Hydrosilylation of Allyl Ethers in the Presence of Supported Sulfur-Containing Platinum(II) Complexes

Article abstract of DOI:10.1134/S107036321801005X

Hydrosilylation of allyl ethyl, allyl butyl, allyl glycidyl, allyl benzyl, and allyl phenyl ethers by 1,1,3,3-tetramethyldisiloxane in the presence of supported sulfur-containing platinum(II) complexes with the general formula [{SiO₂}O_2S

Full text of DOI:10.1134/S107036321801005X

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 1, pp. 25–35. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © D.A. de Vekki, M.A. Il’ina, N.K. Skvortsov, 2018, published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 1, pp. 28–38.
Hydrosilylation of Allyl Ethers in the Presence
of Supported Sulfur-Containing Platinum(II) Complexes
D. A. de Vekki, M. A. Il’ina*, and N. K. Skvortsov
St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
*e-mail: ilina_masha@list.ru
Received November 16, 2017
Abstract—Hydrosilylation of allyl ethyl, allyl butyl, allyl glycidyl, allyl benzyl, and allyl phenyl ethers by
1,1,3,3-tetramethyldisiloxane in the presence of supported sulfur-containing platinum(II) complexes with the
general formula [{SiO2}O2Si(Me)(CH2)3SR]2PtCl2 (R = Bu, Hex, Bn; {SiO2} is silica surface) and side
processes have been studied.
Keywords: hydrosilylation, allyl ethers, tetramethyldisiloxane, supported platinum(II) complexes
DOI: 10.1134/S107036321801005X
Organosilicon compounds have found wide
application as specific materials since their commercial
production in the 1940s. This was determined by their
unique properties such as high thermal stability,
chemical resistance to ozone, atomic oxygen, and
oxygen plasma, excellent hydrophobicity, radiation
stability, low glass transition temperature, low surface
tension, low solubility, low dielectric constant, and non-
flammability. Such properties as solubility, ionic
conductivity, liquid crystallinity, etc., can often be
modified by simple introduction of various functional
groups to the silicon atom, and new materials with
enhanced thermal and hydrolytic stability can be
obtained [1–3].
Interest in the development of new catalytic
systems does not diminish since there is a need to
improve such parameters as catalytic activity, stability,
selectivity, and the possibility of recycling. Up to now,
examples of successful hydrosilylation of allyl ethers
using rhodium siloxide complexes [6–8], including
those immobilized in ionic liquids [9, 10] and silica-
supported [11–13], silica-supported Karstedt’s catalyst
analog [14, 15], arsenide complexes of platinum(IV)
[16] and rhodium(III) [17], phosphine rhodium(III)
complexes [18], nitrogen-containing platinum(IV)
complexes [19], chitosan platinum complexes [20–22],
platinum, palladium, and rhodium complexes with a
mercapto groups [23, 24], and sulfide rhodium com-
plexes [25] have been reported.
Catalytic hydrosilylation of allyl ethers is one of
the methods for the synthesis of organosilicon compounds,
in particular epoxysilanes and epoxysiloxanes (hydro-
silylation of allyl glycidyl ether) that are promising for
industrial production of hybrid materials [4, 5]. The
leading position among catalysts used for the hydro-
silylation of allyl ethers is occupied by Speier’s and
Karstedt’s catalysts [1, 2]; however, these catalysts are
not free from a number of disadvantages related to
difficult control of the reaction rate, necessity of using
inhibitors, in some cases solidification of the reaction
mixture in situ, and isomerization of multiple bond
with subsequent acidic cleavage of functional group,
which could impair properties of the products.
On the other hand, sulfur-containing platinum(II)
complexes are efficient homogeneous catalysts for
hydrosilylation of C=C double bonds [25–31].
Hydrosilylation of allyl ethers over supported sulfur-
containing platinum complexes has been poorly
studied [1] despite known advantages of these catalysts
[23, 24, 32–36]. Therefore, the aim of the present work
was to study the catalytic activity of anchored sulfur-
containing platinum(II) complexes with different
substituents on the sulfur atom with the general
formula [{SiO2}O2Si(Me)(CH2)3SR]2PtCl2 ([(SiO2)–
2SR–PtCl2], R = Bu, Hex, Bn; {SiO2} is a modified
silica surface [37]) in the hydrosilylation of allyl ethers
25

26
DE VEKKI et al.
Markovnikov (β-addition). Monoadducts with
by 1,1,3,3-tetramethyldisiloxane, which was studied by
us in detail previously by spectral methods [38]. The
substrates were allyl ethyl (AllOEt), allyl butyl
(AllOBu), allyl glycidyl (AllOGlyc), allyl benzyl
(AllOBn), and allyl phenyl ethers (AllOPh).
a
reactive Si–H group fairly readily add to the second
allyl ether molecule to give γ,γ- and β,γ-bis-addition
products, whereas no β,β-adduct is formed (Scheme 1).
The target process, hydrosilylation by tetramethyl-
disiloxane, is accompanied by allyl–propenyl iso-
merization, reduction of ether, disproportionation of
tetramethyldisiloxane to HMe2Si(OSiMe2)nH (n = 2–
4), and hydrosilylation of allyl ethers with siloxanes
HMe2Si(OSiMe2)nH by analogy with the hydro-
silylation by 1,1,3,3-tetramethyldisiloxane (Scheme 2).
The qualitative and quantitative compositions of by-
products depend on the substrate structure and catalyst
and will be discussed below. It should be noted that
allyl–propenyl isomerization and reduction products
were also formed in the reactions catalyzed by Speier’s
catalyst [40–44] and platinum(II) and rhodium(I)
complexes [Pt(L1L2)XY], [Rh(Ph3P)3X] (L1, L2 = cod,
dmso, Py, Bn2S, Ph3P; X, Y = Cl, SnCl3) [45], and
CH3
R
O
Si(CH2)3S
Cl
Cl
O
O
SiO2
Pt
Si(CH2)3S
O
R
CH3
[(SiO2)–2SR–PtCl2]
R = Bu, Hex, Bn.
General information on the reaction. The reac-
tions of allyl ethers with 1.5 equiv of 1,1,3,3-tetramethyl-
disiloxane in the presence of [(SiO2)–2SR–PtCl2] (R =
Bu, Hex, Bn) can be successfully accomplished at 80–
100°C, i.e., under milder conditions than in the
presence of most other supported metal complexes
(120°C). The addition of the Si–H group to the allyl
fragment follows two main pathways [38, 39]:
predominant anti-Markovnikov (γ-addition) and
[(diene)Rh(μ-OSiMe3)}2]
[6];
disproportionation
products were detected when siloxide rhodium com-
plexes, chloride and trichlorostannate platinum and
rhodium complexes, and Speier’s catalyst were used
[6, 38, 42, 45], and hydrosilylation of allyl ethers by
Scheme 1.
