result in a uniformed
Recently, we have reported a few methods for the
preparation of silicon-containing dendrimers possessing
allyl-, allyloxy- and alkynyl-groups on the periphery
[16]. The preparation of these dendrimers using
organometallic compounds and hydrosilation with a
platinum catalyst allowed us to prepare a new class of
multi-functionalized dendrimers. The synthesis and
characterization of a dendritic carbosilane with ally-
loxy-groups, derived from 2,4,6,8-tetramethyl-2,4,6,8-
tetravinylcyclotetrasiloxane (Me(CH2ꢀCH)SiO)4 with
trichlorosilane and allylalcohol, were performed only in
the second generation with 36 allyloxy-groups ([16]g).
This result is due to the surface saturation which is
identified from other allyl- and alkynyl-group-contain-
ing carbosilane dendrimers [16]. As an extension of
some of our previous studies ([16]a–f) we now report a
detailed study on the reactions of chlorinated carbosi-
lane dendrimers (GH-nP and GS-nP type) with allylal-
cohol in the presence of TMED and hydrosilation of
double bonds on GS-n and GH-n type dendrimers using
platinum in activated carbon (Pt/C, 10% platinum con-
tent in carbon) as a heterogeneous hydrosilation cata-
lyst. The use of the Pt/C catalyst in hydrosilation
procedure does possess a usable advantage that can
control reaction rate and easily isolate the prepared
G-nP type dendrimers from reaction mixture. The pre-
pared dendrimers were characterized with NMR, Maldi
mass, IR and UV spectroscopy. Considerably interest-
ing results were found in the indirect identification
method of the unified dendritic macromolecules by
using UV spectroscopic attachments. We have obtained
increasing molar absorbities of the given dendrimers by
the increasing number of double bonds.
2. Results and discussion
Our study for the preparation of dendritic carbosi-
lane was established with two core molecules, which
have
2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetra-
siloxane (Me(CH2ꢀCH)SiO)4 with a branching degree
of 4 (Nc=4) and 1,2-bis(triallyloxysilyl)ethane ((CH2ꢀ
CHCH2O)3SiCH2)2 with a branching degree of 6 (Nc=
6). The emanated steps of the given dendritic molecules
used the same methods as those of hydrosilation with
dichloromethylsilane and alcoholysis with allylalcohol
(Nb=2) (Scheme 1).
Scheme 1. Core molecules: (a) 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-
cyclotetrasiloxane represented by GS-0 (Nc=4) (b) 1,2-bis(trially-
loxysilyl)ethane represented by GH-0 (Nc=6).
The synthesis of GS and GH type dendrimers was
based on the complete hydrosilation of the alkenyl-

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
11
Scheme 2. Synthetic way of GS-n type dendrimers utilizing alcoholysis/hydrosilation process.
1
molecule according to the H- and 13C-NMR spectro-
scopic view. Eventually, the synthesis of GS-5P with
128 Si–Cl bonds will result in surface saturation, which
will prevent further growth from all branching points
so that the dendrimer will be difficult to be monodi-
sphersed. But all the other synthetic pathways of lower
generations produced uniformed dendrimers with quan-
titative yields (Fig. 1).
In the next model, the hyperbranched dendrimers to
GH-3 based on 1,2-bis(triallyloxysilyl)ethane as a core
molecule have been synthesized by utilizing the two
alternative hydrosilation-alcoholysis sequences. The

12
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
Scheme 3. Planar view of GS-4 generation: Nc=4, Nb=2, Mw=8457 and 64 allyloxy end groups.
molecule and dichloromethylsilane as a building block
(Nc=6, Nb=2), produced the third generation with 48
allylic end groups by the same manner ([16]a, b, d).
Therefore, the GH-0 (Nb=3) with trichlorosilane did
not produce a unified form with 18 Si–Cl bond-con-
taining generation, but with dichloromethylsilane pro-
duced unified GH-1P (Nb=2) with 12 Si–Cl bonds. By
the same evidence, the GH-3 with dichloromethylsilane
did not have a unified form (GH-4P, Nb=2), but with
dimethylchlorosilane produced a unified form (GH-4P,
Nb=1; Scheme 6). They are cause the same result and
are termed ‘surface congestion’.
