Siloxane-supported organometallic compounds and their catalytic activities for the hydrosilylation of vinylsilanes and dienes

Article abstract of DOI:10.1039/b411123k

Two different classes of silicone-modified ligands were prepared: nitrile derivatives, 4′-[3-(organosilyl)propoxy]-biphenyl-4-carbonitrile R′₃SiC₃H₆OC₆H ₄C₆H₄CN 2 (R′₃Si- = a: Me ₃SiOSiMe₂-, b: (Me₃SiO)₂SiMe-, c: Me₃SiO(Me₂SiO)₃SiMe₂-, d: Me ₃SiO(Me₂SiO)₂₅SiMe₂-); and, pyridine derivatives, isonicotinic acid 2-methoxy-4-[3-(organosilyl)propyl]phenyl ester R′₃SiC ₃H₆Ph(OMe)OC(O)C₅H₄N 6. Compounds 2 and 6 were bound to Pd and Pt using ligand substitution reactions with organometallic precursors to give (R₃SiC₃H ₆OC₆H₄C₆H₄CN) ₂PdCl₂ 3, (R₃SiC₃H ₆OC₆H₄C₆H₄CN) ₂PtCl₂ 4 and (R₃SiC₃H ₆C₆H₃(OMe)OC(O)C₅H ₄N)PtCl₂(η²-1-octene) 8. The polydimethylsiloxane (PDMS)-supported Pt and Pd compounds 3d and 4d had excellent solubility in both organic solvents and polysiloxanes. All the Pt compounds exhibited good catalytic activity for hydrosilylation of vinylsilanes. The PDMS-supported Pd compound 3d also was effective catalyst for hydrosilylation of a diene, isoprene, with 1,1,1,3,3-pentamethyldisiloxane MM^H to produce the 1,4-adduct Me₃SiOSiMe ₂CH₂CH=CMeCH₂-H as a major product.

Full text of DOI:10.1039/b411123k

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F U L L P A P E R
Siloxane-supported organometallic compounds and their catalytic
activities for the hydrosilylation of vinylsilanes and dienes
Masaaki Amako,a,b Jonathan Schinkel,b Lee Freiburgerb and Michael A. Brook*b
a Dow Corning Corporation, 2200, W. Salzburg Rd., Midland, MI, USA.
E-mail: masaaki.amako@dowcorning.com; Fax: +1 989 496 6731; Tel: +1 989 496 4400
b Department of Chemistry, McMaster University, 1280, Main St. W., Hamilton, ON, Canada
L8S 4M1. E-mail: mabrook@mcmaster.ca; Fax: +1 905 522 2509;
Tel: +1 905 525 9140 × 23483
Received 21st July 2004, Accepted 22nd October 2004
First published as an Advance Article on the web 24th November 2004
Two different classes of silicone-modified ligands were prepared: nitrile derivatives, 4ꢀ-[3-(organosilyl)propoxy]-
biphenyl-4-carbonitrile Rꢀ3SiC3H6OC6H4C6H4CN 2 (Rꢀ3Si– = a: Me3SiOSiMe2–, b: (Me3SiO)2SiMe–,
c: Me3SiO(Me2SiO)3SiMe2–, d: Me3SiO(Me2SiO)25SiMe2–); and, pyridine derivatives, isonicotinic acid 2-methoxy-4-
[3-(organosilyl)propyl]phenyl ester Rꢀ3SiC3H6Ph(OMe)OC(O)C5H4N 6. Compounds 2 and 6 were bound to Pd and Pt
using ligand substitution reactions with organometallic precursors to give (R3SiC3H6OC6H4C6H4CN)2PdCl2
2
3, (R3SiC3H6OC6H4C6H4CN)2PtCl2 4 and (R3SiC3H6C6H3(OMe)OC(O)C5H4N)PtCl2(g -1-octene) 8. The
polydimethylsiloxane (PDMS)-supported Pt and Pd compounds 3d and 4d had excellent solubility in both organic
solvents and polysiloxanes. All the Pt compounds exhibited good catalytic activity for hydrosilylation of vinylsilanes.
The PDMS-supported Pd compound 3d also was effective catalyst for hydrosilylation of a diene, isoprene, with 1,1,1,3,3-
H
=
pentamethyldisiloxane MM to produce the 1,4-adduct Me3SiOSiMe2CH2CH CMeCH2–H as a major product.
decomplexation to form colloidal metal particles after reaction,
Introduction
and that themselves are silicone polymers. We describe the
A variety of inorganic and organometallic polymers have been
formation of such compounds based on two different classes
reported. Many different morphologies exist for these materials,
of ligands using both Pt and Pd complexes, and examine
including polymers with side chain or in-chain ligands to which
their solubility, stability and catalytic hydrosilylation activity
the transition metals bind,1 and systems in which the metal is an
in silicones.
integral part of the polymer backbone. Among the best studied
ofthe latter class of polymer are the polyferrocenylsilanes discov-
ered and extensively examined by Manners and co-workers.2 The
materials have been used as starting materials for ceramics, as
semiconductors, metallobiomolecules, and polymer-supported
transition metals, etc.3 Our interest is in the development of
the latter class of polymers where the metals also serve as
immobilized catalysts.
A variety of ligands and their organometallic complexes can
be incorporated into silicones.4 However, metal moieties must
be carefully chosen to avoid compromising the Si–O bonds,
which are known to be very sensitive to both acidic and basic
conditions. Moreover, because of the hydrophobic nature of
silicones, metals must also be complexed with non-polar ligands
or complex precipitates will result.
The Direct Process (Rochow–Muller Process) is the largest
scale reaction for preparing Si–C bonds, but it is only practicable
on a very large scale, only synthetically useful for methylation,
and is, in effect, only practised by the silicone industry. Hydrosi-
lylation, by contrast, is a very generic way to prepare C–Si bonds.
The reaction may be catalyzed by a series of different metal
complexes in homogeneous reactions, of which Wilkinson’s
catalyst (Ph3P)3RhCl, Speier’s catalyst (H2PtCl6 in isopropanol)
Results and discussion
Two structurally different ligand motifs are described in turn:
those based on arylnitriles and on pyridines. In both cases, rigid
linear ligands used to facilitate the hydrosilylation reaction, were
also modified with silicone groups to augment the solubility of
the complexes in silicone polymers that act as solvents.
Synthesis of Pd and Pt compounds with nitrile derivative ligands
The hydroxy group in 4ꢀ-hydroxybiphenyl-4-carbonitrile was
reacted with a halogenated alkane, 1-bromododecane, or allyl
bromide, respectively, using potassium carbonate in acetone,
followed by Kugelrohr distillation (Scheme 1). These Williamson
ether conditions6 led to 1a and 1b, respectively, in good yield.
The subsequent introduction of silicone side chains by hydrosi-
lylation of the allyl ethers occurred quantitatively. Two different
silicone morphologies were utilized, those with an internal SiH
group and three monofunctional, terminal silicones.
Pd compounds 3 and Pt compounds 4, with a variety
of siloxane structures, were prepared by the simple ligand
substitution reaction of benzonitrile by the biphenyl derivative 1
in dry acetone (Scheme 1). In these reactions, however, it was not
possible to complete the exchange reaction and fully remove the
PhCN ligand, which was present as a metal ligand on the starting
materials. On average, approximately 15–30% of the PhCN
ligand remained in the product mixture. The IR spectra of the
Pd and Pt compounds 3b and 4b showed CN stretching at 2279
and 2287 cm−1, respectively, which are approximately 50 cm−1
higher than the frequency of the free CN group, 2228 cm−1. It
is known that the CN stretching band may be shifted to either
higher or lower frequencies upon complexation. A completely
=
=
and Karstedt’s catalyst Ptn(H2C CHSiMe2OSiMe2CH CH2)m
are most commonly used. Rhodium is often avoided because
of its expense. Most commercial silicone elastomer products
prepared by hydrosilylation are catalyzed by platinum catalysts,
which are remarkably effective. However, their use, in some
circumstances, can be compromised by the colloidal platinum
particles that form after reaction,5 which scatter light and which
can render the silicone yellow.