CH3
Si
CH3
Si
R
O
+
H
H
O
n
CH3
CH3
catalyst,
Δ
CH3
CH3
CH3
Si
CH3
Si
R
O
+
O
Si
H
Si n H
CH3
R
O
O
n
CH3
CH3
CH3
CH3
β-addition
γ-addition
R
catalyst,
Δ
O
CH3
CH3
CH3
Si
CH3
Si
R
R
O
O
Si
O
+
Si
O
R
O
n
O
R
n
CH3
CH3
CH3
CH3
CH3
γ,γ-addition
β,γ-addition
n = 1–3; R = Et, Bu, Glyc, Bn, Ph.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

HYDROSILYLATION OF ALLYL ETHERS
27
Scheme 2.
R1
O
[H]
[(SiO2)_2SR2_PtCl2]
R1
O
Δ
R1
O
+
R1
O
E
Z
R1 = Et, Bu, Glyc, Bn, Ph; R2 = Bu, Hex, Bn.
H(Me2SiO)nSiMe2H + H(Me2SiO)mSiMe2H ⇄ H(Me2SiO)(n+1)SiMe2H + H(Me2SiO)(m–1)SiMe2H,
m, n = 1–3.
hydrosiloxanes formed as by-products was observed in
the reactions catalyzed by chloride and trichloro-
stannate platinum and rhodium complexes and Speier’s
catalyst [38, 40].
The selectivity with respect to the γ-adduct, i.e., the
ratio of the yield of the γ-addition product (HMe2Si)2O
to the overall yield of all products fromed from
AllOBu {including by-products and products of mono-
and bis-addition products of HMe2Si(OSiMe2)nH (n =
2, 3) to AllOBu} was 71.0, 74.4, and 76.3% (80°C) for
[(SiO2)–2SBn–PtCl2], [(SiO2)–2SBu–PtCl2], and [(SiO2)–
2SHex–PtCl2], respectively, which was determined
primarily by the side addition of the Si–H group of the
monoadduct (Table 1). Unfortunately, published data
very rarely include information on side processes
accompanying hydrosilylation, whereas the selectivity
is usually given as the ratio of γ- and β-adducts (regio-
selectivity). For example, the selectivity determined in
such a way for the hydrosilylation of AllOBu by
Other possible side reactions, such as oxirane ring
opening and formation of glycidyl acrylate [3, 41], α-
addition [38], dehydrogenative silylation (typical of
rhodium and nickel catalysts) [6, 40], elimination of
propylene [41], dimerization and polymerization of
allyl ethers [6, 38, 44, 45], cyclization of siloxanes
[46], etc., did not occur in our catalytic systems.
Hydrosilylation of allyl butyl ether. Analysis of
the kinetic data for the hydrosilylation of allyl butyl
ether by 1,1,3,3-tetramethyldisiloxane in the presence
of [(SiO2)–2SR–PtCl2] showed the time necessary to
attain maximum conversion of allyl butyl ether almost
does not depend on the substituent R on the sulfur
atom of the ligand; after 8 h at 80°C, the conversion
was 98–99% for R = Bu, Hex, Bn (Fig. 1). In the early
hydrosilylation stage, [(SiO2)–2SHex–PtCl2] is more
active than [(SiO2)–2SBn–PtCl2] (1 h, conversion 42%
against 35%); after 1.5 h, the conversion was the same
in the presence of both catalysts; after 3 h, the
conversion of AllOBu in the presence of [(SiO2)–
2SHex–PtCl2] becomes lower than in the presence of
[(SiO2)–2SBn–PtCl2] (76% against 83%). If the
catalytic activity is estimated by the time necessary for
50% substrate conversion, [(SiO2)–2SHex–PtCl2] and
[(SiO2)–2SBn–PtCl2] are more active than [(SiO2)–
2SBu–PtCl2] (82 and 89 min against 143 min,
respectively). Decrease the reaction temperature to
60°C considerably increased the reaction time: after
10 h in the presence of [(SiO2)–2SBu–PtCl2], the
conversion was 80%. Raising the temperature to
100°C shortened the reaction time almost twofold:
the conversion was 52% after 1 h and 95% after 3.5 h
(Fig. 1).
Conversion, %
Time, h
Fig. 1. Variation of the conversion of allyl butyl ether with
time in the hydrosilylation by (HMe2Si)2O in the presence of
platinum complexes (1, 4, 5) [(SiO2)–2SBu–PtCl2],
(2) [(SiO2)–2SBn–PtCl2], and (3) [(SiO2)–2SHex–PtCl2] at
(1) 100, (2, 3, 4) 80, and (5) 60°C; cPt = 1.8× 10–4 M, molar
ratio AllOBu–(HMe2Si)2O = 1 : 1.5.
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28
DE VEKKI et al.
Table 1. Hydrosilylation of allyl ethers by 1,1,3,3-teramethyldisiloxane (HMe2Si)2O in the presence of [(SiO2)–2SR–PtCl2]a
Product composition, %
Reaction
Allyl ether time,
h
product of (HMe2Si)2O
addition
γΣ-Selectivity,
γ/β, %
%
CH3CH=CHOR′ others
β
γ
β,γ
γ,γ
[(SiO2)–2SHex–PtCl2]
AllOBu
AllOBu
8
8
80
80
99
99
94.7
96.3/3.7 3.0
76.3
71.0
1.1 12.3
1.0 12.5
0.8
1.1
6.5
[(SiO2)–2SBn–PtCl2]
92.6
96.3/3.7 2.7
11.7
[(SiO2)–2SBu–PtCl2]
1
8
100
52
99
99
80
91
74
23
79
96.3
96.2/3.8 3.4
96.2/3.8 3.1
96.3/3.7 2.9
96.6/3.4 2.9
94.5/5.5 4.3
95.5/4.5 3.8
98.2/1.8 1.5
91.8/8.2 6.5
87.2
77.8
74.4
83.0
74.2
79.7
79.8
70.7
0.5
7.1
0.3
0.3
1.4
0.4
3.7
3.1
5.2
5.0
1.5
2.4
96.0
94.9
96.0
89.4
92.1
97.4
84.1
1.2 15.2
1.2 13.1
0.9 10.6
1.4 12.4
AllOBu
8
80
60
7.0
10
1.9
AllOBn
AllOEt
4.0
1.4
0.0
0.0
9.9
1.7
8.3
2.1
11.8
9.5
10
80
AllOPh
AllOGlyc
a R = Bu, Hex, Bn; cPt = 1.8×10–4 M, molar ratio ether–(HMe2Si)2O = 1 : 1.5.