By the reaction of the GS-n and GH-n type den-
drimers with dichloromethylsilane in the presence of a
platinum catalyst, we observed two different branches
in one molecule. One of them is dehydrogenative cou-
pling products as a minor product (Scheme 6, Figs. 1
and 2). There is no doubt that the major compounds
were hydrosilation products. This result indicated that
the hydrosilation process and dehydrogenative coupling
process occurred simultaneously in the reaction
medium. But, the former is faster than the latter in this
condition. Accordingly, the yield of the former is major
(above 95%). If the reaction temperature is low, the
major product is more. Therefore, GH-1 to GH-3 and
GS-2 to GS-4 dendrimers have been ethenyl branches
chlorosilyl-containing dendrimers (GH-1P to GH-3P)
(Scheme 5) were produced by the same method of
hydrosilation process as shown in 2,4,6,8-tetramethyl-
2,4,6,8-tetravinylcyclotetrasiloxane-based dendrimers.
This process also produced quantitative yields. The
silylated generations (Cl2MeSi–: GH-nP) were con-
verted into the corresponding dendritic carbosilanes
with allylether groups by the treatment with allylalco-
hol and TMED in toluene or THF. The formation of
GH-4P by the reaction of GH-3 and HSiMeCl2 did not
result in a uniformed molecule according to the 1H- and
13C-NMR spectroscopic view. The synthesis of GH-4P
with 96 Si–Cl bonds will result in surface saturation,
which will be the same result of GS-n type dendrimers,
preventing further growth from all branching points so
that the dendrimer will be difficult to be monodi-
sphersed. But all the other synthetic pathways of lower
generations produced uniformed dendrimers with quan-
titative yields as in Fig. 1.
In the case of carbosilane dendrimers with allyl
groups derived from 2,4,6,8-tetramethyl-2,4,6,8-te-
travinylcyclotetrasiloxane as a core molecule (Nc=4)
and dichloromethylsilane as a building block (Nb=2),
produced the fifth generation with 64 allylic end
groups. The allyl-group containing carbosilane den-
drimers with ((CH2ꢀCHCH2)3SiCH2)2 as
a
core

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
13
Scheme 4. Synthetic way of GH-n type dendrimers utilizing alcoholization/hydrosilation process.
as minor products. But the dehydrogenative branches
in the prepared dendrimers were small influenced by
molecular mass because the ethenyl-branches kept on
living.
The purification of GS-n and GH-n type dendrimers
was carried out by chromatography after each alcohol-
ysis step. The purification of GS-nP and GH-nP type
dendrimers was not produced because of their sensiti-

14
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
Fig. 1. 13C-NMR spectroscopic view of GS-n type dendrimers (n=1 (up) to 4 (down)).
vity against moisture. But, the NMR spectroscopic
view of them showed a perfect formation of all genera-
tions. The prepared dendrimers were structurally char-
Among the most useful techniques for the characteri-
zation of GH-n and GS-n type dendrimers is matrix
assisted laser desorption ionization (MALDI) mass
spectroscopy. MALDI mass spectroscopy is demon-
strated by the recent investigation of polyesters and
carbosilane-based dendritic polyols, with excellent re-
sults ([13]h). The MALDI mass spectrum of GH-n and
GS-n type dendrimers mainly shows the fragmentation
of the given compounds. Both spectra show a regular
fragmentation with ion mass 157 and m/z within 1%
of the expected molecular weight. The m/z value of
the dominant signal for GH-n type dendrimers corre-
sponds to the fragmentation of the calculated value of
m/z for GH-1 (Mw: 1376) and GH-2 (Mw: 3275)
dendrimers. Signals are observed between these peaks,
which clearly confirms that the fragmentation of
1
acterized by H- and 13C-NMR spectroscopy, elemental
analyses, MALDI mass, IR, and UV-VIS spectroscopy.