We were interested in developing transition metal catalysts
that are soluble and stable in silicones, that do not undergo
7 4
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1
T h i s j o u r n a l i s
T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 5
©

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Scheme 1 Synthesis of 3 and 4.
Scheme 2 Synthesis of 8.
convincing explanation for these effects has not been provided.7
Thus, although free PhCN is not present, it has not been possible
to distinguish between the presence of mono- and disubstituted
PhCN complexes. As noted below, the compounds are soluble
in silicones (Cl2M(PhCN)2 are not very soluble in silicones)
and are effective catalysts. The analogous Pd compound 3e,
which did not possess silicone fragments, was also prepared to
allow a comparison of the catalytic activity. The Pt compounds
4 had slightly better solubility in organic solvents than the
corresponding Pd compounds 3.
compounds (Table 1, Scheme 3). All the Pt compounds showed
good catalytic activity. In addition, the PDMS-supported Pt
compounds 4d and 7d had excellent compatibility with a variety
of solvents.
Synthesis of Pt compounds with pyridine derivatives
The carboxylic group of isonicotinic acid was reacted with
thionyl chloride.8 The resulting acid chloride was subsequently
reacted with the phenol, eugenol, to produce product 5. Hy-
drosilylations on the product pyridine derivatives to add silicone
sidechains were comparably efficient to the biphenyl derivatives.
We note that rather forcing conditions were necessary in this
case: ligands such as pyridine that can bind to the platinum
generally attenuate catalytic activity. Reaction of compound
5 with hydrosilanes based on a disiloxane, an oligomer, or a
macromonomer, respectively, produced viscous liquids 6a–d.
The subsequent reaction with Zeise’s salt produced disiloxane-,
oligosiloxane- and PDMS macromonomer-supported Pt com-
pounds 7a–d, respectively, followed by the ligand substitution to
produce 8 (Scheme 2).9 The Pt compound 7d was characterized
Scheme 3 Hydrosilylation products of MMH with MVi,OEt
.
A related hydrosilylation of MMH was performed with 1-
vinyl-1,1,3,3,3-pentamethyldisiloxane MMVi using a variety of
organometallic compounds (Table 2) in the absence of solvents
to produce two isomers, Si4-a and Si4-b (Scheme 4). The
palladium compounds 3 were not efficient catalysts for this
hydrosilylation. Instead, signals of an ethyl group were observed
and the integral ratio of the SiH signal decreased dramatically in
the 1H NMR spectra. The data indicate that 70–80 mol% of the
SiH groups were oxidized to produce hydrogen, which partially
hydrogenated the vinyl groups (6–17 mol%) in situ.
1
1
by H, 13C and 29Si NMR, in which the H NMR signals of
the ethylene ligand were downfield shifted by 0.78 ppm and the
signals also had a strong Pt–H coupling (63.7 Hz).
Catalytic reactions
Pt0 and PtII compounds, most notably Karstedt’s and Speier’s
catalysts, have a long productive history as hydrosilylation
catalysts with alkenes and alkynes. A variety of other platinum
catalysts have recently been developed to improve reaction
efficiency and reaction selectivity.10 Pd compounds are known
as hydrosilylation catalysts primarily for dienes. For example,
Pd compounds are used to catalyze the hydrosilylation of 1,3-
dienes with trichlorosilane to produce the corresponding cis-1,4-
adducts.11
We examined the utility of Pt and Pd compounds, 3, 4, 7
and 8, as hydrosilylation catalysts. First, a model hydrosilylation
of 1,1,1,3,3-pentamethyldisiloxane, MMH was performed with
dimethylethoxyvinylsilane (MVi,OEt) leading to a mixture of
two isomers, Si3-a and Si3-b using selected organometallic
Scheme 4 Hydrosilylation products of MMH with MMVi.
The Pt compounds 4 and 8 were comparable to Karstedt’s
catalyst in giving the hydrosilylated products, and there was
no evidence of colloidal platinum when 4 and 8 were used as
catalysts. Wilkinson’s catalyst, (Ph3P)3RhCl, which was initially
dissolved in THF prior to its addition in order to create a
homogeneous solution, showed similar reactivity to the Pt
compounds, but its catalytic activity was slightly lower.
Isoprene is a conjugated diene and, therefore, can be hy-
drosilylated by both 1,2- and 1,4-additions leading to six
different compounds (Scheme 5). Some Pd compounds have
been reported to be selective hydrosilylation catalysts for electron
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1
7 5

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Table 1 Hydrosilylation products by different catalystsa
Catalyst
Solvent
Solubility
Conversion (%)
Si3-a (%)
Si3-b (%)
b
(PhCN)2PtCl2
Toluene
Toluene
Toluene
Benzene-d6
N/A
Poor
Good
Excellent
Excellent
N/A
>99
∼0
13
—
10
20
8
87
—
90
80
92
(PhCN)2PdCl2
4d
7d
>99
>99
>99
Karstedt’s cat.c
a The hydrosilylation reaction condition involved MVi, OEt and a catalyst in a flask at room temperature, followed by the addition of MMH (1eq.)
dropwise, and then, the mixture was heated at 85 ◦C for 2 h. b (PhCN)2PtCl2 could not be dissolved in toluene, then, a small amount of dry acetone
was added to dissolve it. c 2 wt% of Pt in xylene. Any additional solvents were not used for this reaction, except this catalyst solution.
Table 2 Hydrosilylation products by different catalystsa
Table 3 Hydrosilylation products by different catalystsa
Catalyst
Conversion (%)
Si4-a (%)
Si4-b (%)
Catalyst
mol% of Cat.
Conversion (%)
Main products
3cb
—
—
—
—
—
—
5
5
5
5
5
5
6
—
—
—
95
95
95
95
95
95
94
94
98
(PhCN)2PdCl2
3d
9.6 × 10−1
∼0
—
3db
6.7 × 10−3
>99
1,4-d (∼60)
3,4-d (∼20)
1,4-d ≈ 3,4-d
3,4-d (∼30)
—
3eb
4a
>99
>99
>99
>99
>99
>99
>99
>99
91
4b
1.5 × 10−2
1.1 × 10−2
2.0 × 10−2
<20
∼80
<20
4b
Karstedt’s cat.b
Karstedt’s cat.c
4c
4d
a The hydrosilylation reaction conditions involved placing MMH and a
catalyst in a flask at 80 ◦C, followed by the addition of isoprene (1 eq.)
dropwise, then the mixture was heated another 2 h at 80 ◦C. b 23 wt%
of Pt in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. c 2 wt% of Pt in 1,3-
divinyl-1,1,3,3-tetramethyldisiloxane.
8a
8b
8d
Karstedt’s catalystc
Wilkinson’s catalyst
6
2
a The hydrosilylation reaction conditions involved addition of MMVi and
a catalyst in a flask at 80 ◦C, followed by the addition of MMH (1 eq.)
dropwise, then the mixture was heated another 2 h at 80 ◦C. b Based on
1H NMR analysis, about 10–20% of the vinyl groups were hydrogenated
to become ethyl groups, and about 70–80% of SiH groups disappeared.
These results indicate that SiH groups generated hydrogen during the
reaction, which led to palladium-catalyzed hydrogenation of the vinyl
group. Hydrosilylation was inefficient (<5%). c 2 wt% of Pt in xylene.
frequently undergoes loss of ligands with concomitant metal
aggregation leading to colloidal platinum.