1,1,1,3,5,5,5-heptamethyltrisiloxane in the presence of
[Rh(cod)(µ-OSiMe3)]2 [6] was 98%, which may ensue
from both lower reactivity of siloxane with an internal
Si–H group in side processes [38] and ignoring
processes accompanying hydrosilylation. We estimated
the regioselectivity of the addition of (HMe2Si)2O
through the γ/β-adduct ratio at 96.3% for all the
examined catalyst, i.e., it does not depend on the
nature of substituent on the sulfur atom and is higher
than in the hydrosilylation in the presence of
homogeneous cyclooctadiene (85%), dibenzyl sulfide
(87%), and dimethyl sulfoxide platinum complexes
(84%); furthermore, it is comparable with the
selectivity reached with the use of Wilkinson’s catalyst
[Rh(Ph3P)3Cl] (95%) and [Pt(dmso)2(SnCl3)Cl] (93%)
[45]. On the other hand, it is interesting to evaluate the
overall γ-addition (γΣ-selectivity, i.e., the contribution
of all hydrosilylation products, including those derived
from side siloxanes, and double addition products) in
order to extrapolate the obtained data to
hydrosilylation by oligomeric and polymeric
hydrosiloxanes since siloxane disproportionation
processes almost do not affect characteristics of the
final product. The reasonability of introducing this
parameter is confirmed by the coincidence of the
results obtained by GLC and 1H NMR. The γΣ-
selectivity was 92.6, 94.7, and 94.9% in the presence
of [(SiO2)–2SBn–PtCl2], [(SiO2)–2SHex–PtCl2], and
[(SiO2)–2SBu–PtCl2], respectively; i.e., it is slightly
lower than the selectivity in the addition of exclusively
(HMe2Si)2O due to increased contribution of β-
addition of HMe2Si(OSiMe2)nH (n = 2, 3) to AllOBu,
which is proportional to the increase of the overall
concentra-tion of the γ- and β-adducts of HMe2Si·
(OSiMe2)nH (n = 2, 3) in the catalyst series [(SiO2)–
2SBu–PtCl2] (4.1%), [(SiO2)–2SHex–PtCl2] (4.2%),
and [(SiO2)–2SBn–PtCl2] (6.9%). On the whole,
siloxanes HMe2Si(OSiMe2)nH formed as a result of
disproportionation add to AllOBu with lower
selectivity, which reduces the γΣ-selectivity.
The kinetic curves for free HMe2Si(OSiMe2)nH
(n = 2–4) and the corresponding hydrosilylation
products smoothly ascend throughout the entire period
of measurements (Fig. 2). After 5 h at 80°C, the yield
of free HMe2Si(OSiMe2)nH, e.g., in the presence of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

HYDROSILYLATION OF ALLYL ETHERS
[(SiO2)–2SBn–PtCl2], is 0.8, 1.2, and 0.6%, and their
29
Yield, %
overall yield (with account taken of their consumption
for hydrosilylation) is 4.6, 2.9, and 0.9% for n = 2, 3,
and 4, respectively. By the end of the reaction (8 h),
the concentration of free siloxanes remains virtually
unchanged (0.9, 1.6, and 0.9%), whereas the amount of
the hydrosilylation products slightly increases (overall
yield 5.3, 4.1, and 1.3%; Table 2). It should be noted
that the amount of free HMe2Si(OSiMe2)2H in the
presence of [(SiO2)–2SHex–PtCl2] and [(SiO2)–2SBu–
PtCl2] is higher than in the presence of [(SiO2)–2SBn–
PtCl2]; the concentration of free HMe2Si(OSiMe2)3H
almost does not depend on the R substituent in the
metal complex, while only traces of HMe2Si(OSiMe2)4H
were detected (or it was not detected at all); after 8 h at
80°C, the yield of free HMe2Si(OSiMe2)nH in the
presence of [(SiO2)–2SHex–PtCl2] and [(SiO2)–2SBu–
PtCl2] was 4.2 and 1.5% or 4.0 and 1.9% at n = 2 and
3, respectively (Table 2). The amount of HMe2Si·
(OSiMe2)2H involved in side hydrosilylation in the
presence of [(SiO2)–2SBn–PtCl2] was larger (the
siloxane conversion to hydrosilylation products was
~83%) than in the cases of [(SiO2)–2SHex–PtCl2] and
[(SiO2)–2SBu–PtCl2] (30–31%), which suggests
higher catalytic activity of [(SiO2)–2SBn–PtCl2]. Thus,
the catalytic activity of supported platinum complexes
in the side reactions of (HMe2Si)2O decreases in the
series [(SiO2)–2SBu–PtCl2] ≈ [(SiO2)–2SBn–PtCl2] >
[(SiO2)–2SHex–PtCl2] (Table 2).
Time, min
Fig. 2. Variation of the yield of HMe2Si(OSiMe2)2H with
time in the hydrosilylation of allyl butyl ether by (HMe2Si)2O in
the presence of platinum complex [(SiO2)–2SBn–PtCl2]
(cPt = 1.8×10–4 M, 80°C); (1) free and consumed for
hydrosilylation HMe2Si(OSiMe2)2H, (2) HMe2Si(OSiMe2)2H
consumed for hydrosilylation, (3) free HMe2Si(OSiMe2)2H.
(yield 7.6, 1.2, and 1.4% for n = 2, 3, and 4,
respectively; reaction time 5 h). Prolonged heating
(15 h) favors formation of HMe2Si(OSiMe2)nH, and
this process is faster in the presence of the
homogeneous platinum complex: yield 19.9, 3.6, and
0.7% over cis-[Pt(Bn2S)2Cl2] against 11.5, 1.6, and
0.4% over [(SiO2)–2SBn–PtCl2] for n = 2, 3, and 4,
respectively.
Decrease the reaction temperature to 60°C reduces
the yield of free HMe2Si(OSiMe2)nH (n = 2–4) and the
corresponding hydrosilylation products (Table 2).
However, as we already noted, the target reaction also
slows down (Fig. 1). The optimal temperature was
100°C. Under these conditions, the maximum
conversion of AllOBu is attained in 5 h, and the overall
yield of HMe2Si(OSiMe2)nH is 3.4, 0.6, and 0.1% for
n = 2, 3, and 4, respectively, which is lower than in 5 h
at 80°C and all the more lower than by the end of the
reaction at 80°C (8 h; Table 2).
