Mechanochemistry-a new powerful green approach to the direct synthesis of alkoxysilanes

Article abstract of DOI:10.1039/c7gc03862c

The present work shows a new one-stage mechanochemical method for the direct synthesis of alkoxysilanes by silicon mechanoactivation followed by a reaction with an alcohol. Alkoxysilanes were obtained with nearly complete silicon and alcohol conversion. This method allows for a considerable simplification of the traditional multistage process by eliminating three stages that include silicon and catalyst preparation, and adapts it to green chemistry requirements. Vibration milling removed the oxide film, and the mechanoactivation of the large silicon fraction (1000-2000 μm) occurs in the reactor working space. Abrasion of the reactor walls and grinding bodies made of brass results in a developed catalytic surface on silicon, as it has been proven by a set of physical analytical methods such as scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS).

Full text of DOI:10.1039/c7gc03862c

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A. Muzafarov, Green Chem., 2018, DOI: 10.1039/C7GC03862C.
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Page 1 of 17
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DOI: 10.1039/C7GC03862C
Mechanochemistry – a new powerful green approach to direct synthesis
of alkoxysilanes
Maxim N. Temnikov1, Anton A. Anisimov1, Pavel V. Zhemchugov1, Dmitry N.
Kholodkov1, Alexander S. Goloveshkin1, Alexander V. Naumkin1, Sergey M.
Chistovalov1, Dimitris Katsoulis3, Aziz M. Muzafarov1,2
1A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences (INEOS RAS)
Moscow, 119991, Russian Federation
2N.S. Enikolopov Institute of Synthetic Polymeric Materials, Russian Academy of Sciences (ISPM RAS)
Moscow, 117393, Russian Federation.
3Dow Corning Corporation. A wholly owned subsidiary of The Dow Chemical Company 2200 W. Salzburg
Rd, Midland, Michigan 48686, USA
Eꢀmail: temnikov88@gmail.com; sm53@ineos.ac.ru; aziz@ineos.ac.ru
Keywords: direct synthesis, mechanochemical, mechanoactivation, alkoxysilanes, ball milling,
vibration milling, one stage method, chlorineꢀfree chemistry, catalytic effect of the abrasion
Abstract: The present work shows a new oneꢀstage mechanochemical method for the
direct synthesis of alkoxysilanes by silicon mechanoactivation followed by reaction with an
alcohol. Alkoxysilanes were obtained with nearly complete silicon and alcohol conversion. This
method allows a considerable simplification of the traditional multistage process by eliminating
three stages that include silicon and catalyst preparation, and adapts it to the green chemistry
requirements. Vibration milling, removed the oxide film, and mechanoactivation of the large
silicon fraction (1000ꢀ2000 µm) occur in the reactor working space. Abrasion from the reactor
walls and grinding bodies made of brass result in a developed catalytic surface on silicon, as it
has been proven by a set of physical analytical methods such as scanning electron microscopy
(SEM), energy dispersive Xꢀray spectroscopy (EDX), powder Xꢀray diffraction (PXRD), and Xꢀ
ray photoelectron spectroscopy (XPS).
Introduction
The discovery of direct synthesis of organochlorosilanes by E. Rochow in
the 1940s made it possible to raise the chemistry and production of silicone
materials to a completely new level.1 As a result, organosilicon compounds found
applications in nearly every area of human activity and in everyday life.
However, the situation concerning the ecological and economic components
of production and further application of organochlorosilanes, which satisfied the
demands of people in the XX century, no longer meets the requirements of green
chemistry principles. This is primarily due to the emission of hydrogen chlorideꢀ
containing waste in the production of silicone polymers from the corresponding
chlorineꢀcontaining organosilicon monomers.

