Nickel(0) catalyzed oxidation of organosilanes to disiloxanes by air as an oxidant

Article abstract of DOI:10.1016/j.tetlet.2019.03.002

We report here an efficient non-aqueous route to symmetrical disiloxanes from their corresponding organosilanes using Ni(COD)₂ with 3,4,7,8-tetramethyl-1,10-phenanthroline in air. Our methodology is very simple and high yielding. The reaction mechanism is also proposed.

Full text of DOI:10.1016/j.tetlet.2019.03.002

Accepted Manuscript
Nickel(0) Catalyzed Oxidation of Organosilanes to Disiloxanes by Air as an
Oxidant
Haiping Lv, Ronibala Devi Laishram, Jiayan Li, Guangrui Shi, Weiqing Sun,
Jianbin Xu, Yong Yang, Yang Luo, Baomin Fan
PII:
S0040-4039(19)30204-7
https://doi.org/10.1016/j.tetlet.2019.03.002
TETL 50643
DOI:
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
10 December 2018
26 February 2019
1 March 2019
Please cite this article as: Lv, H., Laishram, R.D., Li, J., Shi, G., Sun, W., Xu, J., Yang, Y., Luo, Y., Fan, B., Nickel(0)
Catalyzed Oxidation of Organosilanes to Disiloxanes by Air as an Oxidant, Tetrahedron Letters (2019), doi: https://
doi.org/10.1016/j.tetlet.2019.03.002
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Graphical Abstract
Nickel(0) Catalyzed Oxidation of
Organosilanes to Disiloxanes by Air as an
Oxidant
Leave this area blank for abstract info.
Haiping Lva, Ronibala Devi Laishrama, Jiayan Lia, Guangrui Shia, Weiqing Suna*, Jianbin Xua, Yong Yangb,
Yang Luob, Baomin Fana*
aYMU-HKBU Joint Laboratory of Traditional Natural Medicine/ Key Laboratory of Chemistry in Ethnic
Medicinal Resources, Yunnan Minzu University, Kunming, 650500, China
Fax: (+86)-871-65946330; E-mail addresses: 1104059769@qq.com (Weiqing Sun); FanBM@ynni.edu.cn
(Baomin Fan)
bChongqing Academy of Chinese Materia Medica, Chongqing, 400065, China.
R2
R1
R3
R2
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
O
Si
R1
Si
R3
R3 Si R1
R2
H
Air, toluene,70 °C
1a-r
2a-r

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Nickel(0) Catalyzed Oxidation of Organosilanes to Disiloxanes by Air as an Oxidant
Haiping Lva, Ronibala Devi Laishrama, Jiayan Lia, Guangrui Shia, Weiqing Suna*, Jianbin Xua, Yong
Yangb, Yang Luob, Baomin Fana*
aYMU-HKBU Joint Laboratory of Traditional Natural Medicine/ Key Laboratory of Chemistry in Ethnic Medicinal Resources, Yunnan Minzu University,
Kunming, 650500, China
Fax: (+86)-871-65946330; E-mail addresses: 1104059769@qq.com (Weiqing Sun); FanBM@ynni.edu.cn (Baomin Fan)
bChongqing Academy of Chinese Materia Medica, Chongqing, 400065, China.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
We report here an efficient non-aqueous route to symmetrical disiloxanes from their
corresponding organosilanes using Ni(COD)2 with 3,4,7,8-tetramethyl-1,10-phenanthroline in
air. Our methodology is very simple and high yielding. The reaction mechanism is also
proposed.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Disiloxanes
Organosilanes
Bis(cyclooctadiene)nickel(0)
Aerobic
Siloxanes possessing Si-O linkage are ubiquitous in nature.
They have widespread applications in silicone industries,1
pharmaceutical,2 cosmetic industries,3 liquid crystal display
element,4 microelectronic devices and sensor fabrication.5 They
are also used as a coupling partner in Hiyama-type reaction.6
Siloxane like 1,3-bis(phenylethynyl) tetramethyldisiloxane has
also been employed as a building block in the synthesis of novel
macrocycles.7 1,3-diphenyl disiloxane (DPDS) has been used for
preparing phosphine ligands with extremely diverse scaffolds as
well as to recycle phosphine oxides in ambient catalytic
phosphine redox reactions.8
produces no waste or water as the sole by-product.15 Thus, in this
report, we are using bis(cyclooctadiene)nickel(0) with 3,4,7,8-
tetramethyl-1,10-phenanthroline under aerobic condition to
oxidize hydrosilanes (Scheme 1).
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
Si
H
O
Si
Si
Air, toluene, 70 C
Scheme 1: Ni(0) catalyzed air oxidation of hydrosilanes to
symmetrical disiloxanes.
Many methods have been available in the literature for the
preparation of symmetrical disiloxanes like an intermolecular
condensation of silanols,9 reactions of polysiloxanes with
Grignard reagents.10 Chojnowski’s group also used Lewis acid,
tris(pentafluorophenyl)borane as a catalyst to produce disiloxanes
via a coupling reaction of hydrosilanes with alkoxysilanes.11
Transition-metal catalyzed oxidation of hydrosilanes is the most
common strategy to prepare disiloxanes.12 In(III)-catalyzed air
oxidation of hydrosilanes has been reported; however, the
reaction has limited scope and the generation of a full equivalent
of hydrogen gas which is a safety concerned.13
We initiated our study by testing several nickel compounds
using 1,10-phenanthroline for the synthesis of disiloxanes from
organosilanes in toluene at 70 °C. Among the tested compounds
Ni(COD)2 was found to be the best catalyst in promoting the
reaction giving disiloxane in the highest yield of 89% (Table 1,
entry 1). Compounds like Ni(CO)2(PPh3)2, Ni(PPh3)4 were with
good activity for the oxidation giving the desired product 2a in
good yield (Table 1, entries 2 and 3). Nickel powder and
Ni(acac)2 also showed the activities but the results were not
appreciable (Table 1, entries
4 and 5). Ni(OH)(OAc),
Ni(NO3)2.6H2O, Ni(C2O4).H2O, Ni(OAc)2.2H2O were also tested
but failed to catalyze the reaction (Table 1, entries 6-9). We did
not limit our studies to Ni compounds only. Other metals
compounds of Fe and Co were also studied but the results were
not appreciable (Table 1, entries 10 and 11). We also investigated
the ligand on the reactivity of the reaction using optimal catalyst
Ni(COD)2. Ligands like 1,10-phenanthroline-5,6-dione, 4,7-
Although many transition metals have been reported for these
types of transformations, the nickel catalyzed transformation is
much less reported. However, nickel due to its relatively
electropositive nature readily loss electron density in oxidative
addition reaction which allows for the use of cross-coupling
electrophiles, its low cost, easy to handle and also due to the
readily available oxidation states invoked in development of a
broad range of innovative reactions.14 Normally used traditional
oxidants are often toxic and released a considerable amount of
by-products. The oxygen in the air is a cost-free oxidant and
dimethoxy-1,10-phenanthroline,
2,2'-bipyridine
and
tricyclohexylphosphane gave moderate yield, while 3,4,7,8-
tetramethyl-1,10-phenanthroline furnished excellent yield (97%)
and bathophenanthroline gave a good yield (92%). But with