Both reactions with GS-4 and GH-3 generations
seemed to be free of a side reaction except the small
amount of dehydrogenative coupling branches which
were observed by NMR spectroscopy (Figs. 1 and 2).
1
The H- and 13C-NMR spectroscopic analyses of GS-n
(n=1–3) and GH-n (n=2–4) type dendrimers as well
as GS-nP and GH-nP in CDCl3 showed buildings of
dendrimers without defects. The small signals at 105.46
and 137.66 ppm mean dehydrogenative branches of
GH-n and GS-n by hydrosilation procedure (Figs. 1
and 2).

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
15
Scheme 5. Planar view of GH-3 generation: Nc=6, Nb=2, Mw=7074 and 48 allyloxy end groups.
Scheme 6. Mechanistic aspects for synthetic procedure of various dendritic generations.

16
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
Fig. 2. 13C-NMR spectroscopic view of GH-n type dendrimers (n=3 (up) to 0 (down)).
MeSi(OCH2CHꢀCH2)2 groups (m/z, 157) on the molec-
ular surface does not affect the analysis. GH-3 den-
drimer was not observed at the molecular peak.
However, this may be a consequence of aggregation as
we have observed a similar behavior with GH-2. The
m/z value of the dominant signals for GS-n type den-
drimers shows the same evidence in GH-n type den-
drimers. MALDI mass spectrometry was not useful for
GH-3 and GS-4 due to their unusual formation of
matrix (Fig. 3).
difficult. GPC and MALDI mass spectroscopic attach-
ments were used for this purpose [17]. In order to define
dendritic carbosilanes, MALDI mass spectrometry was
employed. So far, the high generation of carbosilane
dendrimers without mass spectroscopic assessment has
been carried out. But, it is very difficult to measure
compounds with high molecular weight. We observed
the phenomena that the molar absorbities of GS-n and
GH-n type dendrimers were proportional to the increas-
ing number of double bonds in UV spectroscopy. The
spectra of the given compounds are similar and consist
of a broad band with a maximum wave length (umax) at
The identification of molecular weight and the
unified character of the prepared dendrimers is very

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
17
Table 1
NMR spectroscopic data of GH-n type dendrimers measured in CDCl3
Compounds
MeSi
CH2
–OCH2–
CH2ꢀ
–CHꢀ
GH–0
1H
0.74
4.24ꢀ4.36
5.04ꢀ5.40
5.76ꢀ6.07
(s, 4H, G0)
1.58 (G0)
(m, 12H, G0)
63.69 (G0)
(m, 12H, G0)
114.63 (G0)
(m, 6H, G0)
136.50 (G0)
13C
1H
GH-1
GH-2
0.14
0.59ꢀ0.78
4.18ꢀ4.31
5.02ꢀ5.36
5.80ꢀ6.03
(s, 18H, G1)
(m, 16H, G0)
1.52–1.80
(m, 12H, G0)
3.61ꢀ3.80
(m, 12H, G0)
1.43 (G0)
9.61, 25.81, 65.11 (G0)
(m, 24H, G1)
(m, 24H, G1)
(m, 12H, G1)
13C
1H
−4.86 (G1)
63.41 (G1)
114.55 (G1)
136.78 (G1)
0.08
0.52ꢀ0.77
4.18ꢀ4.32
5.03ꢀ5.36
5.80ꢀ6.07
(s, 18H, G1)
0.13
(m, 40H, G0–G1)
1.50ꢀ1.78
(m, 48H, G2)
(m, 48H, G2)
(m, 24H, G2)
(s, 36H, G2)
(m, 36H, G0ꢀG1)
3.54ꢀ3.77
(m, 36H, G0ꢀG1)
0.74 (G0)
8.91, 25.18, 64.66
(G0)
13C
−5.61 (G1)
−5.48 (G2)
62.78 (G2)
113.95 (G2)
136.12 (G2)
9.00, 25.27, 64.27
(G1)
GH-3
1H
0.08
0.55ꢀ0.76
4.18ꢀ4.35
5.03ꢀ5.38
5.76ꢀ6.03
(s, 54H, G1ꢀG2)
0.13
(m, 88H, G0ꢀG2)
1.45ꢀ1.79
(m, 96H, G3)
(m, 96H, G3)
(m, 48H, G3)
(s, 72H, G3)
(m, 84H, G0ꢀG2)
3.50ꢀ3.78
(m, 84H, G0ꢀG2)
1.29 (G0)
13C
−5.02
63.40 (G3)
114.58 (G3)
136.74 (G3)
(G1ꢀG2)
−4.87 (G3)
9.38, 25.69, 65.14
(G0)
9.50, 26.00, 65.05
(G1)
9.61, 25.88, 64.89
(G2)
bosilane dendrimers with allyloxy-group have been
critical generations caused by surface congestion. All
dendrimers were soluble in organic solvents, such as
THF, Et2O, and toluene (Tables 1–4, 6 and 7).