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DOI: 10.1039/C7GC03862C
Alkoxysilanes might have become an alternative to chlorosilanes. Numerous
publications on the synthesis of the main organosilicon products from various
esters of orthosilicic acid are available.2–20 Unfortunately, production of the latter is
based on the esterification by alcohols or by esters of the corresponding
chlorosilanes.21–26 This fact makes it doubtful that it is expedient to use alkoxy
derivatives of silicon for synthesizing organosilicon products on their basis.
However, if a new, cheaper and ecologically friendly method for synthesizing
alkoxysilanes is discovered, it might change this situation fundamentally.In this
context, direct synthesis is the most promising method for the preparation of
alkoxysilanes. It is currently a subject of intense development by many research
groups all over the world.27–34 The mechanism of the direct synthesis reaction, both
chloroꢀ and alkoxysilanes, remains open. Many researchers of this topic21,30,35–37
agree that the reaction occurs upon the interaction of the active center Cu3Si with
the organic precursor (RCl in the case of chlorosilanes and ROH in the case of
alkoxysilanes). On the other hand, the following authors27,38 attribute silylene
nature to these active centers.
A few methods to perform this process exist. The most popular ones include
the liquid phase and gas phase techniques, as well as the method performed in
autoclave reactors. The majority of patent publications describe the liquid phase
method that implies the use of a highꢀtemperature heat transfer agent39–55 and thus
necessitates an additional stage of solvent purification,54,56 while the low
conversion of an alcohol considerably complicates the isolation of the target
products.57 The gas phase method performed in a gasꢀsolid reactor appears more
promising29,34 due to the relative simplicity of the hardware along with the high
process intensity that is most important for industrial application. Still, the above
examples require a preliminary preparation of silicon and the siliconꢀcopper
contact mass.
The problems described above can be solved using the mechanochemical
approach. Mechanochemistry is an approach that is being actively developed and
finds use in various fields of chemistry and materials science.58 In fact, the
mechanochemical method finds use in the production of nanomaterials,59,60
MOF,61,62 in catalysis,63,64 organic synthesis,65–67 polymer chemistry,68,69 and in
waste treatment.70,71 Despite the numerous publications on this subject, there were
no successful attempts to use mechanoactivation in the direct synthesis of
alkoxysilanes.
The present work shows a first example of the oneꢀstage mechanochemical
method for the direct synthesis of alkoxysilanes by silicon mechanoactivation
followed by its reaction with an alcohol. As shown below, this approach
considerably simplifies the entire preparation process by reducing it to a single
stage.
Results and Discussion

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Direct synthesis of alkoxysilanes performed in a vibrating reactor
The direct synthesis of alkoxysilanes (Scheme 1) is a laborious and energyꢀ
consuming process. Apart from the main reaction stage, it involves a number of
successive preparation stages (Scheme 2).
Scheme 1: Direct synthesis of alkoxysilanes
Scheme 2: Stages of silicon preparation before a direct synthesis
Scheme 2 shows that, before a direct synthesis is performed, silicon obtained
by SiO2 reduction has to be milled and treated with hydrofluoric acid in order to
remove the thin oxide layer from the surface. This reaction is accompanied by the
evolution of SiF4 that is an undesirable waste product. After that, the soꢀcalled
contact mass has to be prepared by chemical reactions of Si with CuCl. This
reaction creates active sites on the surface. According to literature data, the
composition of these sites is Cu3Si.72
We assumed on the basis of literature data that the soꢀcalled abrasion
effect64,73,74,75 can be used intentionally in the direct synthesis of alkoxysilanes
since it provides a developed silicon surface with catalytic centers. We performed
experiments in a vibration reactor that we designed, with working chamber and
grinding bodies made of brass (please see Supplementary information for a
description). This material mainly consists of copper, a classic catalyst in the
reaction of silicon with alcohols, and zinc that is known to promote this
process.30,76,38 This allowed us to hope that the necessary amount of the catalyst
would enter the reaction directly from the reactor walls.
Largeꢀgrain commercial silicon (grain size 1000ꢀ2000 µm) was used in this
study. It was not treated with HF, hence its surface contained a thin oxide layer that
is known to have a passivating effect on the direct synthesis process.77 However,
as one can see from the experimental results (Table 1), nearly total conversion of
silicon is achieved by mechanochemical direct synthesis in a, both with methanol
and ethanol.

