Hydrosilylation in the presence of platinum(II) and rhodium(I) complexes with chloride and trichlorostannate(II) anions

Article abstract of DOI:10.1134/S1070427210110133

Hydrosilylation of allyl butyl ether and acetophenone with 1,1,3,3-tetramethyldisiloxane in the presence of [Pt(LL′)XY] and [Rh(Ph₃P)₃X] (L, L′ = cod, dmso, Py, Bn ₂S, Ph₃P; X, y = Cl, SnCl₃) was studied.

Full text of DOI:10.1134/S1070427210110133

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 11, pp. 1962−1968. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © S.A. Andreev, M.A. Il’ina, A.M. Volkova, D.A. de Vekki, N.K. Skvortsov, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83,
No. 11, pp. 1830−1836.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Hydrosilylation in the Presence of Platinum(II)
and Rhodium(I) Complexes with Chloride
and Trichlorostannate(II) Anions
S. A. Andreev, M. A. Il’ina, A. M. Volkova, D. A. de Vekki, and N. K. Skvortsov
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received February 18, 2010
Abstract—Hydrosilylation of allyl butyl ether and acetophenone with 1,1,3,3-tetramethyldisiloxane in the presence
of [Pt(LL')XY] and [Rh(Ph3P)3X] (L, L' = cod, dmso, Py, Bn2S, Ph3P; X, y = Cl, SnCl3) was studied.
DOI: 10.1134/S1070427210110133
The modern trend in the development of the catalyst [Rh(Ph3P)3Cl], which is due to the good under-
hydrosilylation reaction is characterized by a search for standing of their catalytic properties in hydrosilylation
comparatively inexpensive and simple catalytic systems of a wide variety of substrates [1, 14, 16–21], and their
capable of yielding the target product in a short time
with high selectivity. Recently, a large number of reports
have been devoted to use of compounds of base metals
for this purpose. However, complexes of platinum and
rhodium still remain the most efficient catalysts and,
therefore, are in the highest demand [1].
trichlorostannate(II) anion derivatives. As the hydrosi-
lylating agent was chosen 1,1,3,3-tetramethyldisiloxane
(TMDS), which, on the one hand, is a model siloxane
caoutchouc with terminal SiH groups and, on the other,
possesses the most favorable combination of properties
(stability in air, low boiling point, simple NMR spec-
trum), which enables a qualitative and quantitative anal-
ysis of the reaction.
–
SnCl3 is efficient in hydroformylation [2–4], alk-
oxycarbonylation [5], and hydrogenation and dehydro-
genation [6–9] it exerts a high trans-influence and trans-
effect, easily dissociates, and promotes coordination of
olefins and stabilization of pentacoordinated transition
states [5, 10–13]. At the same time, there are no unam-
biguous data on the effect of tin on the hydrosilylation
process. For example, it is known the acetylenes are
hydrosilylated in the presence of tin-containing cobalt
carbonyls [14], and in situ addition of tin(II) chlorides
to H2PtCl6 inhibits hydrosilylation [15].
Allyl butyl ether. The hydrosilylation of allyl
butyl ether with TMDS occurs in accordance with
Farmer’s and Markovnikov’s rules (compounds I and
II, respectively), with silicon predominantly added
to the terminal carbon atom, in good agreement with
published data on the hydrosilylation of allyl ethers [1,
22, 23] (Scheme 1).
The presence of two SiH groups in TMDS
predetermines formation of double-addition products
(compounds III–V). The maximum overall yield
of siloxanes III–V is observed in the presence of
cyclooctadiene complexes of platinum(II) (18 %); with
cis-[Pt(Bn2S)2Cl2] or [Pd(dmso)2Cl2], it reaches a value
of 15%. The minimum yield of double-addition products
is observed in the case of hydrosilylation in the presence
of [Rh(Ph3P)3SnCl3] (1%).
Therefore, the goal of our study was to examine the
effect of the trichlorostannate(II) anion on the rate and
selectivity of hydrosilylation of acetophenone and allyl
butyl ether (AllOBu).