240 and 242 nm. The molar absorbities (mmax) of all
allylether-capped dendrimers are approximately in-
creasing according to the number of double bonds (see
Table 5). This shows that there are no unusual effects
and that the allyloxy end groups contribute to the
UV-absorption in an additive manner. We expect the
possibility of determining the molecular mass of these
types of dendrimers by using the increasing phenomena
of molar absorbities of the given compounds.
In conclusion, by the use of hydrosilation and alco-
holysis reaction sequences, carbosilane dendrimers have
been employed to prepare a series of noble dendritic
carbosilanes. Using MALDI mass has been directly
characterized with respect to molecular weight distribu-
tion. By the formation of allyloxy-group containing
dendrimers, we expect the possibility of a determining
method for the molecular mass of these type den-
drimers by using UV spectroscopic attachments. Car-
3. Experimental
All reactions were carried out under dried N2 atmo-
sphere. Ether and THF were dried by sodium-ben-
zophenone ketyl, while solvents, such as pentane,
toluene and benzene, were dried and distilled from Na
metal. All glassware was thoroughly dried with vacuum
before use. Allylalcohol and 2,4,6,8-tetramethyl-2,4,6,8-
tetravinylcyclotetrasiloxane were purchased from
Aldrich. A platinum catalyst (Pt on activated carbon,
10% Pt) was used after vacuum dry at room tempera-
ture. Chlorosilane was distilled before use. NMR spec-

18
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
Fig. 3. MALDI mass spectroscopic view of GS-n type dendrimers.
Table 2
NMR spectroscopic data of GH-nP dendrimers measured in CDCl3
Compounds
MeSi
MeSiCl2
CH2
GH-1P
1H
0.79
0.65 (s, 4H, G0)
(s, 18H, G1P)
1.08ꢀ1.29 (m, 12H, G0)
1.65ꢀ1.91 (m, 12H, G0)
3.66ꢀ3.90 (m, 12H, G0)
1.54 (G0)
13C
5.17 (G1P)
17.69, 25.46, 64.09 (G0)
GH-2P
GH-3P
1H
0.16
(s, 36H, G2P)
0.83
0.52(s, 4H, G0)
(s, 18H, G1)
0.60–0.79 (m, 12H, G0)
1.10ꢀ1.32 (m, 24H, G1)
1.71ꢀ1.92 (m, 36H, G0ꢀG1)
3.65ꢀ3.87 (m, 36H, G0ꢀG1)
1.57(G0)
9.49, 25.91, 65.20 (G0)
17.79, 25.57, 64.22 (G1)
13C
1H
−4.88 (G1)
5.20 (G2P)
0.10
0.78
0.49(s, 4H, G0)
(s, 18H, G1)
0.12
(s, 36H, G2)
(s, 72H, G3P)
0.52ꢀ0.73 (m, 36H, G0ꢀG1)
1.10ꢀ1.25 (m, 48H, G2)
1.69–1.89 (m, 84H, G0ꢀG2)
3.55ꢀ3.82 (m, 84H, G0ꢀG2)
0.38 (G0)
13C
−5.01 (G1)
−4.95 (G2)
5.15 (G3P)
9.51, 25.95, 64.91 (G0ꢀG1)
17.77, 25.42, 63.73 (G2)
tra were recorded on a Bruker AC-200 Spectrometer
in CDCl3. NMR chemical shifts refer to the signals
of the solvents used. FT-IR spectra were measured
by an IFS 55 (Bruker). UV spectra were measured
by a HP 8452A Diode Array UV/VIS. Spectrophoto-
meter (HP). Elemental analysis and MALDI mass
spectroscopy (KRATOS KOMPACKT MALDI 2)
attachments were performed by the Pusan and
Daejon Branches of the Korean Basic Science Insti-
tute.