The silicone-modified compounds described above are highly
active as shown by the low quantities of catalyst necessary for
effective reaction, benefit from their solubility as demonstrated
by the improved reaction of the compounds 3d, 4b, 4d and 7d to
(PhCN)2PdCl2, and are not compromised by the formation of
colloidal platinum or palladium. Although monomeric species
were produced by using monofunctional silicones, the synthesis
is completely compatible with polymer synthesis. In fact, it is
much easier to obtain either di-terminally modified or pendant
modified silicones (hydrosilanes), that can be used to prepare
high molecular weight polymers in which the transition metal-is
a constituent of the backbone. The utilization of the chemistry
described above to synthesize macromolecular catalysts will be
the subject of future reports.
deficient SiH compounds with conjugated alkenes to produce
1,4-adducts as major products (vide supra).11 The hydrosily-
lation of MMH with isoprene was performed using selected
organometallic compounds in the absence of solvents. A mixture
of (PhCN)2PdCl2 and MMH generated a gas, which was likely
hydrogen, by SiH reduction of the PdII compound, to generate a
Pd0 compound: little hydrosilylation was observed. In contrast,
the reaction using PDMS-supported Pd compound 3d (Table 3)
=
produced a 1,4-SiH adduct ofMe3SiOSiMe2CH2CH CMe2 1,4-
d and 3,4-d in a 3 : 1 ratio with no observations of bubbles in
the flask. The result indicated that the PDMS chain protected
its metal center from the SiH reducing group.
Conclusions
Pd and Pt compounds derived from silicone-modified ben-
zonitriles and pyridines exhibited different catalytic reactivities
for hydrosilylation. All Pt compounds, having either nitrile
or pyridine ligands, were excellent catalysts for the reaction
of pentamethyldisiloxane with vinylsilanes. Among them, the
Pt compounds having PDMS chains, 4d, 7d and 8d, showed
excellent solubility, compared with (PhCN)2PtCl2. On the other
hand, the Pd compounds did not show any catalytic activities
for simple hydrosilylation. However, a silicone-modified Pd
compound catalyzed hydrosilylation of pentamethyldisiloxane
with isoprene to produce primarily a 1,4-adduct, whereas the
analogous Pd compound without silicone groups did not show
any catalytic activity.
Scheme 5 Hydrosilylation products of MMH with isoprene.
Experimental
Many platinum catalysts have been developed for hydrosi-
lylation. Supported catalysts are generally less effective than
homogeneous catalysts. Normally, solvents are required with
homogeneous catalysts for high yielding reactions with silicones
because of solubility problems when the reactions are run
under neat conditions. The notable exceptions to this are
Speier’s and Karstedt’s catalysts and analogues. During and
after reaction with these compounds, however, the platinum
Compounds
4ꢀ-Hydroxy-4-biphenylcarbonitrile, potassium carbonate, allyl
bromide, 1-bromododecane, triethylamine, isonicotinic acid,
eugenol, Karstedt’s catalyst (platinum(0)-1,3-divinyl-1,1,3,3,-
tetramethyldisiloxane complex) in xylene, 1,1,1,3,5,5,5-
heptamethyltrisiloxane (MDHM), ethoxydimethylvinylsilane,
7 6
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1

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isoprene, Wilkinson’s catalyst (chlorotris(triphenylphosphine)-
rhodium(I)), activated carbon and Celite 521 were pur-
chased from Aldrich and used as received except as mentioned
below. 1,1,1,3,3-Pentamethyldisiloxane and vinylpentamethyl-
disiloxane were purchased from Gelest. Bis(benzonitrile)-
dichloropalladium(II)andbis(benzonitrile)dichloroplatinum(II),
bis(benzonitrile)dichloroplatinum(II) and Ziese’s salt (potas-
4ꢀ-Dodecyloxybiphenyl-4-carbonitrile 1b. 4ꢀ-Hydroxy-4-bi-
phenylcarbonitrile (1.0083 g, 5.165 × 10−3 mol), potassium
carbonate (2.2524 g, 1.629 × 10−2 mol) and dry acetone (20 mL)
were put in a 50 mL flask and stirred. 1-Bromododecane
(2.6640 g, 1.069 × 10−2 mol) was added and the reaction
was heated to reflux temperature for 35 h, then the flask was
cooled and any volatiles were distilled off. The mixture was
dissolved in dichloromethane and washed with water four times,
and brine two times. The organic residue was distilled with a
microtube oven to give a fraction of 165–180 ◦C/<1 mmHg,
which crystallized as white crystals (1.5144 g, 4.514 × 10−3 mol,
87.4% yield).
=
sium trichloro(ethylene)platinate(II) monohydrate [PtCl3(CH2
CH2)]−K+·H2O) were purchased from Strem Chemicals. Thionyl
chloride was purchased from Alfa Aesar. Karstedt’s catalyst
in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane was obtained from
Dow Corning Corporation.
A PDMS macromonomer
(Me3SiO(Me2SiO)25-SiMe2H) and a pentasiloxane (Me3SiO(-
Me2SiO)5SiMe2H) were obtained from Dow Corning Toray
Silicone Co., Ltd. Reagent grade toluene, anhydrous grade THF
and anhydrous grade diethyl ether were dried over sodium-
benzophenone ketyl and stored under a nitrogen atmosphere.
Distilled grade acetone was dried over calcium sulfate and
stored under a nitrogen atmosphere. Distilled grade methylene
chloride was dried over calcium hydride and stored under a
nitrogen atmosphere. Anhydrous grade hexanes, anhydrous
n-hexane, anhydrous cyclohexane, anhydrous di-n-butyl ether,
anhydrous ethanol and anhydrous grade n-heptane were
purchased from Aldrich and used as received.
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 7.64 (m, 4H), 7.51
(d, J = 8.8 Hz, 2H), 6.97 (d, J = 8.8 Hz, 2H), 3.98 (t, J =
6.5 Hz, 2H, –OCH2CH2–), 1.82 (m, 2H, –OCH2CH2–), 1.24
(br s, 18H), 0.860 (t, J = 6.1 Hz, 3H, –CH2CH3); 13C NMR
(50.3 MHz, CDCl3, 77 ppm): d 159.8, 145.3, 132.5, 131.2, 128.3,
127.0, 119.1, 115.1, 110.0, 68.2, 31.9, 29.6, 29.4, 26.0, 22.7, 14.1.
4ꢀ-[3-(Trimethylsiloxydimethylsilyl)propoxy]biphenyl-4-carbo-
nitrile 2a. 1a (0.2076 g, 8.8235
×
10−4 mol), toluene
(10 mL), MMH (217.2 mg, 1.464 × 10−4 mol) and platinum(0)–
1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylenes
(2 wt% Pt, 20 lL) were charged in a 50 mL Schlenk tube, then
the mixture was heated to 112 ◦C for 2 d, and then cooled
to room temperature. Activated carbon was added and the
Equipment
◦
mixture was again heated to 80 C for 1 h, and then cooled to
1H NMR spectra were recorded on a Bruker AV-500 (500 MHz),
Bruker AV-300 (300 MHz) or Bruker AV-200 (200 MHz)
spectrometer. 13C and 29Si NMR were performed on a Bruker
AV-200 (at 50.3 MHz for carbon), and a Bruker AV-300 (at
room temperature. The activated carbon was filtered through a
0.2 lm-pore PTFE membrane filter and the solution was
distilled off to give of a white solid (0.3344 g, 8.716 × 10−4 mol,
98.8% yield).