As catalysts were chosen cyclooctadiene, dimethyl-
sulfoxide, dibenzyl sulfide, and triphenylphosphine
chloride complexes of platinum(II) and Wilkinson’
1962

HYDROSILYLATION IN THE PRESENCE OF PLATINUM(II)
1963
Scheme 1.
I
II
III
Scheme 2.
Together with the hydrosilylation, there occur
reduction, isomerization, and dimerization of AllOBu,
and dehydrocondensation and disproportionation of
TMDS (Scheme 2).
A large amount of by-products of TMDS conversion
is formed with all pyridine or phosphine complexes of
platinum(II): in the early stage of the reaction (2–3 days),
only 30–40% of the total conversion of TMDS is
expended for the target reaction. In further course of
the reaction, this parameter increases to 70–80% of the
total conversion of TMDS, i.e., the disproportionation
and dehydrocondensation of TMDS in the presence
of pyridine or phosphine complexes of platinum(II)
dominate over hydrosilylation from the very beginning.
For the rest of the catalysts, the fraction of the target-
related conversion of TMDS is originally larger
(in 2–3 days, it is 75–85% of the total conversion of
TMDS), but starts to decrease as the 85–90% conversion
of AllOBu is reached (hydrosilylation comes to its end).
This suggests that the hydrosilylation predominates over
the rate of the side conversion of TMDS in the presence
of cyclooctadiene, dimethylsulfoxide, and dibenzyl
sulfide complexes of platinum(II) and phosphine
complexes of rhodium(I).
The main by-products of TMDS conversion are
1,1,3,3,5,5-hexamethyltrisiloxane
(HMTS)
and
1,1,1,3,3-pentamethyldisiloxane (transformations of
TMDS are described in more detail in [21, 24]). In turn,
HMTS enters into a reaction with AllOBu to give the
corresponding products of addition in accordance with
Farmer’s and Markovnikov’s rules, whose maximum
amount is observed in the presence of [Pt(cod)X2], cis-
[Pt(Bn2S)2Cl2, and cis-[Pt(dmso)2Cl2] (about 4%). It
should be noted that no cyclosiloxanes are formed in
hydrosilylation of AllOBu, in contrast to the case of
hydrosilylation of vinylsiloxanes and α-methylstyrene
[18, 21, 24].
The side processes accompanying the hydrosilylation
depend both on the nature of a catalyst and on the
reaction conditions. Isomerization of AllOBu occurs to
agreaterextenton[Pt(cod)Cl2]andalldimethylsulfoxide
and dibenzyl sulfide platinum catalysts (5–6%
yield of propenyl butyl ether), whereas in the case
of a trichlorostannate cyclooctadiene complex of
platinum(II) or a trichlorostannate phosphine complex
of rhodium(I), the yield of propenyl butyl ether is the
lowest (0.3–0.5%). Propyl butyl ether is formed in the
presence of [Pt(cod)Cl2] (0.7% yield), whereas in the
presence of both the chloride and trichlorostannate
phosphine complexes of platinum(II) or rhodium(I), its
yield is less than 0.1%.
The TMDS-induced competing hydrosilylation
of propenyl butyl ether formed via isomerization of
AllOBu must for the most part yield siloxane (II),
which, in turn, can raise the total amount of siloxane
(II). However, the hydrosilylation of internal C=C bonds
occurs at a substantially slower rate, compared with that
of terminal bonds [25–27]. and, in addition, there is
no correlation between the yields of siloxane (II) and
propenyl butyl ether. This suggests that the contribution
of a parallel reaction, hydrosilylation of propenyl butyl
ether, to the process of interaction between AllOBu and
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

1964
ANDREEV et al.
TMDS is insignificant.