Side transformations of AllOBu in the hydro-
silylation by 1,1,3,3-tetramethyldisiloxane at 80°C,
isomerization and reduction, were observed in the
presence of [(SiO2)–2SHex–PtCl2]: the yield of
isomeric propenyl butyl ethers was 0.8%, and of propyl
butyl ether, 0.5%. Unlike [(SiO2)–2SHex–PtCl2], the
hydrosilylation of AllOBu in the presence of [(SiO2)–
2SBu–PtCl2] and [(SiO2)–2SBn–PtCl2] was accom-
panied by formation of only propenyl butyl ether
isomers (isomerization, 1.1–1.4%). Raising the
temperature to 100°C reduced the contribution of side
process, and the yield of isomerization products in the
presence of [(SiO2)–2SR–PtCl2] (R = Bu, Hex, Bn)
was 3–4 times lower (0.3%). When AllOBu was heated
with [(SiO2)–2SR–PtCl2] in the absence of (HMe2Si)2O
(8 h, 80°C), only isomeric propenyl butyl ethers were
formed, and their yield in the presence of [(SiO2)–
2SHex–PtCl2] was comparable with that obtained in
the hydrosilylation (0.7%); however, in the case of
[(SiO2)–2SBu–PtCl2] and [(SiO2)–2SBn–PtCl2] their
yield was twice as low as that in the hydrosilylation
Heating of (HMe2Si)2O in the presence of [(SiO2)–
2SBn–PtCl2] without AllOBu at 80°C accelerates the
formation of HMe2Si(OSiMe2)nH (n = 2–4), which is
especially noticeable for HMe2Si(OSiMe2)2H. For
example, the yield of HMe2Si(OSiMe2)nH in 5 h is 7.6,
1.2, and 0.1% for n = 2, 3, and 4, respectively (Fig. 2).
Similar results were obtained in the hydrosilylation
catalyzed by homogeneous dibenzyl sulfide platinum
complex cis-[Pt(Bn2S)2Cl2] with the only difference
that the amount of HMe2Si(OSiMe2)4H was larger
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

30
DE VEKKI et al.
Table 2. Yields of HMe2Si(OSiMe2)nH (n = 2–4) in the hydrosilylation of allyl ethers by 1,1,3,3-teramethyldisiloxane
(HMe2Si)2O in the presence of [(SiO2)–2SR–PtCl2]a
Yield of HMe2Si(OSiMe2)nH,b %
n = 3
Reaction
time, h
Allyl ether
R
Temperature, °C
n = 2
n = 4
I
II
I
II
I
II
0.9
1.3
–
5
8
5
8
5
8
5
8
5
0.8
0.9
3.7
4.2
1.3
2.5
3.1
4.0
2.6
0.1
0.6
2.1
0.6
4.6
5.3
5.1
6.0
1.5
3.0
4.6
5.8
3.4
0.6
1.0
3.4
3.5
1.2
1.6
0.9
1.5
0.2
0.3
0.9
1.9
0.3
0.3
0.7
6.4
0.6
2.9
4.1
2.5
3.9
0.3
0.5
2.2
4.2
0.6
0.2
1.2
6.5
0.9
0.6
0.9
–
Bn
80
60
Hex
–
–
AllOBu
0.1
0.1
–
0.1
0.1
Traces
0.6
0.1
0.1
0.4
0.3
–
80
0.3
0.1
0.1
–
Bu
100
AllOEt
AllOBn
AllOPh
AllOGlyc
10
80
–
–
a
cPt = 1.8×10–4 M, molar ratio ether–(HMe2Si)2O = 1 : 1.5.
I: yield of free siloxane HMe2Si(OSiMe2)nH; II: overall yield of free siloxane HMe2Si(OSiMe2)nH and the corresponding hydrosilylation
products.
b
(0.8 and 0.6%, respectively). Further rise in the
reaction temperature (120°C, 8 h) did not affect the
yield of propenyl butyl ether isomers, which was also
lower {0.5%, [(SiO2)–2SBn–PtCl2]} than in the hydro-
silylation. The observed reduction of the yield of pro-
penyl butyl ether isomers in the absence of (HMe2Si)2O
as compared to the hydrosilylation suggests parti-
cipation of a silicon hydride intermediate in the iso-
merization process accompanying hydrosilylation.
the synthesis of the monoadduct. The yield of the γ-
addition product increases to 77.0% at 100°C in the
presence of [(SiO2)–2SBu–PtCl2]. Analogous yields of
the γ-adduct were achieved under conditions of
homogeneous catalysis by [Pt(cod)Cl2] (64.0%),
[Pt(Bn2S)2(SnCl3)Cl] (64.5%), [Pt(dmso)2Cl2] (65.9%),
and [Pt(cod)(SnCl3)Cl] (74.4%); rhodium complexes
[Rh(Ph3P)3Cl] (88%) and [Rh(Ph3P)3(SnCl3)] (90.5%)
were more efficient [45].
The hydrosilylation of AllOBu with Si–H-
containing monoadducts in the presence of [(SiO2)–
2SR–PtCl2] leads to the formation of γ,γ-bis-adducts
[yield 12.3 (80°C) or 15.2% (100°C)] and β,γ-bis-
adducts (≤1.2%). As a result, the yield of the target
product decreases. In the reaction of AllOBu with
(HMe2Si)2O catalyzed by [(SiO2)–2SBu–PtCl2] and
[(SiO2)–2SHex–PtCl2], the yield of the target hydro-
silylation product is 73.8 and 73.3%, respectively,
while the yield of the γ-adduct in the presence of
[(SiO2)–2SBn–PtCl2] is slightly lower (70.7%) despite
similar conversion of AllOBu. This suggests lower
catalytic efficiency of the benzyl sulfide complex in
Hydrosilylation of allyl ethyl ether. As in the
reaction with AllOBu, the kinetic curve for the
hydrosilylation of allyl ethyl ether by 1,1,3,3-
tetramethyldisiloxane in the presence of [(SiO2)–2SBu–
PtCl2] (80°C) has logarithmic shape. The time
necessary for 50% conversion of AllOEt (330 min) is
considerably longer than in the hydrosilylation of
AllOBu (143 min); after 10 h, the conversion of
AllOEt reaches 74%, whereas the maximum con-
version of AllOBu is attained in 8 h (99%, Fig. 3). The
regioselectivity (95.5%) and γΣ-selectivity (92.1%) in
the presence of [(SiO2)–2SBu–PtCl2] are lower, while
the selectivity for the γ-adduct is higher (79.7%, 80°C;
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

HYDROSILYLATION OF ALLYL ETHERS
Table 1), than the corresponding parameters in the hydro-
31
Conversion, %
silylation of AllOBu.