2
Tetrahedron Letters
ligand 3,8-dibromo phenanthroline the yield was poor. We next
screened different solvents to find that toluene was the best-
performing medium. The reaction was found to proceed with
lower efficiency in solvents like 1,4-dioxane and DMF, moderate
reactivity in MeCN and no reaction in DCE. We also investigated
the effect of temperature on the reactivity by varying the
temperature from 30-90 °C. However, the best result was
obtained at 70 °C.
effect on the reactivities of the organosilanes; ortho, meta or
para-methyl aryl substituents gave almost comparably excellent
yields (Table 2, entries 2-4). It also tolerates the bulky aryl
substituents like para-tert-butyl phenyl dimethyl silane and gave
excellent yield (Table 2, entry 8). Even the sterically hindered
silanes such as diphenyl methyl silane, triphenylsilane can also
tolerate the reaction conditions giving the corresponding
oxidative coupling product in moderate yields (Table 2, entries
12 and 13). Long chain alkyl substituted silanes like
trihexylsilane and triethylsilane also furnished good results
(Table 2, entries 16 and 17). The cyclohexylsilane gave the
corresponding disiloxane greater than 99% yield. Interestingly,
ortho-phenylene bis(dimethylsilane) offered cyclic disiloxane
with moderate yield (Table 2, entry 18). The applicability of the
reaction condition for the preparation of unsymmetrical
disiloxane was tested by coupling aryldimethylsilane 1a with p-
methyl aryldimethylsilane 1d, a mixture of the unsymmetrical
disiloxane 3 with self-coupling products 2a and 2d was obtained
in 84% total yield (Scheme 2). Judged from the ratio of the
products, the reaction between two different silanes showed no
selectivity.
Having found the optimal conditions, we investigated the
oxidative coupling of an array of organosilanes (Table 2). The
oxidative coupling, which is different from the traditional
coupling, occurs between two nucleophiles in presence of an
appropriate oxidant. Oxidative coupling reactions received great
attention for their exemplary potential in carbon-carbon
and carbon-heteroatom bond formation.16 The reaction was
found to be very general and not sensitive to the electronic nature
of the substituents. It also tolerates various aryldimethylsilanes
having activating and deactivating group on the aryl moiety like
methyl, ethyl, methoxy, fluoro, chloro, and cyano at para-
position giving the corresponding disiloxanes in excellent yield
(Table 2, entries 2, 6-11). Position of substituents has no much
Table 1. Optimization of organosilane oxidation to disiloxanea
Metal/ Ligand
Si H
O
Si
Si
Air, Solvent, 70 C
1a
2a
Entry
1
Metal
Ni(COD)2
Ligand
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
Bathophenanthroline
Solvent
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Time (h)
Yield (%)b
9
89
67
87
8
2
Ni(CO)2(PPh3)2
Ni(PPh3)4
46
9
3
4
Ni(powder)
Ni(acac)2
72
72
72
72
72
72
72
72
4
5
20
0
6
Ni(OH)(OAc)
Ni(NO3)2.6H2O
Ni(C2O4).H2O
Ni(OAc)2.2H2O
Fe catalyst
Co catalyst
Ni(COD)2
7
0
8
0
9
0
10c
11d
12
13
14
15
16
0-18
0-13
97
92
7
Ni(COD)2
6
Ni(COD)2
72
72
9
3,8-Dibromophenanthroline
Ni(COD)2
1,10-phenanthroliine-5,6-dione
58
75
67
Ni(COD)2
4,7-Dimethoxy-1,10-phenanthroline
2,2'-Bipyridine
Ni(COD)2
60
17
18
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Ni(COD)2
Tricyclohexylphosphane
Toluene
1,4-Dioxane
DCE
48
18
72
5
48
92
NR
82
91
32
57
19
20
21
22
23
24
3,4,7,8-Tetramethyl-1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
3,4,7,8-Tetramethyl-1,10-phenanthroline
MeCN
DMF
4
DMSO
6
Pentanol
6
aReaction condition:1a (0.4mmol), metal (5%), ligand (6%), solvent (1 mL), under air (1 atm); bIsolated yields; cFe(powder), FeCl2, FeBr2, FeI2, Fe(OTf)2, FeCl3,
FeBr3 used. dCoF3, CoCl2, CoBr2, CoI2, Co(acac)3, Co(SCN)2.(H2O)3, Co(OAc)2·4 H2O, CoCO3 used.