The catalytic activity of cis-[Pt(Bn2S)2Cl2] and
1
cis-[Pt(dmso)2Cl2] is lower than that of [Pt(cod)
Cl2]. Replacement of Cl with SnCl3 in the dibenzyl
The H NMR spectrum of the reaction mixture
–
contain singlets and triplets of methyl groups at silicon
atoms (δH 0.03–0.19 ppm) and of methyl groups
unbound to silicon (δH 0.84–1.23 ppm); signals of SiCH2
(δH 0.40–0.56 ppm), methylene protons (δH 1.29–1.67,
3.30–3.93, and 5.14–5.27 ppm), and methine protons
(δH 5.85–5.95 ppm); and a characteristic multiplet of the
SiH group (δH 4.7 ppm). However, application of the
NMR technique to monitoring of the reaction course is
exceedingly inconvenient, because most of signals of the
starting compounds and the compounds being formed
are superimposed. Only the following signals can be
rather clearly distinguished (δH, ppm; J, Hz): –CH=CH2
fragment of the starting compound [5.17 d (1H, CH2,
J 37.6), 5.22 d (1H, CH2, J 45.0), 5.89 dq (1/2H, CH,
J 17.0, 5.6), and 5.92 dq (1/2H, CH, J 17.0, 5.8)], part of
methylene protons of propenyl butyl ether [3.62 t (2H,
OCH2, J 6.6], and some groups of propyl butyl ether
[1.22 dt (6H, CH3, J 6.3, 1.3), 3.67 t (2H, OCH2, J 6.2),
and 3.71 t (2H, OCH2, J 5.9)].
sulfide catalyst makes it activity lower, but not so
strongly as it occurs in hydrosilylation in the presence
of a cyclooctadiene complex of platinum(II). At the
same time, presence of SnCl3 in the dimethylsulfoxide
catalyst exerts a strong negative influence on its activity
–
(Table 1).
The rate of hydrosilylation in the presence of cis-
[Pt(Py)2Cl2] and cis-[Pt(Ph3P)2Cl2] is rather low,
with a lower activity exhibited by cis-[Pt(Py)2Cl2].
The activity of the pyridine catalyst can be raised by
introduction of the trichlorostannate(II) anion, but this
procedure is inefficient in the case of phosphine-type
and other platinum catalysts (Table 1).
Thus, the activity of chloride platinum catalysts in
the interaction of allyl butyl ether with TMDS decreases
in the following order of ligands: cod > dmso > Bn2S >
Ph3P > Py; for trichlorostannate complexes, the order is
somewhat modified: cod > dmso > Bn2S > Py > Ph3P.
In the case under consideration, IR spectroscopy is
inefficient because it gives no way of clearly determining
the way in which silicon hydride groups are consumed
and the amount of the products being formed.
Wilkinson’s catalyst exhibits a substantially higher
activity in the interaction of allyl butyl ether with TMDS,
compared with the phosphine complex of platinum(II);
nevertheless, the activity of [Rh(Ph3P)Cl] is lower
than that of the most active platinum catalyst, [Pt(cod)
Cl2]. [Rh(Ph3P)3(SnCl3)] is inferior to [Rh(Ph3P)3Cl]
in catalytic activity; however, the yield of the target
product I was the highest (90.5%) in the presence of the
former.
The most convenient monitoring technique is gas
chromatography. A typical chromatogram contains the
following peaks (retention times, RT, min): PrOBu
(3.3); TMDS (4.7); HMe2SiOSiMe3 (5.7); toluene (9.1,
internal standard); AllOBu (9.8); HMe2SiOSi(Me2)
OSi(Me)2H (10.3); propenyl butyl ether (11.1);
BuO(CH2)2–CH=CH–(CH2)2OBu (22.6); siloxanes: II
(24.2), I (25.4), IV (39.4), V (38.7), and, in some cases,
product III (38.7); and products of α- and β-addition of
HMTS (32.9 and 33.3, respectively). In addition, the
chromatogram shows unidentified peaks with retention
times of 11.0, 13.1, 15.5, 22.1, 29.7, 29.8, and 46.9
min, which appear as a result of side transformations
of TMDS (these peaks are observed in chromatograms
of products formed in interaction between TMDS and
catalysts without allyl butyl ether and are absent in
chromatograms of products of interaction between allyl
butyl ether and catalysts without TMDS).
The hydrosilylation selectivity, i.e., the share of the
hydrosilylation reaction in the observed processes of
AllOBu conversion is, on average, 84–95% (Table 1).