The contribution of side processes related to
transformations of HMe2Si(OSiMe2)nH in the hydro-
silylation of AllOEt by 1,1,3,3-tetramethyldisiloxane
in the presence of [(SiO2)–2SBu–PtCl2] is smaller than
in the hydrosilylation of AllOBu (after 10 h at 80°C,
the overall yield of HMe2Si(OSiMe2)nH with a
correction for their consumption for hydrosilylation
was 0.6, 0.2, and 0.1% for n = 2, 3, and 4, respectively,
i.e., 10–12 times lower than in the reaction with
AllOBu; Table 2). The small contribution of the
secondary transformations of (HMe2Si)2O in the
hydrosilylation of AllOEt in the presence of [(SiO2)–
2SBu–PtCl2] increases the selectivity with respect to
the γ-adduct, as compared to the reaction with AllOBu.
Time, h
Fig. 3. Variation of the conversion of (1) allyl butyl ether,
(2) allyl benzyl ether, (3) allyl glycidyl ether, (4) allyl ethyl
ether, and (5) allyl phenyl ether with time in the hydro-
silylation by (HMe2Si)2O in the presence of platinum
complex [(SiO2)–2SBu–PtCl2]; cPt = 1.8×10–4 M, molar ratio
allyl ether–(HMe2Si)2O = 1 : 1.5, 80°C.
In contrast, isomerization of AllOEt in the hydro-
silylation over [(SiO2)–2SBu–PtCl2] is more
significant than it would be expected on the basis of
the data for AllOBu. The concentration of propenyl
ethyl ethers reaches 3.1% which is twice as high as
that of propenyl butyl ethers; in addition, traces of
propyl ethyl ether were detected. Heating of AllOEt
with [(SiO2)–2SBu–PtCl2] in the absence of (HMe2Si)2O
(10 h, 80°C) afforded only traces of propenyl ethyl ether.
The selectivity for the γ-adduct in the presence of
[(SiO2)–2SBu–PtCl2] was 74.2%, and the γΣ-selec-
tivity, 89.4%. The regioselectivity of the addition of
(HMe2Si)2O in the hydrosilylation of AllOBn in the
presence of [(SiO2)–2SBu–PtCl2] (94.5%) was the
lowest among the examined ethers.
The contribution of side processes (transformations
of Si–H siloxanes) in the hydrosilylation of AllOBn in
the presence of [(SiO2)–2SBu–PtCl2] was smaller than
in the hydrosilylation of AllOBu but greater than in the
reaction with AllOEt; after 10 h, the concentration of
all siloxane by-products did not exceed 2.6%. After
10 h at 80°C, the overall yield of HMe2Si(OSiMe2)nH
with account taken of their consumption for
hydrosilylation was 1, 1.2, and 0.4% for n = 2, 3, and
4, respectively (Table 2).
The overall concentration of products of AllOEt
hydrosilylation by monoadducts containing active
Si–H bonds in the presence of [(SiO2)–2SBu–PtCl2]
(10 h, 80°C) was slightly lower than in the reaction
with AllOBu (9.9 and 1.4% of the γ,γ- and β,γ-bis-
adducts, respectively; Table 1) due to lower conversion
of the initial ether.
Hydrosilylation of allyl benzyl ether. The
hydrosilylation of allyl benzyl ether by 1,1,3,3-
tetramethyldisiloxane follows the same pattern as that
established for AllOBu and AllOEt. In the reaction
catalyzed by [(SiO2)–2SBu–PtCl2], allyl benzyl ether
is considerably more reactive than AllOEt: the 50%
conversion is achieved in 137 min against 330 min for
AllOEt; after 10 h at 80°C, the conversion of AllOBn
was 91%, while the conversion of AllOEt was 74%
(Fig. 3, Table 1). During the first two hours, AllOBn
was more reactive than AllOBu (in 1 h at 80°C, the
conversion of AllOBn was 33% against 24%
conversion of AllOBu), but the reaction slowed down
when a conversion of 50% was reached; as a result, the
conversion of AllOBu after 10 h was higher than that
of AllOBn by 9% (Fig. 3).
The isomerization and reduction of AllOBn were
twice as intense as the corresponding side processes in
the hydrosilylation of AllOEt; after 10 h at 80°C in the
presence of [(SiO2)–2SBu–PtCl2], the overall con-
centration of the isomerization and reduction products
was 5.7%. Therefore, the reaction selectivity for the
γ-adduct was even lower than those found for AllOEt
and AllOBu (Table 1). Heating of AllOBn in the
presence of [(SiO2)–2SBu–PtCl2] without (HMe2Si)2O
(10 h, 80°C) gave 1.9% of isomeric propenyl benzyl
ethers; i.e., their amount was almost twice as low as
that obtained in the hydrosilylation.
The yield of the γ,γ-adduct in the reaction catalyzed
by [(SiO2)–2SBu–PtCl2] (10 h, 80°C) almost coincided
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

32
DE VEKKI et al.
with the results of hydrosilylation of AllOBu (12.4%),
whereas the yield of the β,γ-adduct was twice as large
(3.7%).
PtCl2] (its concentration was 1.7% after 10 h at 80°C
and 8.5% after 22.5 h).
Hydrosilylation of allyl glycidyl ether. The
reactivity of AllOGlyc in the hydrosilylation by 1,1,3,3-
tetramethyldisiloxane in the presence of [(SiO2)–2SBu–
PtCl2] was comparable with that of AllOEt: AllOBu >
AllOBn > AllOEt ≈ AllOGlyc >> AllOPh. The
selectivity of [(SiO2)–2SBu–PtCl2]-catalyzed hydro-
silylation (70.7%), γΣ-selectivity (84.1%), and regio-
selectivity of the addition of (HMe2Si)2O (91.8%) were
the lowest in the examined series of allyl ethers (Table 1).
Hydrosilylation of allyl phenyl ether. Allyl phenyl
ether showed the lowest reactivity among the
examined allyl ethers; after 10 h at 80°C, its
conversion was as low as 23% (Fig. 3); cor-
respondingly the reactivity series of allyl ethers in the
presence of [(SiO2)–2SBu–PtCl2] is as follows:
AllOBu > AllOBn > AllOEt >> AllOPh. This series is
hardly consistent with published data according to
which there is no relation between the reactivity of
allyl ethers in hydrosilylation and the structure of
catalysts and Si–H reagents. The maximum yield of
the target product in the hydrosilylation of AllOPh is
often achieved in almost the same time as with other
allyl ethers; in the presence of siloxide rhodium
complexes, the hydrosilylation of AllOPh is faster than
the reaction with other ethers [6], whereas the
reactivity of AllOPh in the presence of [(SiO2)–2SBu–
PtCl2] is the lowest.