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
19
Table 3
1H- and 13C-NMR spectroscopic data of GS-n type dendrimers measured in CDCl3
Dendrimers
MeSi
CH2CH2
OCH2CH2CH2
CH2
ꢀCH2
CHꢀ
GS-1
1H
0.07
0.43ꢀ0.69
4.20ꢀ4.29
5.06ꢀ5.37
5.83ꢀ6.01
(s, 12H, G0)
0.13
(m, 16H, G0)
(m, 16H, G1)
(m, 16H, G1)
(m, 8H, G1)
(s, 12H, G1)
13C −5.59 (G1)
−1.54 (G0)
4.98 (G0)
8.04 (G0)
63.47 (G1)
114.54 (G1)
136.89 (G1)
GS-2
1H
0.07
0.43ꢀ0.54
0.56–0.70
4.20ꢀ4.24
5.05ꢀ5.37
5.78ꢀ6.03
(s, 12H, G0)
0.08
(m, 16H, G0)
(m, 16H, G1)
1.51–1.71
(m, 32H, G2)
(m, 32H, G2)
(m, 16H, G2)
(s, 12H, G1)
0.13
(m, 16H, G1)
3.58–3.72
(s, 24H, G2)
(m, 16H, G1)
9.72 (G1)
25.94 (G1)
13C −1.57 (G0)
−5.71 (G1)
4.88 (G0)
8.13 (G0)
64.94 (G1)
63.44 (G2)
114.55 (G2)
136.82 (G2)
−4.84 (G2)
GS-3
1H
0.06
0.45ꢀ0.54
0.54–0.70
4.20ꢀ4.31
5.06ꢀ5.37
5.70ꢀ6.02
(s, 24H, G0ꢀG1)
0.09
(m, 16H, G0)
(m, 48H, G1–G2)
1.53–1.70
(m, 64H, G3)
(m, 64H, G3)
(m, 32H, G3)
(s, 24H, G2)
1.14
(m, 48H, G1–G2)
3.58–3.70
(s, 48H, G3)
(m, 48H, G1–G2)
9.76, 26.11
65.14 (G1)
13C −1.52 (G0)
−5.64 (G1)
4.89 (G0)
8.15 (G0)
63.48 (G3)
114.59 (G3)
136.86 (G3)
−4.92 (G2)
9.67, 25.97
−4.79 (G3)
64.94 (G2)
GS-4
1H
0.06
0.42ꢀ0.59
0.60–0.72
4.20ꢀ4.29
5.05ꢀ5.35
5.68ꢀ6.03
(s, 24H, G0ꢀG1)
0.08
(m, 16H, G0)
(m, 112H, G1–G3)
1.50–1.71
(m, 128H, G4)
(m, 128H, G4)
(m, 64H, G4)
(s, 72H, G2ꢀG3)
0.13
(m, 112H, G1–G3)
3.52–3.71
(s, 96H, G4)
(m, 112H, G1–G3)
65.17, 8.98
25.84 (G1)
13C −1.59 (G0)
−5.75 (G1)
4.87 (G0)
8.13 (G0)
63.45 (G4)
114.56 (G4)
136.83 (G4)
−4.94 (G2ꢀG3)
−4.81 (G4)
65.07, 9.64
26.07 (G2)
9.74, 25.94
64.92 (G3)
The combination of hydrosilation and alcoholysis
reactions has been recently described in other arti-
cles[16]. Therefore, we only show a representative ex-
ample of the slightly modified procedure for the
preparation of all dendrimers.