For cis-[Pt(Py)2Cl2] and the phosphine complex of
platinum(II) with the trichlorostannate(II) anion,
the selectivity was fund to be below this range. The
highest selectivity is observed when the reaction is
performed in the presence of Wilkinson’s catalyst or its
trichlorostannate analog.
It is the most convenient to evaluate the selectivity
of addition of silicon hydrides (TMDS and HMTS)
to the C=C bond by the α-/β-addition ratio (Table 1).
For almost all of the catalysts under consideration, the
selectivity of β-addition is 96.5–97.5% and only slightly
depends on the catalyst structure. The best result was
obtained in the presence of a phosphine complex of
rhodium(I) with the trichlorostannate anion (98%).
The highest activity in the interaction of allyl
butyl ether with TMDS is exhibited by [Pt(cod)Cl2];
however, replacement of the chloride anion with
the trichlorostannate anion markedly diminishes the
catalytic activity of the complex (Table 1).
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

HYDROSILYLATION IN THE PRESENCE OF PLATINUM(II)
1965
Table 1. Characteristics of allyl butyl ether hydrosilylation with 1,1,3,3-tetramethyldisiloxane. Temperature 20°C, All–O–Bu :
TMDS = 1 : 1.5
Yield, %
AllOBu
Time, days conversion,
%
Catalyst
Х
Cl
Selectivity,* %
α-/β- ratio
I
II
V
[Rh(Ph3P)3X]
4
7
97
100
10
98
19
51
70
15
19
25
90
99
100
29
88
91
87
98
74
2
89.0
88.2
5.5
2.2
2.6
0
1.0
2.7
95
95
71
95
82
83
91
88
82
76
90
85
84
88
93
93
89
87
86
59
52
90
92
89
85
92
93
3.3/96.7
3.7/96.3
–
SnCl3
Cl
4
0.7
7
90.5
13.5
36.6
56.2
12.3
13.7
14.4
66.0
65.9
65.9
21.7
69.9
70.5
59.9
64.5
54.7
0.3
1.7
0
0.7
2.0/98.0
–
[Pt(Ph3P)2(Cl)X]
[Pt(dmso)2(Cl)X]
2
2.0
7
0.7
1.2
0.6
0.8
1.1
1.9
2.0
2.0
0.6
1.9
1.9
2.5
2.0
0.8
0
4.4
2.3/97.6
2.7/97.2
3.9/96.1
3.8/96.2
4.1/95.9
3.0/97.0
3.2/96.8
3.2/96.8
3.5/96.5
3.4/96.6
3.1/96.9
3.5/96.5
2.8/97.2
2.3/97.7
–
10
2
5.2
SnCl3
Cl
0.2
7
0.5
10
2
2.0
10.5
11.3
11.5
0.7
7
10
2
SnCl3
Cl
7
9.0
10
2
10.0
13.6
17.5
7.9
[Pt(Bn2S)2(Cl)X]
[Pt(Py)2(Cl)X]
15
2
SnCl3
Cl
2
0.8
9
14
17
56
97
100
67
100
6.8
0.2
0.2
1.2
1.9
1.9
1.3
1.8
0.1
2.7/97.3
3.5/96.5
3.4/96.6
3.1/96.9
3.2/96.8
2.8/97.2
3.2/96.8
SnCl3
Cl
2
14.8
45.9
68.9
64.0
55.0
74.4
0.3
10
2
3.7
[Pt(cod)(Cl)X]
12.3
14.4
4.2
7
SnCl3
2
7
12.1
a The selectivity is defined as the sum of hydrosilylation products divided by the sum of al products formed from the allyl ether.
clearly reflects the conversion of the acetophenone
reaction mixture, compared with that containing
AllOBu, and, for a reaction performed in an excess of
TMDS, enables easy determination of the conversion
and the reaction selectivity [with or without toluene
as internal standard (δH 2.36 ppm)]. In the course of
the reaction, the area of the singlet associated with the
methyl group of acetophenone (δH 2.60 ppm) decreases
and there appear a characteristic doublet of the methyl
group of product VI (δH 1.49 ppm, J 6.3 Hz) and two
characteristic doublets of the methylene group of enol
VII (δH 4.47 and 4.97 ppm, J 1.2 Hz). However, the
Acetophenone. Interaction of acetophenone with
TMDS in the presence of the catalysts considered above
yields silyl ethers of 1-phenylethanol (VI) and enol
(VII). Together with ethers VI and VII, the reaction
mixture contains products of TMDS disproportionation
and dehydrocondensation, similar to those produced
in hydrosilylation of AllOBu, and, additionally, 1–3%
octamethylcyclotetrasiloxane. This means that, in the
given case, TMDS is partly converted to cyclosiloxanes,
primarily because of the change in the temperature mode
of the process (80°C instead of 20°C) (Scheme 3).