The contribution of side processes in the hydro-
silylation of AllOGlyc by 1,1,3,3-tetramethyldi-
siloxane in the presence of [(SiO2)–2SBu–PtCl2] was
larger than in the reactions with AllOEt and AllOBn
but smaller than in the hydrosilylation of AllOBu and
AllOPh; after 10 h at 80°C, the overall yield of
HMe2Si(OSiMe2)nH (including their consumption for
hydrosilylation) was 3.5, 0.9, and 0% for n = 2, 3, and
4, respectively (Table 2). Correspondingly, the effect
of initial allyl ethers on the side transformations of
siloxanes [estimated by the overall yield of HMe2Si
(OSiMe2)nH at the maximum ether conversion]
decreases in the series AllOPh > AllOBu > AllOGlyc >
AllOBn > AllOEt.
After 10 h, the selectivity in the hydrosilylation of
AllOPh was 79.8% (conversion 23%), which
coincided with the selectivity found for AllOEt but
was higher than those for other ethers (70.7–74.4%);
the γΣ-selectivity (97.4%) was slightly lower than that
for AllOBu, and the regioselectivity of the addition of
(HMe2Si)2O (98.2%) exceeded the corresponding
values for the other ethers.
Secondary transformations of AllOGlyc provide a
larger contribution to the reduction of selectivity. The
yield of propenyl glycidyl ether isomers reaches 5.0%,
which is 3.5 times higher than, e.g., the yield of
propenyl butyl ether isomers), and the yield of propyl
glycidyl ether is 3.3%. Heating of AllOGlyc with
[(SiO2)–2SBu–PtCl2] in the absence of (HMe2Si)2O for
10 h at 80°C afforded 2.3% of propenyl glycidyl ether,
which is twice as low as in the hydrosilylation.
Despite low rate of hydrosilylation of AllOPh in the
presence of [(SiO2)–2SBu–PtCl2], after 10 h the
reaction mixture contained both free oligosiloxanes
HMe2Si(OSiMe2)nH (yield 2.1 and 6.4% for n = 2 and
3, respectively) and the corresponding hydrosilylation
products. The overall yield of HMe2Si(OSiMe2)nH
(3.4, 6.5, and 0.3% for n = 2, 3, and 4, respectively)
was comparable with that observed in the
hydrosilylation of AllOBu (tabl. 2), and the amount of
octamethyltetrasiloxane (n = 4) was the largest among
all the examined catalytic systems. Side processes in
the hydrosilylation of AllOPh catalyzed by [(SiO2)–
2SBu–PtCl2] included only the formation of propenyl
phenyl ether isomers (0.4%) whose yield was 3–
7 times lower than the yield of the corresponding
isomeric ethers in the hydrosilylation of other allyl
ethers.
The hydrosilylation of AllOGlyc by Si–H-
containing monoadducts in the presence of [(SiO2)–
2SR–PtCl2] (10 h at 80°C) produced exclusively the
γ,γ-adduct whose concentration was 8.3%; it is slightly
lower than in the reactions with AllOEt, AllOBu,
AllOBn.
Reused of the [(SiO2)–2SR–PtCl2] catalysts
resulted in gradual reduction of their activity (3 cycles,
TOFAllOBu 0.1794 s–1, TOFAllOBn 0.2105 s–1, TOFAllOGlyc
0.0958 s–1, TOFAllOEt 0.0938 s–1, TOFAllOPh 0.0398 s–1,
TON > 2560), and the ether conversion decreased in
the catalyst series [(SiO2)–2SBn–PtCl2] > [(SiO2)–
2SHex–PtCl2] > [(SiO2)–2SBu–PtCl2], the reaction
time being the same.
Among all possible products of hydrosilylation by a
reactive Si–H group of the monoadduct, only γ,γ-
adduct was detected in the presence of [(SiO2)–2SBu–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

HYDROSILYLATION OF ALLYL ETHERS
Neither selectivity nor regioselectivity nor γΣ-selec-
EXPERIMENTAL
33
tivity changed to an appreciable extent upon catalyst
recycling; the amount of by-products resulting from
secondary transformations of siloxanes and allyl ethers
also remained virtually unchanged.
The IR spectra (4000–400 cm–1) were recorded in
KBr on a Shimadzu FTIR-8400S spectrometer. The
product mixtures were analyzed by GLC on an Agilent
7890A chromatograph equipped with a thermal
conductivity detector; DB-1 capillary column,
30 m×0.32 mm, film thickness 1 μm; sample volume
0.5 μL; injector temperature 250°C. The reaction
mixtures obtained from AllOPh and AllOBn were
analyzed under temperature programming from 150°C
(4 min) to 290°C at a rate of 42 deg/min, followed by
35 min at 290°C; carrier gas helium, split ratio 1:300.
The reaction mixtures obtained from AllOEt, AllOBu,
and AllOGlyc were analyzed under temperature
programming from 70°C (5 min) to 200°C at a rate of
5 deg/min and then to 225°C at a rate of 25 deg/min,
followed by 45 min at 225°C; carrier gas helium, split
ratio 1:250.
Interaction between the catalysts and reactants.
In order to understand the catalytic mechanism we
studied the reactions of [(SiO2)–2SBu–PtCl2] with
1,1,3,3-tetramethyldisiloxane and allyl butyl ether, and
the obtained products were involved in comparative
hydrosilylation.
The IR spectrum of the platinum complex treated
with (HMe2Si)2O and then thoroughly washed with
methylene chloride displayed a new absorption band at
2146 cm–1, which can be assigned to Si–H stretching
vibrations of the siloxane; simultaneously, the intensity
of bands at 2931 and νas(C–S) 2858 cm–1 typical of the
initial complex decreased. The catalytic activity of the
preliminarily treated complex (2 h at 80°C) was higher
than before the treatment; after 2.5 h at 80°C, the
conversion of AllOBu was 55 against 38% (when both
reactants were added simultaneously). The reaction
selectivity with respect to the γ-adduct was signi-
ficantly lower (46.5%) due to increased yield of the
γ,γ-adduct (by a an order of magnitude, 33%); the
regioselectivity slightly decreased (95.1 against
96.3%), and the γΣ-selectivity insignificantly increased
(from 94.9 to 96.6%).