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Table 1: Results of direct synthesis of alkoxysilanes performed with various
vibration intensity
No. Alcohol
type used
Process
temperature,
oC
Experiment
duration, min acceleration,
g
Vibrational
Silicon
conversion,
%
Selectivity
with respect with
to
Selectivity
respect to
trialkoxysila tetraalkoxy
ne, %*
0
silane, %*
100
1
2
3
MeOH
EtOH
EtOH
250
250
250
150
200
250
19
19
7,5
91
94
65
0
100
77
23
*ꢀ without consideration for highꢀmolecular condensation products
Most likely, the adverse effect of the presence of SiO2 is diminished since
the original silicon surface is small and hence it contains a small amount of silicon
dioxide. The silicon surface increases considerably during the reaction due to
grinding, which results in the formation of a developed reaction surface free from
SiO2.
Analysis of volatile reaction products has shown that a tetraalkoxysilane is
the main product. Furthermore, a minor amount (>0.5%) of a Si–Cꢀcontaining
product and (0.5 ꢀ 2%) of higherꢀmolecular components were detected. The
absence of compounds containing a SiꢀH group in the case of high vibration
intensity can be explained by the presence of a considerable amount of Cu(0) that
catalyzes the trialkoxysilaneꢀtoꢀtetraalkoxysilane conversion.78 If lowerꢀintensity
vibrations were used (7.5g), triethoxysilate appeared in the reaction products with
23% selectivity but the conversion was lower, i.e., ~65%. Probably, this difference
may be explained by the formation of the more reactive Cu(0) in the synthesis at
the higher vibrational acceleration. This experiment shows that it is principally
possible to obtain triethoxysilane by the method suggested in this study.
At a vibration intensity of 19g, the process had high activity, as it is evident
from the insignificant alcohol amount in samples that were withdrawn during
nearly the entire synthesis, Fig. 1, a and b.

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100
80
60
40
20
0
a)
MeOH
Si(OMe)4
Other
0
50
100
150
200
Time, min
100
80
60
40
20
0
b)
EtOH
Si(OEt)4
Other
0
50
100
150
200
250
300
Time, min
100
80
60
40
20
0
c)
EtOH
Si(OEt)4
HSi(OEt)3
Other
0
50
100
150
200
250
Time, min

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Fig. 1: Plots of reaction product and alcohol concentrations in samples
withdrawn during the synthesis vs. time: a) with MeOH at 19g; b) EtOH at 19g; c)
EtOH at 7.5g.
As the intensity of mechanical vibrations decreases from 19g to 7.5g, the
alcohol conversion and hence the reaction rate decrease (Fig. 1, c). It is evident
from the plots that the maximum alcohol conversion is later achieved in the case
“c” than in the cases “a” and “b”. This can be explained by the increase of time of
mechanical activation in reducing intensity oscillations and, consequently, the
collision force of grinding bodies. On the other hand, this phenomenon may be due
to an induction period77,79,80 that appears at a lower vibration intensity and hence
lower activity of the contact mass.
Thus, the use of mechanoactivation in the direct synthesis of alkoxysilanes
allows one to obtain tetraalkoxysilanes in high yield with nearly complete
conversion of silicon and without the need for a special preparation of the latter.
By decreasing the vibrations frequency, triethoxysilane was obtained with 23%
selectivity, but this results in a decrease in the silicon and alcohol conversions and
in a lower reaction rate. This experiment shows that the method suggested in this
paper can be efficiently used to obtain triethoxysilane, too. However, at this stage
we did not perform any experiments for process optimization in order to shift the
selectivity towards the formation of the SiꢀH containing monomer.
Analysis of spent mass
After completion of the reaction, the spent mass (SM) was withdrawn from
the reactor and analyzed by a set of physical methods, such as: scanning electron
microscopy (SEM), energy dispersive Xꢀray spectroscopy (EDX), Powder Xꢀray
diffraction (PXRD), and Xꢀray photoelectron spectroscopy (XPS).
Scanning electron microscopy (SEM-EDX)
One can see in electronic images (Fig. 2) that the SM surface (Fig. 2b) is
well developed and, unlike the initial silicon (Fig. 2a), has nanometerꢀsized pores
(Fig. 2c):

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a
b
c
Fig. 2: SEM images: a – silicon before the reaction; b and c – SM after the
reaction
One can see from EDX data (Fig. 3b) that the SM contains a considerable
amount of copper and zinc that appeared due to abrasion of reactor walls and
grinding bodies. The presence of Fe and Al can be explained by the composition of
the starting commercial silicon and the brand of brass used as the material for the
reactor and grinding bodies (see Supplementary information).

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a
b
Fig. 3: EDX spectra: spent silicon - a; spent mass - b.
Powder Xꢀray diffraction
EDX data are in good agreement with PXRD data (Fig. 4). A study of the
spent mass by this method has shown that the sample contains the following
phases: copper, various alloys of copper and zinc, Cu3Si, and a small amount of the
initial silicon. All phases except silicon have small crystal sizes (Table 2).