1
In the case under consideration, H NMR more
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

1966
ANDREEV et al.
Scheme 3.
conversion and reaction selectivity calculated from the
1H NMR data nearly always differ by 2–5% from the
results of the chromatographic analysis, which is due to
the higher sensitivity of the latter method.
(Table 2), in good agreement with the known high
activity of rhodium catalysts in hydrosilylation of
ketones [1, 14, 26]. Replacement of the chloride anion
with a trichlorostannate anion leads to a decrease in the
reaction rate, similarly to the case in which AllOBu is
hydrosilylated.
A typical chromatogram of the reaction mixture
contains the following peaks (RT, min): TMDS (2.67);
HMTS (2.98); toluene (3.03); octamethylcyclotetra-
siloxane (3.57); acetophenone (4.12); ether VI (5.33);
enol VII (6.05); silyl ethers of 1-phenylethanol and enol,
formedasaresultofhydrosilylationofacetophenonewith
HMTS (5.57 and 6.76, respectively). The chromatogram
also shows peaks we could not identify, with retention
times of 4.43, 7.76, 8.82, 9.12, and 10.24 min.
Platinum catalysts are less active than[Rh(Ph3P)3Cl].
The best performance among these catalysts is exhibited
by the dibenzyl sulfide complex of platinum(II) with
a chloride anion (80%), and the minimum conversion
of acetophenone is observed for phosphine complexes
of platinum(II) (Table 2). The latter is presumably due
to the long induction period (incomplete during the
time interval under consideration) whose existence
is characteristic of hydrosilylation in the presence of
phosphine complexes of platinum(II) [16, 19].
The highest activity in the reaction under
consideration was exhibited by Wilkinson’s catalyst
Table 2. Characteristics of acetophenone hydrosilylation with
1,1,3,3-tetramethyldisiloxane. Time 6 h, temperature 80°C,
acetophenone : TMDS = 1 : 1.5
The catalytic activities of [Pt(cod)Cl2], cis-
[Pt(Py)2Cl2], and cis-[Pt(dmso)2Cl2 are lower than that
of cis-[Pt(Bn2S)2Cl2] (the corresponding conversions
are 58, 55, 54, and 80%, respectively, Table 2).
Presence of the trichlorostannate anion in the catalysts
under consideration makes the hydrosilylation rate
lower, which is especially strongly pronounced for the
dimethylsulfoxide and pyridine complexes. It should
be noted that the behavior of pyridine complexes
of platinum(II) strongly depends on the nature of
reactants: they exhibit zero activity in siloxane systems
[16, 18, 28], are the most active in hydrosilylation of
α-methylstyrene [21], and their activity additionally
depends on the nature of the anionic ligand in the case
of acetophenone and AllOBu.
Acetophenone
conversion
Addition
selectivity
Catalyst
%
[Pt(dmso)2Cl2]
54
9
88
~100
81
[Pt(dmso)2(SnCl3)Cl]
[Pt(Bn2S)2Cl2]
80
56
55
10
58
20
4
[Pt(Bn2S)2(SnCl3)Cl]
[PtPy2Cl2]
~100
~100
94
[PtPy2(SnCl3)Cl]
[Pt(cod)Cl2]
Thus, the activity of the platinum catalysts in
hydrosilylation of acetophenone with TMDS differs
from that in the reaction of allyl butyl ether with TMDS
and decreases in the following order of ligands: Bn2S >>
94
[Pt(cod)(SnCl3)Cl]
[Pt(Ph3P)2Cl2]
~100
~100
~100
98
–
cod > Py ≈ dmso > Ph3P; Cl > SnCl3 .