The hydrosilylation of allyl ethers was carried out
in ampules at 60–100°C. An ampule was charged with
a required amount of catalyst, and a preliminarily
prepared mixture of 1,1,3,3-tetramethyldisiloxane,
allyl ether, and toluene at a molar ratio of 6:4:1 was
added; the concentration of platinum in the reaction
mixture was (1.8–5)×10–4 M, and the platinum content
of the supported catalyst was cPt (2.8–4.1)×10–5 mol/g.
The conversion and selectivity were determined by
GLC from the kinetic data using toluene as internal
standard according to the procedure described in [38].
Secondary catalytic transformations of (HMe2Si)2O
and allyl ethers were studied by analogy with the main
hydrosilylation process.
Analogous treatment of [(SiO2)–2SBu–PtCl2] with
allyl butyl ether produced no appreciable changes in
the IR spectrum, but the conversion of AllOBu
increased as compared to the untreated complex (41%
after 2.5 h). In this case, the selectivity with respect to
the γ-adduct, regioselectivity, and γΣ-selectivity were
lower by 1.4, 2.7, and 2.6%, respectively, due to larger
contribution of secondary transformations of AllOBu
(the yields of propenyl butyl and propyl butyl ethers
were 12.0 and 2.9%, respectively).
Commercial 1,1,3,3-tetramethyldisiloxane, allyl
glycidyl ether (Acros Organics), allyl butyl, allyl
phenyl, and allyl benzyl ethers (Aldrich), allyl ethyl
ether (Fluka), and toluene and methylene chloride of
analytical grade were used. The complexes [(SiO2)–
2SR–PtCl2] (R = Bu, Hex, Bn) were synthesized as
described in [37], and cis-[Pt(Bn2S)2Cl2] was prepared
according to [47].
Taking into account the known concept of the
hydrosilylation mechanism, the results of our study
suggest that the initial platinum complex reacts with
both allyl ether and 1,1,3,3-tetramethyldisiloxane.
Primary coordination of allyl ether facilitates isomeriza-
tion of the double bond, and the subsequent attack of
the intermediate complex by siloxane promotes reduc-
tion of the unsaturated ether. In its turn, primary
formation of silicon hydride complex is the key stage
of hydrosilylation and side transformations of
siloxanes.
ACKNOWLEDGMENTS
This study was performed in the framework of state
assignment of the Ministry of Education and Science
of the Russian Federation (project no. 11.5362.2017/8.9)
and the integrated program for the development of
high tech production of the Ministry of Education and
Science (contract no. 03.G25.31.0237).
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34
DE VEKKI et al.
16. Liu, G., Huang, B., and Cai, M., React. Funct. Polym.,
REFERENCES
2007, vol. 67, no. 4, p. 294. doi 10.1016/
j.reactfunctpolym.2007.01.006
1. Hydrosilylation. A Comprehensive Review on Recent
Advances (Advances in Silicon Science series, vol. 1),
Marciniec, B., Ed., Springer, 2009.
17. Liu, G. and Cai, M., J. Mol. Catal. A: Chem., 2006, vol. 258,
nos. 1–2, p. 257. doi 10.1016/j.molcata.2006.04.039
2. Putzien, S., Nuyken, O., and Kühn, F.E., Prog. Polym.
Sci., 2010, vol. 35, no. 6, p. 687. doi 10.1016/
j.progpolymsci.2010.01.007
3. Safa, K.D., Bahadori, A., Tofangdarzadeh, S., and
Nasirtabrizi, M.H., J. Iran. Chem. Soc., 2008, vol. 5,
no. 1, p. 37. doi 10.1007/BF03245813
18. Hu, R., Hao, W., and Cai, M., Chin. J. Chem., 2011,
vol. 29, no. 8, p. 1629. doi 10.1002/cjoc.201180292
19. Li, J., Yang, C., Zhang, L., and Ma, T., J. Organomet.
Chem., 2011, vol. 696, no. 9, p. 1845. doi 10.1016/
j.jorganchem.2011.02.021
20. Jiang, H., Wu, G., Cheng, P., Deng, F., and Deng, A.,
4. Galhenage, T.P., Hoffman, D., Silbert, S.D., Stafslien, Sh.J.,
Daniels, J., Miljkovic, T., Finlay, J.A., Franco, S.C.,
Clare, A.S., Nedved, B.T., Hadfield, M.G., Wendt, D.E.,
Waltz, G., Brewer, L., Teo, S.L.M., Chin-Sing, L., and
Webster, D.C., ACS Appl. Mater. Interfaces, 2016,
vol. 8, no. 42, p. 29025. doi 10.1021/acsami.6b09484
Youjigui Cailiao, 2006, vol. 20, no. 1, p. 57.
21. Zhao, J., Sun, Y., Xie, B., Wu, S., and Sun, H., Xiandai
Huagong, 2007, vol. 27, no. 1, p. 42.
22. Zhao, J., Xie, B., Wang, G., Song, S., and Sun, Y.,
React. Kinet. Catal. Lett., 2009, vol. 96, no. 1, p. 101.
doi 10.1007/s11144-009-5360-8
5. Lejars, M., Margaillan, A., and Bressy, Ch., Chem. Rev.,
23. Wang, L.-Z. and Jiang, Y.-Y., J. Organomet. Chem.,
1983, vol. 251, no. 1, p. 39. doi doi.org/10.1016/0022-
328X(83)80241-1
2012, vol. 112, no. 8, p. 4347. doi 10.1021/cr200350v
6. Marciniec, B., Walczuc, E., Blazejewska-Chadyniak, P.,
Kujawa-Welten, M., and Krompiec, S., Organosilicon
Chemistry V: From Molecules to Materials, Auner, N.