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Figure 4. PXRD data of samples: spent mass (blue line), b) initial silicon
(red line).
Table 2. Composition of the contact mass studied after the reaction.
Phase
Content %
26(1)
35(1)
28.5(5)
5.6(2)
Size, nm
4.4(2)
20.8(7)
27.5(6)
12(1)
Cu
Cu0.7Zn0.3
CuZn (Zhanghengite)
Cu3Si
Si
5.4(2)
62(7)
The presence of peaks at 44.6° and 45.1° corresponding to a reactive
intermetallide, Cu3Si,30,31,79,81 in the spectrum of the spent mass indicates that
active catalytic sites are formed on silicon surface during mechanical grinding. The
data obtained in the present study are consistent with existing ideas about the
mechanism of the reaction through Cu3Si, but do not give any additional
information about it. The presence of these centers in the SM is indicative of the
efficiency of the direct synthesis process during the entire reaction, since its
absence would mean that the contact mass is deactivated.
Xꢀray photoelectron spectroscopy

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It is evident from the overview spectrum of the spent mass (see Fig. 5) that
the surface contains Zn, Cu, Si, O, and C atoms.
Zn 2p
O 1s
3
O KVV
KVV
2
1
0
Cu 2p
Cu LMM
Ca LMM
Zn LMM
C 1s
Si 2s
Zn 3p
Cl 2P
Cu 3p
1200
800
400
Binding energy, eV
0
Fig. 5. Overview spectrum of the surface of the spent contact mass
The elementary composition of the SM surface determined by XPS is
presented in Table 3:
Table 3. Elementary composition of the sample surface determined by XPS
Cu, at.%
1.18
Zn, at.% C, at.% O, at.% Si, at.%
6.35 37.70 40.62 14.14
The small amount of copper and zinc on the contact mass surface in
comparison with the content of elements such as C, Si and O indicates that
organosilicon oligomers are deposited. They can be formed due to side reactions
with liberation of water.82
Figure 6 demonstrates the C1s and Si2p photoelectron spectra of the starting
silicon and the spent contact mass. They considerably differ in shape due to
different relative contributions of carbonꢀcontaining groups and chemical states of
Si atoms.

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15000
Initial Silicon
Spent mass
Initial Silicon
Spent mass
10000
5000
0
10000
5000
0
296
292
288
284
280
106
104
102
100
98
96
94
Binding energy, eV
Binding energy, eV
Fig. 6. C 1s and Si 2p photoelectron spectra of the samples studied.
Table 4 shows the percentage ratio of their content on the surface of the
initial silicon and the spent mass:
Table 4. Relative concentrations of the carbon-containing groups and
various silicon states.
Cꢀ
Si
ꢀ
CꢀC/CꢀH
CꢀOꢀC
/CꢀOH
6.3
C=O
C(O)O
Si0,
Si2p3/2
23.5
Si0,
Si2p3/2
11.7
Si+ Si3+ Si4+
Initial Silicon, %
Spent mass, %
26.6
38.8
1.8
1.0
2.0
2.4
0.9
3.8 22.9
3.9 24.6
7.4
2.0
18.2
1.4
0.8
It is evident from the table that the spent mass surface after the reaction
mostly contains silicon in oxidized form, which also indicates that siloxane
deposits are formed during the direct synthesis. Furthermore, the surfaces of both
the contact mass after the reaction and of initial silicon contain a considerable
number of Cꢀcontaining compounds. For more details, please see Supplementary
information.
As it is evident from the above, XPS analysis allows one to conclude that the
SM surface contains Cu and Zn, which proves the fact of abrasion from the
grinding bodies and reactor walls during the direct synthesis. The presence of a
considerable amount of Cꢀcontaining products and Si4+ indicates that siloxane
products are formed during the reaction.
Thus, the integrated study of the spent contact mass by EDX, XPS and
PXRD methods proves the formation of catalytic centers on silicon surface due to
abrasion from reactor walls and grinding bodies made of brass. This allows one to
perform a direct synthesis without adding a copper catalyst or promoting agents.
Acknowledgments
This study was supported by the Russian Science Foundation (grant no. 14ꢀ
23ꢀ00231). Electron microscopy characterization was performed at the Department
of Structural Studies of Zelinsky Institute of Organic Chemistry, Moscow. The
NMR and IR spectroscopic data were obtained using the equipment of Center for
molecule composition studies of INEOS RAS.