The following abbreviations are used in the experi-
ments: GS-n refers to each generation of dendritic
silane with 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclo-
tetrasiloxane in the core molecule. GS-nP refers to the
generation of dendritic silane with dichloromethylsilyl
groups in GS-n type dendrimers. GH-n refers to each
generation of dendritic silane with 1,2-bis(triallyloxysi-
lyl)ethane groups in the core molecule. GH-nP refers to
the generation of dendritic silane with dichloromethylsi-
lyl groups in GH-n type dendrimers. Nc refers to the
number of the initiator core (in the case of GS-n,
Nc=4; GH-n, Nc=6). Nb refers to the number of
branching for each new layer (in our experiment, all Nb
is 2). G-n refers to each generation of dendritic silane
with all GH-n and GS-n types. Full experimental details
will appear elsewhere but the following may serve as an
example:
3.1. General procedure of GS-nP type dendrimers
GS-1P. A mixture of 5.20 g (14.94 mmol) of 2,4,6,8-
tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 8.90 g
(77.39 mmol) of HSiMeCl2 and 0.10 g of a hydrosila-
tion catalyst (10% Pt content on activated carbon) was
stirred for 12 h at room temperature. When the reac-

20
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
Table 4
1H- and 13C-NMR spectroscopic data of GS-nP type dendrimers measured in CDCl3
Compounds
MeSi
MeSiCl2
CH2CH2
OCH2CH2CH2
GS-1P
1H
0.13
0.43
0.49ꢀ0.62
(s, 12H, G0)
(s, 12H, G1P)
(m, 8H, G0)
0.69ꢀ0.85
(m, 8H, G0)
8.41, 10.58 (G0)
13C
1H
−1.47 (G0)
0.95 (G1P)
GS-2P
GS-3P
0.09
0.78
0.43ꢀ0.60
1.11ꢀ1.22 (m, 16H, G1)
1.70ꢀ1.82 (m, 16H, G1)
3.65ꢀ3.75 (m, 16H, G1)
(s, 12H, G0)
0.11
(s, 12H, G1)
−1.48 (G0)
−5.72 (G1)
(s, 24H, G2P)
(m, 16H, G0)
13C
1H
5.19 (G2P)
4.88, 8.11 (G0)
17.86, 25.63, 63.81 (G1)
0.06
(s, 12H, G0)
0.09
(s, 12H, G1)
0.12
0.78
(s, 48H, G3P)
0.41ꢀ0.54
(m, 16H, G0)
0.54ꢀ0.69 (m, 16H, G1)
1.10ꢀ1.20 (m, 32H, G2)
1.47ꢀ1.82 (m, 48H, G1–G2)
3.57ꢀ3.80 (m, 48H, G1–G2)
(s, 24H, G2)
−1.51 (G0)
−5.70 (G1)
−4.99 (G2)
13C
1H
5.19 (G3P)
4.80, 8.06 (G0)
9.52, 25.99, 65.00 (G1)
17.79, 25.56, 63.78 (G2)
GS-4P
0.06
(s,24H,G0ꢀG1)
0.10
(s, 24H, G2)
0.12
0.78
(s, 96H, G4P)
0.40ꢀ0.51
(m, 16H, G0)
0.51ꢀ0.68 (m, 48H, G1–G2)
1.09ꢀ1.21 (m, 64H, G3)
1.48ꢀ1.81 (m, 112H, G1–G3)
3.52ꢀ3.79 (m, 112H, G1–G3)
(s, 48H, G3)
−1.19 (G0)
−5.37 (G1)
−4.55 (G2)
1.01 (G3)
13C
5.22 (G4P)
5.01, 8.54 (G0)
13.60, 30.89, 67.97 (G1)
9.60, 26.02, 64.97 (G2)
17.85, 25.61, 63.80 (G3)
tion was completed (by 1H-NMR), excess HSiMeCl2
was removed under vacuum. The platinum catalyst
was filtered off with pentane. The volatile compo-
nents were removed under reduced pressure, leaving
11.67 g (97%) of GS-1P as a colorless liquid. Further
purification was not available because of their sensi-
tivity against moisture. But, the 13C-NMR spectrum
of GS-1P showed only one dendrimer. For the char-
acterization of GS-nP type dendrimers, (Table 4) (1H-
and 13C-NMR). Reaction conditions and yields of all
GS-nP type dendrimers were recorded in Table 8.