and Weis, J., Eds., Weinheim: Wiley, 2003, p. 415. doi
10.1002/9783527619924.ch67
7. Marciniec, B., Blazejewska-Chadyniak, P., and Kubicki, M.,
Can. J. Chem., 2003, vol. 81, no. 11, p. 1292. doi
10.1139/V03-145
8. Maciejewski, H., Marciniec, B., Blazejewska-
Chadyniak, P., and Dabek, I., Organosilicon Chemistry
VI: From Molecules to Materials, Auner, N. and Weis, J.,
Eds., Weinheim: Wiley, 2005, p. 408. doi 10.1002/
9783527618224.ch3
24. Hu, R., Zha, L., and Cai, M., Catal. Commun., 2010,
vol. 11, no. 6, p. 563. doi 10.1016/j.catcom.2009.12.020
25. Zha, L.F., Yang, W.S., Hao, W.Y., and Cai, M.Z., Chin.
Chem. Lett., 2010, vol. 21, no. 11, p. 1310. doi 10.1016/
j.cclet.2010.06.007
26. Zuev, V.V., de Vekki, D.A., Kuchaev, E.A., Vorob’ev, M.V.,
and Skvortsov, N.K., Russ. J. Gen. Chem., 2004,
vol. 74, no. 11, p. 1679. doi 10.1007/s11176-005-0083-7
27. de Vekki, D.A., Ol’sheev, V.A., Spevak, V.N., and
Skvortsov, N.K., Russ. J. Gen. Chem., 2001, vol. 71,
no. 12, p. 1912. doi 10.1023/A:1014292310639
9. Marciniec, B., Maciejewski, H., Szubert, K., and
Kurdykowska, M., Monatsh. Chem., 2006, vol. 137,
no. 5, p. 605. doi 10.1007/s00706-006-0461-9
28. Albeniz, A.C., Espinet, P., Lin, Y.-S., Orpen, A.G., and
Martin, A., Organometallics, 1996, vol. 15, no. 23,
p. 5003. doi 10.1021/om960406d
10. Maciejewski, H., Szubert, K., Marciniec, B., and
Pernak, J., Green Chem., 2009, vol. 11, no. 7, p. 1045.
doi 10.1039/b819310j
11. Marciniec, B., Szubert, K., Potrzebowski, M.J.,
Kownacki, I., and Lecszczak, K., Angew. Chem., Int.
Ed., 2008, vol. 47, no. 3, p. 541. doi 10.1002/
anie.200704362
12. Marciniec, B., Szubert, K., Fiedorow, S., Kownacki, I.,
Potrzebowski, M.J., and Dutkiewicz, M., J. Mol. Catal.
A: Chem., 2009, vol. 310, nos. 1–2, p. 9. doi 10.1016/
j.molcata.2009.05.013
13. Marciniec, B., Szubert, K., Potrzebowski, M.J.,
Kownacki, I., and Maciejewski, H., ChemCatChem,
2009, vol. 1, no. 2, p. 304. doi 10.1002/cctc.200900111
14. Miao, Q.J., Fang, Z.-P., and Cai, G.P., Catal. Commun.,
2003, vol. 4, no. 12, p. 637. doi 10.1016/
j.catcom.2003.10.006
29. Basato, M., Biffis, A., Martinati, G., Zecca, M., Ganis, P.,
Benetollo, F., Aronica, L.A., and Caporusso, A.M.,
Organometallics, 2004, vol. 23, no. 8, p. 1947. doi
10.1021/om0342560
30. de Vekki, D.A. and Skvortsov, N.K., Russ. J. Gen.
Chem., 2006, vol. 76, no. 1, p. 116. doi 10.1134/
S107036320601021X
31. Downing, Ch.M. and Kung, H.H., Catal. Commun.,
2011, vol. 12, no. 12, p. 1166. doi 10.1016/
j.catcom.2011.03.041
32. Bayon, J.C., Claver, S., and Masdeu-Bulto, A.M.,
Coord. Chem. Rev., 1999, vols. 193–195, p. 73. doi
10.1016/S0010-8545(99)00169-1
33. Hu, C.-Y., Han, X.-M., and Jiang, Y.Y., J. Mol. Catal.,
1986, vol. 35, no. 3, p. 329. doi 10.1016/0304-5102(86)
87080-8
34. Kann, C., Kong, X., Du, C., and Liu, D., Polym. J.,
15. Fang, Z.P., Yang, H.T., Miao, O.J., and Cai, G.P., Chin.
Chem. Lett., 2006, vol. 17, no. 9, p. 1155.
2002, vol. 34, no. 3, p. 97. doi 10.1295/polymj.34.97
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 1 2018

HYDROSILYLATION OF ALLYL ETHERS
35. de Vekki, D.A., Spevak, V.N., Kuchaev, E.A., and
35
S1070363210040079
Skvortsov, N.K., Russ. J. Gen. Chem., 2005, vol. 75,
no. 11, p. 1757. doi 10.1007/s11176-005-0505-6
41. Chernyshev, E.A., Belyakova, Z.V., Knyazeva, L.K.,
and Khromykh, N.N., Russ. J. Gen. Chem., 2007,
vol. 77, no. 1, p. 55. doi 10.1134/S1070363207010082
36. de Vekki, D.A., Kuchaev, E.A., Afonin, M.V., and
Simanova, S.A., Russ. J. Gen. Chem., 2008, vol. 78,
no. 4, p. 575. doi 10.1134/S1070363208040105;
de Vekki, D.A., Spevak, V.N., Kuchaev, E.A., and
Skvortsov, N.K., Russ. J. Gen. Chem., 2005, vol. 75,
no. 11, p. 1757. doi 10.1007/s11176-005-0505-6.
37. de Vekki, D.A. and Il’ina, M.A., Russ. J. Gen. Chem.,
2014, vol. 84, no. 8, p. 1580. doi 10.1134/
S1070363214080246
38. Il’ina, M.A., de Vekki, D.A., and Skvortsov, N.K., Russ.
J. Gen. Chem., 2014, vol. 84, no. 1, p. 40. doi 10.1134/
S1070363214010095
39. de Vekki, D.A., Il’ina, M.A., and Skvortsov, N.K., Izv.
Sankt-Peterb. Gos. Tekhnol. Inst., 2015, no. 32 (58),
p. 54. doi 10.15217/issn998984-9.2015.32.54
42. Schilling, C.L., J. Organomet. Chem., 1971, vol. 29,
no. 1, p. 93.
43. Chernyshev, E.A., Belyakova, Z.V., Knyazeva, L.K.,
Pomerantseva, M.G., and Efimova, L.A., Russ. Chem.
Bull., 1998, vol. 47, no. 7, p. 1374. doi 10.1007/
BF02495569
44. Feng, S. and Cui, M., React. Funct. Polym., 2000,
vol. 45, no. 2, p. 79. doi 10.1016/S1381-5148(00)00013-4
45. Andreev, S.A., Il’ina, M.A., Volkova, A.M., de Vekki, D.A.,
and Skvortsov, N.K., Russ. J. Appl. Chem., 2010,
vol. 83, no. 11, p. 1962. doi 10.1134/S1070427210110133
46. de Vekki, D.A. and Skvortsov, N.K., Russ. J. Gen.
Chem., 2009, vol. 79, no. 4, p. 762. doi 10.1134/
S107036320904015X
40. Belyakova, Z.V., Pomerantseva, M.G., Efimova, L.A.,
Chernyshev, E.A., and Storozhenko, P.A., Russ. J. Gen.
Chem., 2010, vol. 80, no. 4, p. 728. doi 10.1134/
47. Inorganic Syntheses, Coucouvanis, D., Ed., New York:
Wiley, 2002, vol. 33.
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