1
59.6 MHz for silicon), respectively. H NMR Chemical shifts
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 7.65 (m, 4H), 7.50
(d, J = 8.9 Hz, 2H), 6.97 (d, J = 8.9 Hz, 2H), 3.96 (t, J =
6.9 Hz, 2H, –OCH2CH2–), 1.82 (m, 2H, –OCH2CH2–), 0.63
(m, 2H, –SiCH2–), 0.10–0,02 (br s, 15H, SiCH3); 13C NMR
(50.3 MHz, CDCl3, 77 ppm): d 159.8, 145.3, 132.5, 131.2, 128.3,
127.1, 119.1, 115.1, 110.0, 70.6, 23.3, 14.2, 2.0, 0.3; 29Si NMR
(59.6 MHz, CDCl3, d/ppm): 7.8, −21.7, Mass spectra (CI) m/z :
383 (M+), 401 (M+ + NH4+).
are reported with respect to tetramethylsilane as standard, set to
0 ppm, CHCl3 at 7.24 or C6H6 at 7.15 ppm. Coupling constants
(J) are recorded in Hertz (Hz). The abbreviations s = singlet, d =
doublet, t = triplet, dd = doublet of doublets, m = multiplet, are
used in reporting the spectra. Electron impact (EI) and chemical
ionization (CI, NH3) mass spectra were recorded at 70 eV with
a source temperature of ca. 200 ◦C on a VG analytical ZAB-E
mass spectrometer equipped with a VG11-250 data system. IR
spectra were runona PerkinElmer 283spectrometer and Fourier
spectra on a BIO RAD FTS-40 spectrometer (neat film or KBr
disc). GC analysis was carried out using a Hewlett Packard 5890
gas chromatograph using FID detector and equipped with DB-
1 capillary column (30 m × 0.53 mm i.d. × 0.5 lm film, J&W
Scientific) and HP integr◦ator (3393A). The initial temperature
4ꢀ-[3-(Bis(trimethylsiloxy)methylsilyl)propoxy]biphenyl-4-car-
bonitrile 2b. 1a (0.2102 g, 8.822 × 10−4 mol), toluene (10 mL),
1,1,1,3,5,5,5-heptamethyltrisiloxane (349.0 mg, 1.568
×
10−3 mol) and platinum(0)–1,3-divinyl-1,1,3,3,-tetramethyl-
disiloxane complex in xylenes (2 wt% Pt, 20 lL) were charged
in a 50 mL Schlenk tube, then the mixture was heated to 112 ◦C
for 2 d, and then cooled to room temperature. Activated carbon
was added and the mixture was heated to 80 ◦C for 1 h, and
then cooled to room temperature again. The activated carbon
was filtered through a 0.2 lm-pore PTFE membrane filter and
the solution was distilled off to give a white solid (0.3888 g,
8.504 × 10−4 mol, 96.4% yield).
◦
was 8◦0 C and final 250 C with a temperature increment rate
of 20 C min−1. Helium gas was used as the carrier gas.
Syntheses
4ꢀ -Allyloxybiphenyl-4-carbonitrile 1a. 4ꢀ -Hydroxy-4-bi-
phenylcarbonitrile (5.515 g, 2.826 × 10−2 mol), potassium
carbonate (8.094 g, 5.856 × 10−2 mol) and acetone (90 mL)
were put in a 250 mL flask and stirred. Allyl bromide (5.8 mL,
6.7 × 10−2 mol) was added and the mixture was heated to
56 ◦C overnight, then the flask was cooled and any volatiles
were distilled off under vacuum. The mixture was dissolved
in dichloromethane and washed with water four times. The
solvents were distilled off and the residue was distilled by a
microtube oven to collect a fraction (6.181 g, 2.627 × 10−2 mol,
93.0% yield, white crystals) at 135–155 ◦C/<1 mmHg.
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 7.65 (m, 4H), 7.49
(m, 2H), 6.98 (m, 2H), 3.95 (t, J = 7.8 Hz, 2H, –OCH2CH2–),
1.81 (m, 2H, –OCH2CH2–), 0.57 (m, 2H, –SiCH2–), 0.20 to
−0,02 (br s, 21H, SiCH3); 13C NMR (50.3 MHz, CDCl3,
77 ppm): d 159.8, 145.3, 132.5, 131.2, 128.3, 127.1, 119.1, 115.1,
110.0, 70.4, 23.0, 13.5, 1.8, 1.6, Mass spectra (CI): m/z 457 (M+).
4ꢀ -(3-Undecamethylpentasiloxyl)propoxy)biphenyl-4-carboni-
trile 2c. 1a (0.9119 g, 0.003876 mol) and toluene (20 mL)
were charged into a 50 mL RBF, followed by 50 lL of
a solution containing 2% Karstedt’s catalyst, and finally
Me3SiO(Me2SiO)3SiMe2H (1.46 g, 3.94 × 10−4 mol) was added.
The reaction mixture was refluxed for 3 h. One scoop (0.01 g)
of activated carbon was added to the flask, and the mixture
was kept for 30 min at 80 ◦C. The mixture was filtered through
a PTFE membrane filter (0.45 lm pore) and the solution
was distilled off using a rotary evaporator. A white solid was
obtained (2.0424 g, 3.369 mmol, 86.9%).
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 7.65 (m, 4H), 7.51
=
(m, 2H), 7.00 (m, 2H), 6.05 (m, 1H, –CH2CH CH2), 5.42 (dd,
=
J = 17.3, 1.5 Hz, 1H, –CH2CH CH2), 5.31 (dd, J = 10.5,
=
1.5 Hz, 1H, –CH2CH CH2), 4.58 (d, J = 5.2 Hz, 2H, –CH2O–);
13C NMR (50.3 MHz, CDCl3, 77 ppm): d 159.2, 145.2, 132.9,
132.6, 128.4, 128.3, 127.0, 119.1, 118.0, 115.3, 110.1, 68.9, Mass
spectra m/z: (calc.: 235.1) TOF MS CI− 235.1, TOF MS EI+
235.1 (M+), IR (cm−1): 2225 (mCN, vs), 1605, 1493, 1456, 1291,
1249, 1180, 995, 940, 834.
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1
7 7

View Article Online
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 0.54 (s, 33H,
CH3Si), 0.65 (t, 2H, J = 8.3 Hz, SiCH2CH2–), 1.83 (m, 2H,
CH2CH2CH2), 3.96 (t, 2H, J = 6.8 Hz, OCH2CH2), 6.98 (d, 2H,
J = 8.7 Hz, Ph), 7.51 (d, 2H, J = 8.8 Hz, Ph), 7.62 (d, 2H, J =
8.1 Hz, Ph), 7.68 (d, 2H, J = 8.4 Hz, Ph); 13C NMR (50.3 MHz,
CD2Cl2): d 0.6 (q, J = 118 Hz, CH3Si), 1.6 (q, J = 118 Hz,
CH3Si), 2.2 (q, J = 118 Hz, CH3Si), 14.7 (t, J = 117 Hz, CH2),
23.8 (t, J = 127 Hz, CH2), 71.0 (t, J = 143 Hz, CH2O), 110.7
(s, ipso-PhCN), 115.6 (d, J = 159 Hz, Ph), 119.4 (s, CN), 127.4
(d, J = 151 Hz, Ph), 128.8 (d, J = 157 Hz, Ph), 131.5 (s, Ph),
133.0 (d, J = 165 Hz, Ph), 145.5 (s, Ph), 160.4 (s, ipso-PhO); 29Si
NMR (59.6 MHz, CDCl3): 7.6, −21.3, Mass spectra (EI): m/z
605.2 (M+), (CI): m/z 605.2 (M+)
and heated at 110 ◦C for 20 h. The solution was distilled off
under vacuum. The residue was washed twice by ethanol,
followed by removal in vacuo to produce a brownish white solid
1
(0.0310 g, 3.00 × 10−5 mol, 95% yield). H NMR (200 MHz,
CDCl3): d 7.80–7.44 (m, 12H), 6.97 (m, 4H), 3.95 (m, 4H), 1.82
(m 4H), 0.64 (m, 4H), 0.10–0.04 (30H, SiCH3)
[4ꢀ -{3-(Bistrimethylsiloxymethylsilyl)propoxy}-4-carboni-
trile]2PdCl2 4b. Bis(benzonitrile)dichloroplatinum(II) (0.0233 g,
5.21 × 10−5 mol) and toluene (10 mL) was charged in a Schlenk
tube. 2b (0.0479 g, 1.046 × 10−4 mol) was added and heated at
◦
110 C for 20 h. The solution was distilled off under vacuum.
The residue was washed twice by ethanol, and removed by
distillation to produce a brownish white solid (0.0561 g, 4.75 ×
10−5 mol, 91% yield). 1H NMR (200 MHz, CDCl3): d 7.80–7.48
(m, 12H), 6.98 (m, 4H), 3.95 (t, J = 6.8 Hz, 4H), 1.82 (m, 4H),
0.57 (t, J = 8.4 Hz, 4H), 0.11–0.22 (42H, SiMe)
4ꢀ-[3-(Polydimethylsiloxy)propoxy]biphenyl-4-carbonitrile 2d.