Table 5
UV spectroscopic data of GH-n and GS-n type dendrimers measured
in toluene
Table 6
Elemental analysis data of GH-n and GS-n type dendrimers
Compounds
(Mw)a

umax (nm) mmax (l mol−1
mmax/
cm−1
)
Compounds Formular
C (found/calcu- H (%) (found/
lated)
calculated)
GH-0 (426.70)
GH-1 (1376)
GH-2 (3275)
GH-3 (7074)
GS-1 (977.75)
GS-2 (2243)
GS-3 (4776)
6
240
240
240
240
242
242
242
678
1953
4547
9414
902
113
162
189
196
112
144
216
12
24
48
8
16
32
GH-0
GH-1
GH-2
GH-3
GS-1
GS-2
GS-3
GS-4
C20H34Si2O6
C62H118Si8O18
C146H286Si20O42 53.40/53.54
C314H622Si44O90 53.05/53.31
C40H80Si8O12
C96H192Si16O28
C208H416Si32O60 52.15/52.31
C432H864Si64O124 52.63/52.73
56.03/56.30
54.16/54.11
8.05/8.03
8.63/8.64
8.34/8.80
8.69/8.86
8.53/8.25
8.85/8.62
8.92/8.78
8.76/8.85
2307
6913
48.95/49.14
50.88/51.39
, Number of double bond.
a All compounds were colorless oil.

C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
21
Table 7
3.3. GH-0P
IR spectroscopic data of GH-n and GS-n type dendrimer measured in
KBr neat
A mixture of 6.38 g (39.5 mmol) of trichlorovinylsi-
lane, 7.58 g (55.96 mmol) of trichlorosilane, and 0.07 g
of platinum based on a hydrosilation catalyst was
stirred for 12 h at room temperature. When the com-
Compounds
wCꢀC, (cm−1
)
GH-0
GH-1
GH-2
GH-3
GS-1
GS-2
GS-3
GS-4
1640.1 (s)
1648.0 (w), 1667.0 (s)
1647.8 (w), 1668.7 (s)
1642.0 (s), 1660.0 (w)
1646.7 (s)
1663.3 (s), 1646.8 (w)
1663.5 (s), 1646.8 (w)
1663.5 (w), 1646.9 (w)
1
pleted reaction was checked by H-NMR spectroscopy,
excessive trichlorosilane was removed under vacuum.
The catalyst was filtered off with pentane. The product
was crystallized with pentane. Yields: 10.80g (36.34
mmol, 92%) of GH-0P Cl3SiCH2CH2SiCl3 as white
crystals (mp, 41°C). The preparation of GH-n and
GH-nP type dendrimers used the same methods in
GS-n and GS-nP dendrimers under the following con-
ditions (as in Table 8).
3.2. General procedure of GS-n type dendrimers
Acknowledgements
GS-1. Allylalcohol (5.40 g, 92.9 mmol) in 50 ml
toluene was slowly added to a mixture of 9.34 g (11.6
mmol) of G1P and 10.80 g of TMED in 150ml toluene
for about 2 h. After the addition was finished, the
reaction mixture was warmed to about 50°C for 30 min.
This study is supported by the Korean Science &
Engineering Foundation (Grant No.: 97-0101-07-01-5)
and Dong-A University (1997).