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The authors acknowledge Dow Corning Corporation for the support of the
initial phases of this work.
Conclusion
Thus, in this study we have developed and implemented a new method for
synthesizing alkoxysilanes based on the utilization of mechanochemical activation.
This approach allowed us to considerably simplify the multistage and laborious
preparation process preceding the direct synthesis of alkoxysilanes. The coarse
silicon fraction (1000ꢀ2000 µm) is simultaneously ground in the vessel and
removed the oxide film. After that, the synthesis is started by feeding an alcohol to
the vessel without any preparation of the contact mass. This became possible
because of the catalytic effect of the abrasion of brass from which the grinding
bodies and reactor walls are made. During the reaction a very well developed
catalytic surface is formed on silicon, as we showed by the set of physical analysis
methods. The suggested approach makes it possible to obtain tetraethoxyꢀ and
tetramethoxysilane in high yields with nearly full silicon conversion.
Triethoxysilane was obtained with 23% selectivity when the vibration intensity
was decreased from 19g to 7.5g, which demonstrates the capabilities of this
method for synthesizing SiꢀH containing monomers.
References
1
2
E. G. Rochow, J. Am. Chem. Soc., 1945, 67, 963–965.
A. A. Kalinina, D. N. Kholodkov, I. B. Meshkov, M. A. Pigaleva, I. V.
Elmanovich, Y. A. Molodtsova, M. O. Gallyamov and A. M. Muzafarov,
Russ. Chem. Bull., 2016, 65, 1104–1109.
3
4
5
6
S. A. Milenin, A. A. Kalinina, N. V. Demchenko, N. G. Vasilenko and A. M.
Muzafarov, Russ. Chem. Bull., 2013, 62, 705–709.
M. A. Soldatov, N. A. Sheremetéva, A. A. Kalinina, N. V. Demchenko, O.
A. Serenko and A. M. Muzafarov, Russ. Chem. Bull., 2014, 63, 267–272.
A. Kalinina, N. Strizhiver, N. Vasilenko, N. Perov, N. Demchenko and A.
Muzafarov, Silicon, 2014, 7, 95–106.
A. A. Kalinina, E. V. Talalaeva, A. I. Demchenko, N. G. Vasilenko, Y. A.
Molodtsova, N. V. Demchenko and A. M. Muzafarov, Russ. Chem. Bull.,
2016, 65, 1013–1019.
7
8
S. A. Milenin, A. A. Kalinina, V. V. Gorodov, N. G. Vasilenko, M. I. Buzin
and A. M. Muzafarov, Russ. Chem. Bull., 2015, 64, 2498–2504.
E. V Egorova, N. G. Vasilenko, N. V Demchenko, E. A. Tatarinova and A.

Page 13 of 17
Green Chemistry
View Article Online
DOI: 10.1039/C7GC03862C
M. Muzafarov, Dokl. Chem., 2009, 424, 15–18.
9
K. Kuroda, A. Shimojima, K. Kawahara, R. Wakabayashi, Y. Tamura, Y.
Asakura and M. Kitahara, Chem. Mater., 2013, 26, 211–220.
10 E. Y. Ladilina, T. S. Lyubova, V. V. Semenov, A. I. Kirillov, D. V.
Skamnitskiy, A. P. Kasatkin, S. A. Lermontova, O. N. Gorshkov and M. E.
Shenina, Glas. Phys. Chem., 2012, 38, 347–355.
11 A. Y. Khalimon, W. E. Piers, J. M. Blackwell, D. J. Michalak and M. Parvez,
J. Am. Chem. Soc., 2012, 134, 9601–9604.
12 L. L. Xunjun C, Yingde C, Guoqiang Y, J Appl Polym Sci, 2007, 106, 1007–
1013.
13 F. B. Madsen, I. Javakhishvili, R. E. Jensen, A. E. Daugaard, S. Hvilsted and
A. L. Skov, Polym. Chem., 2014, 5, 7054–7061.
14 J. B. Grande, A. S. Fawcett, A. J. McLaughlin, F. Gonzaga, T. P. Bender and
M. A. Brook, Polymer (Guildf)., 2012, 53, 3135–3142.
15 S. E. Laengert, A. F. Schneider, E. Lovinger, Y. Chen and M. A. Brook,
Chem. - An Asian J., 2017, 12, 1208–1212.
16 R. Wakabayashi and K. Kuroda, Chempluschem, 2013, 78, 764–774.
17 D. B. Thompson and M. A. Brook, J. Am. Chem. Soc., 2008, 130, 32–33.
18 S. Rubinsztajn and J. A. Cella, Macromolecules, 2005, 38, 1061–1063.
19 M. A. Brook, J. B. Grande and F. Ganachaud, in Advances in Polymer
Science, 2010, vol. 235, pp. 161–183.
20 A. A. Kalinina, I. V. Elmanovich, M. N. Temnikov, M. A. Pigaleva, A. S.
Zhiltsov, M. O. Gallyamov and A. M. Muzafarov, RSC Adv., 2015, 5, 5664–
5666.
21 M. A. Brook, Silicon in Organic, Organometallic, and Polymer Chemistry, J.
Wiley, 2000.
22 R. Wakabayashi, Y. Sugiura, T. Shibue and K. Kuroda, Angew. Chemie - Int.
Ed., 2011, 50, 10708–10711.
23 R. Wakabayashi, K. Kawahara and K. Kuroda, Angew. Chemie - Int. Ed.,
2010, 49, 5273–5277.
24 WO2012091154A1, 2011.
25 E. Sugawara and H. Nikaido, Antimicrob. Agents Chemother., 2014, 58,
7250–7.
26 A. V. Lebedev, R. M. Minas’yan, A. M. Abramkin, V. D. Sheludyakov, N.