1a (0.4706 g, 2.00 × 10−3 mol), toluene (50 mL), Me3SiO(Me2Si–
O)25SiMe2H (4.0243 g, 2.00 × 10−3 mol) and Karstedt’s catalyst
in xylenes (2 wt% Pt, 50 lL) were placed in a 100 mL flask, then
[4ꢀ -{3-Undecamethylpentasiloxy)propoxy}biphenyl-4-carbo-
nitrile]2PtCl2 4c. Bis(benzonitrile)dichloroplatinum(II) (0.0444 g,
9.40 × 10−5 mol) and CH2Cl2 (10 mL) was added to a Schlenk
tube. Compound 2c (0.1146 g, 1.89 × 10−4 mol) was added and
reacted for 1 h. The solution was distilled off under vacuum
conditions for 30 h. A white–brown solid (0.1513 g), containing
benzonitrile (ca. 0.01 g) was obtained.
◦
the mixture was heated to 112 C for 19 h, and then cooled to
room temperature. Activated carbon was added and the mix-
ture was heated to 80 ◦C for 1 h, and then cooled to room
temperature again. The activated carbon was filtered through a
0.2 lm-pore PTFE membrane filter and the solution was distilled
off to give a viscous liquid (4.495 g, 2.00 × 10−3 mol, 100% yield).
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 7.65 (m, 4H), 7.51
(m, 2H), 6.98 (m, 2H), 3.95 (t, J = 6.8 Hz, 2H, –OCH2CH2–),
1.84 (m, 2H, –OCH2CH2–), 0.66 (m, 2H, –SiCH2–), 0.25 to
−0,05 (br s, 165H, SiCH3); 13C NMR (50.3 MHz, CDCl3,
77 ppm): d 159.8, 145.3, 132.5, 131.2, 128.3, 127.1, 119.1, 115.1,
110.1, 70.6, 23.2, 14.2, 1.8–0.1.
1H NMR (CDCl3, 200 MHz): d 0.09 (m, 66H, SiCH3), 0.69
(m, 4H, SiCH2), 1.85 (m, 4H, SiCH2CH2), 3.98 (t, J = 6.8 Hz,
4H, CH2O), 6.99 (d, J = 6.7 Hz, 4H, Ph-H), 7.69 (m, 12H)
[4ꢀ -{3-(Polydimethylsiloxy)propoxy}biphenyl-4-carboni-
trile]2PtCl2 4d. Bis(benzonitrile)dichloroplatinum(II) (0.0429 g,
9.084 × 10−5 mol) and toluene (20 mL) was added to a Schlenk
tube. 2d (0.4089 g, 1.824 × 10−4 mol) was added and reacted
for 14 h at 111 ◦C. The solution was distilled off under vacuum
[4ꢀ -(3-Undecamethylpentasiloxy)propoxy)biphenyl-4-carbo-
nitrile]2PdCl2 3c. A Schlenk tube was charged with bis-
(benzonitrile)dichloropalladium(II) (0.0393 g, 1.024 × 10−4 mol)
and CH2Cl2 (10 mL). 2c (0.1360 g, 2.24 × 10−4 mol) was added
and reacted for 1 h. The solution was distilled off under vacuum
over 30 h. A brownish white solid (0.1576 g), which included
benzonitrile (ca. 0.003 g) was obtained.
1
over 30 h. A brown liquid was obtained (0.4472 g). H NMR
(200 MHz, CDCl3): d −0.06 to 0.14 (330H, –SiCH3), 0.65 (m,
4H, –SiCH2–), 1.84 (m, 4H, –SiCH2CH2–), 3.95 (t, J = 7.0 Hz,
4H, –CH2CH2O–), 6.97 (m, 4H), 7.45–7.84 (m, 12H)
1H NMR (CDCl3, 200 MHz): d 0.10 (s, 66H, SiCH3), 0.70 (m,
4H, SiCH2), 1.87 (m, 4H, SiCH2CH2), 3.98 (t, J = 6.8 Hz, 4H,
CH2O), 7.00 (d, J = 8.7 Hz, 4H, OCCH), 7.62 (m, 12H).
Isonicotinic acid 4-allyl-2-methoxyphenyl ester 5. SOCl2
(3.0 mL, 4.11 × 10−2 mol) was added dropwise over 1 min to
a stirred suspension of isonicotinic acid (4.1203 g, 3.3468 ×
10−2 mol) in n-Bu2O (40 mL). The reaction mixture was allowed
to stir for 1 h at 80 ◦C, and the solvents distilled off in vacuo. After
this time, the compound was dispersed into dichloromethane
(100 mL) and was added to a stirred solution of eugenol
(5.4618 g, 3.3263 × 10−2 mol) and triethylamine (3.4029 g,
3.3629 × 10−2 mol) in dichloromethane (30 mL) and stirring was
continued for a further 36 h. Then, the solution was distilled off
in vacuo and toluene was added. Finally, HClNEt3 was filtered
off through Celite and the material was distilled in vacuo at
100 ◦C using a microdistillation oven to give 5 (3.1034 g, 34.4%).
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 8.832 (br s, 2H,
–CHNCH–), 8.104 (d, J = 5.6 Hz, –CHCHN–), 7.048 (d,
J=7.7 Hz, 1H, Ph-H), 6.827 (s, 1H, Ph-H) 6.808 (d, J = 7.7 Hz,
[4ꢀ -(3-(Polydimethylsiloxy)propoxy)biphenyl-4-carbonitrile]2
PdCl2 3d. A Schlenk tube was charged with bis(benzo-
nitrile)dichloropalladium(II) (0.1085 g, 2.828 × 10−4 mol) and
acetone (10 mL). 2d (1.2632 g, 5.654 × 10−4 mol) was added
and reacted for 2 h. The solution was distilled off under vacuum
1
over 20 h. A brownish white gel was obtained (1.3249 g). H
NMR (200 MHz, CDCl3): d 7.66 (m, 8H), 7.49 (m, 4H), 6.97
(d, J = 8.6 Hz, 4H), 3.95 (t, J = 6.9 Hz, 4H), 1.83 (m, 4H), 0.65
(m, 4H), 0.2 to −0.1 (s, 330H); 13C NMR (50.3 MHz, CDCl3):
d 160.3, 145.3, 133.8, 132.2 128.6, 127.1, 120.6, 115.1, 106.3,
70.6, 23.2, 14.2, 1.8, 1.0, 0.3, 0.1.
[4ꢀ-Dodecyloxybiphenyl-4-carbonitrile]2PdCl2 3e. A Schlenk
tube was charged with bis(benzonitrile)dichloro palladium(II)
(0.0137 g, 3.572 × 10−5 mol) and acetone (10 mL). 1b (0.0271 g,
7.15 × 10−5 mol) was added and reacted for 30 min. The
solution was distilled off under vacuum. A white–brown solid
=
1H, Ph-H), 5.947 (m, 1H, CH2 CH–), 5.135 (dd, J = 7.0 Hz,
=
=
1H, CH2 CH–), 5.068 (br s, 1H, CH2 CH–), 3.786 (s, 3H,
MeO–), 3.396 (d, J = 6.7 Hz, 2H, CH2 CHCH2–); 13C NMR
=
(50.3 MHz, CDCl3, 77 ppm): d 163.4, 150.5, 139.5, 137.6, 136.9,
123.5, 122.3, 120.7, 116.3, 112.8, 55.8, 40.1, MS (EI) m/z: calc.
for mass 12C16H15NO3 269.1052 amu; found 269.1055; MS (CI)
m/z: calcd. for mass 12C16H16NO3 270.1130 amu; found 270.1114
amu.
1
was obtained (0.0341 g). H NMR (200 MHz, CDCl3): d 7.9–
7.4 (m, 12H), 6.97 (d, J = 7.6 Hz, 4H), 3.98 (t, J = 6.4 Hz,
4H), 1.79 (m, 4H), 1.6–1.1 (m, 36H), 0.86 (t, J = 6.1 Hz, 6H);
13C NMR (50.3 MHz, CDCl3, 77 ppm): d 160.3, 145.3, 133.8,
130.4 128.5, 127.2, 122.8, 115.2, 106.3, 68.2, 31.9, 29.6, 29.3,
29.2, 26.0, 22.7, 14.1, IR (m/cm−1): 3437, 2924, 2852, 2296(s),
2229(w), 1599, 1527, 1490, 1471, 1400, 1296, 1256, 1184, 1094,
1030, 817.