1
When the reaction was completed by H-NMR, the salt
was filtered off and washed with pentane. The volatile
components were removed under reduced pressure,
leaving a colorless liquid. All yielded compounds were
chromatographed on silica gel with toluene as an elu-
ent. The product, GS-1, was obtained as a clear and
colorless oil. Yields: 8.41 g (8.6 mmol, 74%). For the
characterization of all dendrimers, see Table 3 (1H- and
13C-NMR), 5 (UV), 7 (IR), and 6 (EA).
References
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1, JAI, London, 1994. (b) J. Issberner, R. Moore, F. Vo¨gtle,
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Table 8
Reaction condition and yields of GH and GS type dendrimers
Compounds No Reactantsa g (mmol)
(Mw)
Reaction conditions solvent (ml)/ T (°C) h−1
Yieldsb g (mmol,
%)
GS-1P (804.80)
GS-1 (977.75)
GS-2P (1898)
GS-2 (2244)
GS-3P (4084)
GS-3 (4776)
S, 5.2 (14.94); D, 6.9 (59.8); C, 0.10
GS-1P, 9.34 (11.6); A, 5.40 (92.9); T, 10.8
GS-1/ 8.40 (8.6); D, 7.9 (69.0); C: 0.15
GS-2P, 14.7 (7.8); A, 7.2 (124.0); T, 14.4
GS-2, 1.93 (0.86); D, 1.6 (13.8); C, 0.1
GS-3P, 3.50 (0.86); A, 1.6 (27.5); T, 3.2
GS-3, 1.20 (0.14); D, 0.87 (7.5); C, 0.1
GS-4P, 1.20 (0.14); A, 0.88 (15.1); T, 1.8
H, 11.0 (37.04); A, 13 (222); T, 25
GH-0, 2.7 (6.40); D, 4.4 (38.4); C, 0.10
GH-1P, 6.3 (5.60); A, 3.9 (67.6); T, 7.5
GH-1, 6.6 (4.80); D, 6.7 (57.8); C, 0.12
GH-2P, 11.7 (4.24); A, 5.9 (101.8); T, 11.8
GH-2, 11.7 (3.57); D, 4.4 (38.4); C, 0.10
GH-3P, 5.29 (0.9), A:2.4 (42.06); T, 4.9
THF (50)/RT–reflux/3
Toluene (150)/RT–60/2
THF (50)/RT–60/2
Toluene (150)/RT–50/1
THF (50)/RTꢀ60/3
Toluene (150)/RT–50/1
THF (50)/RT/3
Toluene (100)/RT–60/3
Toluene (50)/0–50/1
THF (50)/RT/2
11.67 (14.5, 97)
8.4 1 (8.6, 74)
14.9 (7.9, 91)
13.27 (5.9, 76)
3.20 (0.78, 90)
2.45 (0.51, 60)
1.82 (0.22, 92)
0.85 (0.09, 64)
7.8 (18.35, 50)
6.3 (5.6, 90)
11.7 (4.2, 86)
11.7 (4.24, 88)
11.7 (3.57, 84)
18.32 (3.03, 85)
5.1 (0.72, 82)
GS-4P (8457)
GS-4 (9841)
GH-0 (426.70)
GH-1P (1116)
GH-1 (1376)
GH-2P (2756)
GH-2 (3275)
GH-3P (6036)
GH-3 (7074)
Toluene (150)/RT–50/1
THF (50)/RT/3
Toluene (150)/RT/12
THF (50)/RT/2
Toluene (150)/RT/12
a A, Allylalcohol; D, Dichloromethylsilane; C, Catalyst; H, Hexachloroethylenedisilane; S, 2,4,6,8-Tetramethyl-2,4,6,8-tetravinyl-2,4,6,8-tetesila-
1,3,5,7-teteraoxacyclooctane; T, TMED.
b The GH-0 type dendrimer was obtained as colorless crystals; GH-n (n=1–3) and GS-n dendrimers were obtained as colorless oil; GH-nP and
GS-nP were obtained as colorless glass.

22
C. Kim et al. / Journal of Organometallic Chemistry 570 (1998) 9–22
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