[Pt(Ph3P)2(SnCl3)Cl]
[Rh(Ph3P)3Cl]
3
The selectivity of hydrosilylation in the presence
of the catalysts under consideration was found to be
sufficiently high, which is primarily due to the chosen
87
72
[Rh(Ph3P)3(SnCl3)]
97
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

HYDROSILYLATION IN THE PRESENCE OF PLATINUM(II)
1967
conditions: aerobic hydrosilylation without any special
pretreatment of solvents and reactants, rather than
to the structure of the catalysts. In this case, we have
rather readily occurring hydrolysis of enol silyl ether,
i.e., regeneration of acetophenone [1, 29, 30], which
positively affects the selectivity of the process. It
can, however, be easily noticed that the selectivity of
hydrosilylation in the presence of chloride complexes
exceeds that for catalysts with the trichlorostannate(II)
anion (Table 2). The only exception is the pyridine
complex of platinum(II), for which the “anomalous”
behavior remains an empirical factor so far.
Acros and allyl butyl ether from Aldrich; acetophenone,
methylene chloride, and toluene were of chemically
pure grade. The chloride platinum and rhodium catalysts
were synthesized by methods described in [31, 32], and
the platinum(II) and rhodium(I) complexes with the
trichlorostannate anion, by those reported in [33, 34].
CONCLUSIONS
(1) The highest activity in the interaction between
allyl butyl ether and 1,1,3,3-tetramethyldisiloxane is
exhibited by the [Pt(cod)Cl2] catalyst; however, the
maximum yield of the target product is observed in the
presence of [Rh(Ph3P)3(SnCl3)].
EXPERIMENTAL
(2) The hydrosilylation ofAllOBu is accompanied by
intense disproportionation and dehydrocondensation of
TMDS and reduction, isomerization, and dimerization of
AllOBu; in the case of hydrosilylation of acetophenone,
the highest activity is exhibited by[Rh(Ph3P)3Cl].
1H NMR spectra were recorded on a Bruker WM-400
instrument with a storage unit at a working frequency of
400 (1H) Hz in CDCl3 with internal deuterium lock and
no additional references.
The reaction mixture was subjected to
(3) In most cases, the rate of hydrosilylation in the
presence of platinum(II) and rhodium(I) complexes
with the trichlorostannate anion is lower than that on
chloride catalysts, i.e., the increase in the trans-effect
and trans-influence adversely affects the hydrosilylation,
presumably via stabilization of transition states.
a
gas-chromatographic analysis on an Agilent
7890 A chromatograph with a katharometer: DB-1
column (30 m × 0.32 mm); carrier-gas, helium (pressure
283.93 Pa [5.93 psi]); evaporator temperature 250°C,
detector temperature 255°C; sample volume 1 μl; flow
split ratio 250 : 1. In the case of AllOBu, the column
was kept at a temperature of 70°C for 5 min, heated to
200°C at a rate of 5 deg min–1 and then to 225°C at
25 deg min–1, and kept at 225°C for 16 min; in the case
of acetophenone, it was heated from 150 to 200°C at
15 deg min–1 and kept at 225°C for 35 min. Calculations
and peak assignment were made relative to signals of
individual compounds and toluene.
ACKNOWLEDGMENTS
The study was financially supported by the Russian
Foundation for Basic Research (grant no. 09-03-
00341a).
REFERENCES
The hydrosilylation was performed in sealed ampules
at a catalyst concentration of (1.0–1.5) × 10–6 M. The first
to be poured-in was the less volatile component of the
mixture, a catalyst dissolved in methylene chloride was
added at the end. The AllOBu (acetophenone) : TMDS :
toluene molar ratio was 1 : 1.5 : 0.25. The reaction course
wasmonitoredby1HNMRspectroscopy(acetophenone)
and gas chromatography (AllOBu and acetophenone).
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determined relative to toluene. The reaction selectivity
was found as the sum of hydrosilylation products divided
by the sum of all products formed from allyl butyl ether
for AllOBu, and as the ratio between ethers VI and VII
for acetophenone.
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