Isonicotinic acid 2-methoxy-4-[3-(pentamethyldisiloxane)pro-
pyl]phenyl ester 6a. 5 (white crystals, 1.728 g, 6.4166 ×
10−3 mol), anhydrous n-Bu2O (20 mL), pentamethyldisiloxane
(1.428 g, 9.9595 × 10−3 mol) and Karstedt’s catalyst in xylene
(2 wt% Pt, 100 lL) were placed in a 50 mL Schlenk tube.
It was heated at reflux for 14 h, then cooled to ambient
temperature. Activated carbon was added and the tube was
heated to 80 ◦C/1 h, then cooled again to room temperature.
[4ꢀ-{3-(Trimethylsiloxydimethylsilyl)propoxy}biphenyl-4-carbo-
nitrile]2PtCl2 4a. A Schlenk tube was charged with bis-
(benzonitrile)dichloroplatinum(II) (0.0150 g, 3.15 × 10−5 mol)
and toluene (10 mL). 2a (0.0242 g, 6.31 × 10−5 mol) was added
7 8
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1

View Article Online
The obtained solution was filtered through a 0.45 lm pore
membrane filter and the solvents were distilled off in vacuo,
then the compound was distilled using a microtube oven to
(d, J = 5.7 Hz, 2H), 7.06 (d, J = 8.0, 1H), 6.87 (s, 1H), 6.83
(d, J = 8.0 Hz, 1H), 4.92 (s, 2JPt–H = 61.6 Hz, 4H, CH2 CH2),
=
3.79 (s, 3H), 2.66 (t, J = 7.5Hz, 2H), 1.68 (m, 2H), 0.60 (t, J =
8.4 Hz, 2H), 0.07 (s, 9H), 0.07 (s, 6H); 13C NMR (50.3 MHz,
CD2Cl2): d 154.9, 152.7, 150.8, 143.3, 140.6, 137.5, 125.7, 122.2,
120.9, 113.2, 75.9 (1JPt–C = 166.3 Hz) 56.1, 39.9, 25.8, 18.5, 2.0,
0.4; 29Si NMR (59.6 MHz, C6D6): d 7.3
◦
give a yellow–orange transparent liquid (∼160 C/<1 mmHg,
2.2333 g, 5.347 × 10−3 mol, 83.3% yield).
1H NMR (200 MHz, CDCl3, 7.24 ppm): d 8.83 (dd, J = 4.5,
1.5 Hz, 2H), 8.00 (dd, J = 4.4, 1.6 Hz, 2H), 7.03 (d, J = 8.0 Hz,
1H), 6.81 (s, 1H), 6.79 (d, J = 8.0 Hz, 1H), 3.79 (s, 3H), 2.62
(t, J = 7.6 Hz, 2H), 1.646 (m, 2H), 0.563 (m, 2H), 0.05 (s, 9H),
[Isonicotinic acid 2-methoxy-4-(3-polydimethylsiloxyprop-
2
=
oxyl)phenyl ester]PtCl2(g -CH2 CH2) 7d. Ziese’s salt, [PtCl3-
1
0.04 (s, 6H); H NMR (200 MHz, CD2Cl2, 5.32 ppm): d 8.84
(CH2 CH2)] K , (0.0427 g, 1.161 × 10−4 mol) was dissolved in
acetone (10 mL) and cooled to −78 ◦C. 6d (2.643 g, 1.161 ×
10−4 mol) was added. After addition, the flask was gradually
heated to room temperature and stirred for 1 h. The solvents
were distilled off in vacuo, and the resultant residual solid
was dissolved in n-hexanes and filtered through a 0.45 lm-
pore PTFE membrane filter, and the solvents were removed to
produce a lemon-yellow highly viscous liquid (0.2873 g, 1.118 ×
10−4 mol, 96% yield). 1H NMR (200 MHz, CDCl3): d 9.14 (m,
2H), 8.21 (d, 5.3 Hz, 2H), 7.03 (d, J = 8.1 Hz, 1H), 6.81 (br s,
1H), 6.79 (d, J = 8.1 Hz, 1H), 4.95 (s, 2JPt–H = 61.6 Hz, 4H), 3.78
(s, 3H), 2.63 (t, J = 7.7 Hz, 2H), 1.65 (m, 2H), 0.58 (m, 2H),
1.12 to −0.01 (165H, SiMe)
−
+
=
(dd, J = 4.4, 1.6 Hz, 2H), 7.98 (dd, J = 4.4, 1.6 Hz, 2H), 7.067
(d, J = 7.9 Hz, 1H), 6.89 (d, J = 1.7 Hz, 1H), 6.84 (dd, J = 8.0,
1.9 Hz, 1H), 3.81 (s, 3H), 2.68 (t, J = 7.7 Hz, 2H), 1.71 (m, 2H),
0.63 (m, 2H), 0.10 (s, 9H), 0.09 (s, 6H), 13C NMR (50.3 MHz,
CD2Cl2, 53.8 ppm): d 163.9, 151.2, 142.9, 137.8, 137.1, 123.5,
122.5, 120.9, 113.2, 56.1, 40.0, 25.9, 18.5, 2.0, 0.4.