Green Chemistry
Page 14 of 17
View Article Online
DOI: 10.1039/C7GC03862C
E. Kuzmina, A. B. Lebedeva, G. E. Surikov and V. B. Rybakov, Russ. J.
Gen. Chem., 2016, 86, 1859–1863.
27 M. Okamoto, Res. Chem. Intermed., 2006, 32, 317–330.
28 N. Y. Adonin, S. A. Prikhod’ko, A. Y. Shabalin, I. P. Prosvirin, V. I.
Zaikovskii, D. I. Kochubey, D. A. Zyuzin, V. N. Parmon, E. A. Monin, I. A.
Bykova, P. O. Martynov, S. L. Rusakov and P. A. Storozhenko, J. Catal.,
2016, 338, 143–153.
29 F. Chigondo, B. Zeelie and P. Watts, ACS Sustain. Chem. Eng., 2016, 4,
6237–6243.
30 S. H. Kareem, F. A. ALSaady and N. A. Hikmat, J. Assoc. Arab Univ. Basic
Appl. Sci., 2012, 12, 27–32.
31 G. J. Wang, F. X. Zhang, G. Y. Liu and X. N. Liu, Adv. Mater. Res., 2012,
455, 80–86.
32 Z. Lei, H. Sue, Y. Chunhui, L. Ji, Y. Kai, H. Chenfa and G. Shibin, Appl.
Organomet. Chem., 2011, 25, 508–513.
33 J. S. Han, J. H. Cho, M. E. Lee and B. R. Yoo, Bull. Korean Chem. Soc.,
2009, 30, 683–686.
34 M. N. Temnikov, A. S. Zhiltsov, V. M. Kotov, I. V. Krylova, M. P. Egorov
and A. M. Muzafarov, Silicon, 2015, 7, 69–78.
35 D. Sun and B. E. B. Ã, Thin Solid Films, 1997, 46, 127–132.
36 M. P. Clarke, J. Organomet. Chem., 1989, 376, 165–222.
37 L. Zhang, J. Li, K. Yang, C. Hu, S. Ge and C. Yang, Adv. Mater. Res., 2011,
233–235, 1534–1539.
38 M. P. Clarke and I. M. T. Davidson, J. Organomet. Chem., 1991, 408, 149–
156.
39 RU Patent 2476435C1, 2013.
40 RU Patent 2468865 C1, 2012.
41 US Patent 7.582.788 B2, 2009.
42 US Patent 200808192 3A1, 2008.
43 US Patent 7.429.672 B2, 2008.
44 US Patent 2008/0132721 A1, 2008.
45 US Patent 2007/0060764 A1, 2007.