Isonicotinic acid 2-methoxy-4-[3-(bistrimethylsiloxymethyl-
silyl)propoxy]phenyl ester 6b. 5 (7.6039 g, 2.8236 × 10−2 mol),
anhydrous n-Bu2O (60 mL), 1,1,1,3,5,5,5-heptamethyl-
trisiloxane (7.64 g, 3.43 × 10−2 mol) and Karstedt’s catalyst in
xylene (2 wt% Pt, 0.40 mL) were placed in a 100 mL Schlenk
tube. The mixture was heated at reflux for 12 h, then cooled
to ambient temperature. Activated carbon was added and the
tube was heated to 80 ◦C/1 h, then cooled again to room
temperature. The obtained solution was filtered through a
0.45 lm-pore PTFE membrane filter and the solvents were
distilled off in vacuo, then the compound was distilled using
a microtube oven to give a yellow transparent liquid (145–
[Isonicotinic acid 2-methoxy-4-(3-pentamethyldisiloxanepro-
2
=
pyl)phenyl ester]PtCl2(g -CH2 CHC6H13) 8a. Ziese’s salt,
−
+
−3
=
[PtCl3(CH2 CH2)] K , (0.5931 g, 1.534 × 10 mol) was
dissolved in acetone (20 mL) and cooled to −78 ◦C. 6a (0.6413 g,
1.535 × 10−3 mol) was added. After the addition, the flask was
gradually heated to room temperature and stirred for 4 h. The
solvents were distilled off in vacuo, and the resulting residual
solid was dissolved in toluene (15 mL) and filtered through a
0.45 lm-pore PTFE membrane filter to produce a toluene
solution of 7b, and, then, 1-octene (3 mL) was added. The solvent
and volatiles were removed to produce a lemon yellow solid
◦
160 C/<1 mm Hg, 11.930 g, 2.426 × 10−2 mol, 85.9% yield).
1H NMR (200 MHz, CDCl3): d 8.84 (dd, J = 4.6, 1.8 Hz, 2H)
8.06 (dd, J = 4.6, 1.8 Hz, 2H), 7.03 (d, J = 7.6 Hz, 1H), 6.81
(s, 1H), 6.79 (d, J = 7.6 Hz, 1H), 3.79 (s, 3H), 2.62 (t, J =
7.3 Hz, 2H), 1.65 (m, 2H), 0.51 (m, 2H), 0.07 (s, 18H), 0.00
(s, 3H); 13C NMR (50.3 MHz, CDCl3): d 163.0 (s), 150.4 (s),
150.4 (d, 1JC–H = 181.0 Hz), 141.8 (s), 137.1 (s), 136.4 (s), 122.9
(1.1184 g, 1.532 × 10−3 mol, 99% yield). H NMR (200 MHz,
1
C6D6): d 8.69 (d, J = 6.7 Hz, 2H), 7.21 (d, J = 6.7 Hz, 2H),
6.99 (d, J = 8.1 Hz, 1H), 6.71 (br d, J = 8.1 Hz, 1H), 6.62 (br s,
1H), 5.90 (br m, 1H), 4.81 (br m, 2JPt–H = 58.0 Hz, 2H), 3.27 (s,
3H), 2.57 (t, J = 7.5 Hz, 2H), 2.05–1.42 (m, 6H), 1.42–1.03 (m,
6H), 0.89 (t, J = 6.5 Hz, 3H), 0.62 (t, J = 8.4 Hz, 2H), 0.13 (s,
9H), 0.13 (s, 6H); 13C NMR (50.3 MHz, C6D6, 128.0 ppm): d
161.3 (s, –OC(O)–), 152.2 (d, 1JC–H = 190.9 Hz), 151.1 (s), 142.5
1
1
(d, JC–H = 165.6 Hz), 121.8 (d, JC–H = 161.0 Hz), 120.3 (d,
1JC–H = 160.3 Hz), 112.4 (d, 1JC–H = 156.4 Hz), 55.3 (q, 1JC–H
=
144.7 Hz), 39.0 (t, 1JC–H = 126.5 Hz), 24.9 (t, 1JC–H = 127.3 Hz),
1
1
17.0 (t, JC–H = 115.8 Hz), 1.6 (q, JC–H = 118.1 Hz, SiMe3),
−0.5 (q, 1JC–H = 118.3 Hz, SiMe); 29Si NMR (59.6 MHz, C6D6):
d 6.9, −20.1.
1
Isonicotinic acid 2-methoxy-4-[3-(polydimethylsiloxy)propoxy]-
phenyl ester 6d. 5 (0.2319 g, 8.611 × 10−4 mol), toluene (10 mL),
Me3SiO(Me2SiO)25SiMe2H (1.778 g, 8.611 × 10−4 mol) and
Karstedt’s catalyst in xylene (2 wt% of Pt, 10 lL) were placed in a
50 mL Schlenk tube. This was heated at reflux for 48 h, and then
cooled to ambient temperature. Activated carbon was added and
the tube was heated to 85 ◦C/1 h, then cooled again to room tem-
perature. The obtained solution was filtered through a 0.2 lm-
pore PTFE membrane filter and the solvents were distilled off in
vacuo to give a yellow transparent liquid (1.9705 g, 98% yield).
1H NMR (200 MHz, CDCl3): d 8.82 (d, J = 6.0 Hz, 2H), 7.99
(d, J = 6.0 Hz, 2H), 7.03 (d, J = 7.8 Hz, 1H), 6.81 (s, 1H),
6.78 (d, J = 7.8 Hz, 1H), 3.79 (s, 3H), 2.64 (t, J = 7.6 Hz, 2H),
1.69 (m, 2H), 0.61 (m, 2H), 0.2 to −0.0 (165H, SiMe); 13C NMR
(50.3 MHz, CDCl3): d 163.4, 150.7, 142.2, 137.5, 136.9, 130.4,
123.3, 122.2, 120.7, 112.7, 55.7, 39.7, 25.4, 18.1, 1.8, 1.0, 0.2.
(s), 139.3 (s), 137.9 (s), 124.8 (d, JC–H = 171.8 Hz), 122.4 (d,
1JC–H = 161.0 Hz), 120.8 (d, 1JC–H = 159.5 Hz), 113.0 (d, 1JC–H
=
155.7 Hz), 104.1 (d, 1JC–H = 160.3 Hz, 1JPt–C = 162.2 Hz), 70.1 (t,
1JC–H = 162.2 Hz, 1JPt–C = 159.5 Hz), 55.2 (q, 1JC–H = 144.4 Hz),
1
1
39.9 (t, JC–H = 126.5 Hz), 35.2 (t, JC–H = 129.6 Hz), 32.0 (t,
1JC–H = 131.9 Hz), 29.8 (t, JC–H = 123.5 Hz), 29.3 (t, JC–H
=
1
1
126.5 Hz), 25.9 (t, 1JC–H = 126.5 Hz), 22.9 (t, 1JC–H = 127.7 Hz),
1
1
18.5 (t, JC–H = 117.3 Hz), 14.3 (q, JC–H = 122.7 Hz), 2.1 (q,
1JC–H = 117.3 Hz, SiMe3), 0.5 (q, 1JC–H = 117.3 Hz, SiMe)
[Isonicotinic acid 2-methoxy-4-(3-bistrimethylsiloxymethyl-
2
=
silylpropoxy)phenyl ester]PtCl2(g -CH2 CHC6H13) 8b. Ziese’s
−
+
−3
=
salt, [PtCl3(CH2 CH2)] K , (0.8472 g, 2.191 × 10 mol) was
dissolved in acetone (10 mL) and cooled to −78 ◦C. 6b (1.0734 g,
2.183 × 10−3 mol) was added. After addition, the flask was
gradually heated to room temperature and stirred for 3 h. The
solvents were distilled off in vacuo, and the resulted residual solid
was dissolved in toluene (13 mL) and filtered through a 0.45 lm-
pore PTFE membrane filter to produce a toluene solution of 7b,
and then, 1-octene (5 mL) was added. The solvent and volatiles
were removed to produce a lemon-yellow solid (1.8770 g, 2.124 ×
10−3 mol, 96% yield). 1H NMR (200 MHz, C6D6): d 8.70 (d, J =
[Isonicotinic acid 2-methoxy-4-(3-pentamethyldisiloxanepro-
2
=
pyl)phenyl ester]PtCl2(g -CH2 CH2) 7a. Ziese’s salt, [PtCl3-
−
+
−4
=
(CH2 CH2)] K , (0.1740 g, 4.72 × 10 mol) was dissolved in
acetone 10 mL and cooled to −78 ◦C. 6a (0.1997 g, 4.72 ×
10−4 mol) was added, and then, the mixture was gradually
heated to room temperature and stirred for 2 h. The solvents
were distilled off in vacuo, and the resulted residual solid was
dissolved in toluene and filtered through a 0.2 lm-pore PTFE
membrane filter, and the solvents were removed to produce a
lemon coloured solid (0.3207 g, 4.506 × 10−4 mol, 95% yield).
1H NMR (200 MHz, CD2Cl2): d 9.15 (d, J = 5.7 Hz, 2H), 8.21
3
6.2 Hz, JPt–H = 29 Hz, 2H), 7.19 (d, J = 6.2 Hz, 2H), 6.97
(d, J = 8.1 Hz, 1H), 6.73 (br d, J = 8.1 Hz, 1H), 6.63 (br s,
2
1H), 5.89 (br m, 1H), 4.84 (br m, JPt–H = 58.3 Hz, 2H), 3.28
(s, 3H), 2.59 (t, J = 7.6 Hz, 2H), 1.80 (m, 4H), 1.53 (m, 2H),
1.45–1.20 (m, 6H) 0.89 (t, J = 6.4 Hz, 3H), 0.67 (t, J = 8.2 Hz,
2H), 0.18 (s, 18H), 0.16 (s, 3H); 13C NMR (50.3 MHz, C6D6): d
D a l t o n T r a n s . , 2 0 0 5 , 7 4 – 8 1
7 9

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Table 4 Hydrosilylation of MMH with isoprene
Table 5 Hydrosilylation of MMH with MVi,OEt
Catalyst
Quantity
Catalyst
Quantity
mol%
(PhCN)2PdCl2
3d
3.7 mg
31.6 mg
0.7 mg
2.1 mg Pt
0.4 mg Pt
(PhCN)2PtCl2
(PhCN)2PdCl2
4d
9.3 mg
7.7 mg
6.4 mg
3.5 mg
0.5 mg Pt
9.8 × 10−1
1.0
4b
6.9 × 10−2
1.3
Karstedt’s cat.a
Karstedt’s cat.b
7d
Karstedt’s cat.a
1.3 × 10−1
a 23 wt% of Pt in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
a 23 wt% of Pt in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. b 2 wt% of Pt
in 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.
(50.3 MHz, CDCl3, 77 ppm): d 58.2, 18.6, 9.6, 7.6, 2.0, −0.4,
−2.8
161.2 (s, –OC(O)–), 152.1 (d, 1JC–H = 185.5 Hz), 151.1 (s), 142.5
1
(s), 139.3 (s), 137.9 (s), 124.8 (d, JC–H = 173.2 Hz), 122.4 (d,
Hydrosilylation of MMH with MVi: characterization of
Me3SiOSiMe2CH(Me)SiMe2OSiMe3 Si4-a and Me3SiOSiMe2
CH2CH2SiMe2OSiMe3 Si4-b. 1H NMR (200 MHz, CDCl3,
7.24 ppm): d 0.98 (d, J = 7.6 Hz, Si4-a, 3H, CHCH3), 0.38 (s,
Si4-b, 4H, CH2CH2), 0.05 (s, 18H, SiMe3), 0.02 (s, 12H, SiMe2);
13C NMR (50.3 MHz, CDCl3, 77 ppm): d 12.3 (Si4-a, CHCH3),
1JC–H = 161.7 Hz), 120.8 (d, 1JC–H = 160.9 Hz), 112.9 (d, 1JC–H
=
156.4 Hz), 104.1 (d, 1JC–H = 159.4 Hz, 1JPt–C = 160.2 Hz), 70.0 (t,
1JC–H = 162.5 Hz, 1JPt–C = 157.1 Hz), 55.2 (q, 1JC–H = 144.3 Hz),
1
1
39.7 (t, JC–H = 126.5 Hz), 35.2 (t, JC–H = 131.1 Hz), 32.0 (t,
1JC–H = 126.5 Hz), 29.8 (t, JC–H = 127.2 Hz), 29.3 (t, JC–H
=
1
1
124.9 Hz), 25.7 (t, 1JC–H = 127.2 Hz), 22.9 (t, 1JC–H = 130.3 Hz),
1
1
1
10.0 (t, JCH = 118.9 Hz, Si4-b, CH2), 8.4 (Si4-a, CHCH3), 2.2
17.8 (t, JC–H = 115.7 Hz), 14.3 (q, JC–H = 121.9 Hz), 2.0 (q,
1JC–H = 118.0 Hz, SiMe3), 0.0 (q, 1JC–H = 118.0 Hz, SiMe); 29Si
NMR (59.6 MHz, C6D6): d 5.1, −23.8
(q, 1JCH = 118.1 Hz, SiMe), 0.2 (q, 1JCH = 118.1 Hz, SiMe).
Hydrosilylation of MMH with isoprene: characterization
=
[Isonicotinic acid 2-methoxy-4-(3-polydimethylsiloxyprop-
of Me3SiOSiMe2CH2CH CMe2 1,4-d and Me3SiOSiMe2
CH2CH2C(Me) CH2 3,4-d. The characterization was per-
2
=
=
oxy)phenyl ester]PtCl2(g -CH2 CH–C6H13) 8d. Ziese’s salt,
−
+
−3
formed after trap-to-trap distillation. 1,4-d: 1H NMR (200 MHz,
=
[PtCl3(CH2 CH2)] K , (0.7867 g, 2.035 × 10 mol) was
dissolved in acetone (10 mL) and cooled to −78 ◦C. 6d (4.6736 g,
2.054 × 10−3 mol) was added. After addition, the flask was
gradually heated to room temperature and stirred for 4 h. The
solvents were distilled off in vacuo, and the resultant residual
solid was dissolved in toluene (12 mL) and filtered through
a 0.45 lm-pore PTFE membrane filter to produce a toluene
solution of 7d, and then, 1-octene (5 mL) was added. The
solvent and volatiles were removed to produce a pale amber
=
CDCl3, 7.24 ppm): d 5.12 (t, J = 8.4 Hz, 1H, CH2CH CMe2),
=
=
1.68 (s, 3H, CH2CH CMe2), 1.56 (s, 3H, CH2CH CMe2), 1.41
=
(d, 2H, CH2CH CMe2), 0.06 (s, 6H, SiMe2), 0.05 (s, 9H, SiMe3):
the doublet at d 5.12 and 1.41 were correlated as shown by 1H–1H
gradient COSY spectra.
3,4-d: 1H NMR (200 MHz, CDCl3, 7.24 ppm): d 4.69 (br s, 1H,
=
=
CH2C(Me) CH2), 4.65 (br s, 1H, CH2C(Me) CH2), 2.00 (m,
2H, SiCH2CH2), 1.72 (br s, 3H, CH2C(Me) CH2), 0.65 (m, 2H,
=
transparent liquid (5.0907 g, 1.967 × 10−3 mol, 97% yield). H
1
SiCH2CH2): the SiMe resonance at d was overlapped with the
other isomers. H–1H gradient COSY spectra showed that the
1
NMR (200 MHz, C6D6) d 8.70 (d, J = 6.5 Hz, 2H), 7.20 (d,
J = 6.5 Hz, 2H), 7.00 (d, J = 8.0 Hz, 1H), 6.74 (dd, J = 8.0,
1.6 Hz, 1H), 6.63 (d, J = 1.6 Hz, 1H), 5.89 (br m, 1H), 4.82
resonance at d 4.65 was correlated with that at d 1.72; similarly,
d 2.00 correlated with d 0.65.
2
(br m, JPt–H = 57.4 Hz, 2H), 3.30 (s, 3H), 2.60 (t, J = 7.5 Hz,
2H), 1.98–1.68 (m, 4H), 1.55 (m, 2H), 1.46–1.17 (m, 6H) 0.89
(t, J = 6.4 Hz, 3H), 0.70 (m, 2H), 0.33–0.16 (SiMe, 165H); 13
C
Acknowledgements
NMR (50.3 MHz, C6D6, 128.0 ppm) d 161.2 (s, –OC(O)–), 152.2
We thank Dow Corning Toray Silicone Co., Ltd. for financial
support of this research. We thank Gregg A. Zank, Steven
A. Snow, and Toshio Suzuki of Dow Corning Corporation for
helpful discussion.
1
(d, JC–H = 188.5 Hz), 151.2 (s), 142.5 (s), 139.4 (s), 138.0 (s),
124.8 (d, 1JC–H = 180.0 Hz), 122.4 (d, 1JC–H = 164.4 Hz), 120.8
1
1
(d, JC–H = 159.8 Hz), 113.0 (d, JC–H = 155.8 Hz), 103.9 (d,
1JC–H = 155.8 Hz, 1JPt–C = 155.8 Hz), 69.9 (t, 1JC–H = 160.1 Hz,
1JPt–C = 173.0 Hz), 55.3 (q, JC–H = 144.3 Hz), 40.0 (t, JC–H
=
1
1
125.3 Hz), 35.2 (t, 1JC–H = 129.9 Hz), 32.0 (t, 1JC–H = 126.7 Hz),
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Hydrosilylation reactions were performed with MVi,OEt, solvents
and a catalyst in a flask at room temperature, followed by the
addition of MMH (1 eq.) dropwise. Then, the mixture was heated
◦
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Hydrosilylation of MMH with MVi,OEt
: characterization
of Me3SiOSiMe2CH(Me)SiMe2OEt Si3-a and Me3SiOSiMe2
CH2CH2SiMe2OEt Si3-b. 1H NMR (200 MHz, CDCl3,
7.24 ppm): d 3.64 (q, J = 7.0 Hz, 2H, SiOCH2CH3), 1.17 (t,
J = 7.0 Hz, 3H, SiOCH2CH3), 1.00 (d, J = 7.6 Hz, Si4-a, 3H,
CHCH3), 0.38–0.49 (br m, Si3-b, 4H, CH2CH2), 0.07 (s, 6H,
SiMe2), 0.04 (s, 6H, SiMe2), 0.02 (s, 9H, SiMe2); 13C NMR
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