Page 15 of 17
Green Chemistry
View Article Online
DOI: 10.1039/C7GC03862C
46 US Patent RE39.650 E, 2007.
47 RU Patent 2277537 C1, 2006.
48 US Patent 6.727.375 B2, 2004.
49 RU Patent 2235726 C1, 2004.
50 RU Patent 2196142C2, 2003.
51 US Patent 6.380.414 B2, 2002.
52 US Patent 6.410.771 B1, 2002.
53 RU Patent 2185384C1, 2002.
54 WO Patent 01/12635 A1, 2001.
55 EP Patent 2319851 A1, 2001.
56 A. S. Gorshkov, V. M. Kopylov, A. A. Markacheva and A. N. Polivanov,
Russ. J. Appl. Chem., 2002, 75, 1196–1197.
57 US2007073076A1, 2007.
58 J.ꢀL. Do and T. Friščić, ACS Cent. Sci., 2017, 3, 13–19.
59 J. Yu, B. W. McMahon, J. A. Boatz and S. L. Anderson, J. Phys. Chem. C,
2016, 120, 19613–19629.
60 B. W. McMahon, J. P. L. Perez, J. Yu, J. A. Boatz and S. L. Anderson, ACS
Appl. Mater. Interfaces, 2014, 6, 19579–19591.
61 P. A. Julien, C. Mottillo and T. Friščić, Green Chem., 2017, 19, 2729–2747.
62 F. Qi, R. S. Stein and T. Friščić, Green Chem., 2014, 16, 121–132.
63 J.ꢀB. Yu, Y. Zhang, Z.ꢀJ. Jiang and W.ꢀK. Su, J. Org. Chem., 2016, 81,
11514–11520.
64 T. L. Cook, J. A. Walker and J. Mack, Green Chem., 2013, 15, 617.
65 K.ꢀY. Jia, J.ꢀB. Yu, Z.ꢀJ. Jiang and W.ꢀK. Su, J. Org. Chem., 2016, 81, 6049–
6055.
66 S.ꢀJ. Lou, Y.ꢀJ. Mao, D.ꢀQ. Xu, J.ꢀQ. He, Q. Chen and Z.ꢀY. Xu, ACS Catal.,
2016, 6, 3890–3894.
67 S. Gupta and J. M. Khurana, Green Chem., 2017, 19, 4153–4156.
68 H. Oka, K. Imato, T. Sato, T. Ohishi, R. Goseki and H. Otsuka, ACS Macro
Lett., 2016, 5, 1124–1127.
69 A. N. Maratkanova, A. V. Syugaev, A. A. Shakov, O. Y. Vilkov and S. F.
Lomayeva, J. Phys. Chem. C, 2012, 116, 14005–14013.

Green Chemistry
Page 16 of 17
View Article Online
DOI: 10.1039/C7GC03862C
70 Q. Tan and J. Li, Environ. Sci. Technol., 2015, 49, 5849–5861.
71 Q. Lu, Z. Cai, F. Lin, L. Tang, S. Wang and B. Huang, ACS Sustain. Chem.
Eng., 2016, 4, 2165–2172.
72 B. Gillot, G. Weber, H. Souha and M. Zenkouar, J. Alloys Compd., 1998,
270, 275–280.
73 L. Chen, M. O. Bovee, B. E. Lemma, K. S. M. Keithley, S. L. Pilson, M. G.
Coleman and J. Mack, Angew. Chemie Int. Ed., 2015, 54, 11084–11087.
74 R. A. Haley, A. R. Zellner, J. A. Krause, H. Guan and J. Mack, ACS Sustain.
Chem. Eng., 2016, 4, 2464–2469.
75 V. A. Chlenol and N. V. Mikhaylov, Vibrokipyashchiy sloy, Nauka, 1972.
76 H. Ehrich, D. Born, K. Richter, J. RichterꢀMendau and H. Lieske, Appl.
Organomet. Chem., 1997, 11, 237–247.
77 E. Suzuki, M. Okamoto and Y. Ono, Solid State Ionics, 1991, 47, 97–104.
78 M. Okamoto, H. Abe, Y. Kusama, E. Suzuki and Y. Ono, J. Organomet.
Chem., 2000, 616, 74–79.
79 E. Suzuki and Y. Ono, J. Catal., 1990, 125, 390–400.
80 W. Luo, G. Zhang, G. Wang and J. Wang, Tsinghua Sci. Technol., 2006, 11,
252–258.
81 M. Okamoto, N. Mimura, E. Suzuki and Y. Ono, Catal. Letters, 1995, 33,
421–427.
82 I. V Krylova, M. P. Egorov, O. M. Nefedov and N. D. Zelinsky, Russ. Chem.
Bull. Int. Ed. Izv. Akad. Nauk. Seriya Khimicheskaya, 2017, 66, 260–266.

Page 17 of 17
Green Chemistry
View Article Online
DOI: 10.1039/C7GC03862C