3
Table 2: Scope of the substrates for the synthesis of disiloxanea
R2
R1
R3
O
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
O
Si
Si
Si
Si
R1
Si
R3
R3 Si R1
R2
R2
H
Air, toluene,70 °C
2a
, 25% yield
1a-r
2a-r
Si
H
+
Time
(h)
Yield
(%)c
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
Entry
Substrate
Product
1a
O
Si
+
Air, toluene, 70 C
SiH
SiH
1
2a
3
97
3
Si
H
, 43% yield
1a
1b
+
1d
2b
2b
2c
2d
5
94
O
Si
2d
Si
, 18% yield
3
4
3
3
92
92
SiH
Scheme 2: Preparation of unsymmetrical disiloxane
1c
To identify the oxygen source, we investigated the reaction
by a set of control experiments (Scheme 3). When the reaction
was carried out under O2 atmosphere, 2a was obtained in 72%
yield. By using 5 equivalents of water instead of other oxygen
sources, no product was detected. The reaction was also carried
out in presence of MS 4A° giving 2a in high yield. These control
experiments had ruled out the possibility that water served as an
oxygen source. Thus, confirmed the current reaction is the
aerobic oxidation reaction.
SiH
1d
SiH
5
2e
3.5
89
1e
O
SiH
6
7
2f
5
3
82
98
1f
SiH
2g
1g
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
O
Si
H
a
SiH
Si
Si
8
9
2h
2i
3.5
5
>99
94
O2, toluene, 70 C
1h
1j
2
2a, 72% yield
None
1a
F
SiH
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
1i
b
Si
H
H2O, toluene, 70 C
Cl
SiH
1a
10
11
2j
6
92
Ni(COD)2/ 3,4,7,8-Tetramethyl-1,10-phenanthroline
O
Si
H
Si
Si
c
NC
SiH
2k
8
95
Air, MS 4A, toluene, 70 C
1k
2a, 95% yield
1a
SiH
Scheme 3: Control experiments.
We are tempted to assume the mechanism for the oxidative
12
2l
4
5
85
69
1l
coupling of organosilane as follows (Scheme 4). A nickel(0)
species initially reacts with ligand 3,4,7,8-tetramethyl-1,10-
phenanthroline to generate complex A which undergo oxidative
addition to the organosilane 1 to form nickel (II) square planer
intermediate B, followed by addition of molecular oxygen in
between Ni and hydrogen bond to form nickel (II) peroxide C.17
Another molecule of organosilane may enter the catalytic cycle to
form ether D with the release of water molecule which finally
furnished the oxidative coupling product disiloxane 2 and
regenerates the nickel complex A.
SiH
13b
2m
3
1m
H
Si
14
2n
2o
5
4
82
1n
1o
15b
>99
SiH
SiH
16b
17b
2p
4
8
82
83
1p
Ni(0)+L
SiR3
R3Si
O
H-SiR3
1
Ni(0)L2
2
SiH
A
2q
1q
II
SiR3
O
N
N
N
N
II
H
Ni
Ni
SiR3
D
B
SiR3
SiH
SiH
Si
O
Si
18b
6
76
H2O
1r
2r
O2
II
OH
O
aReaction condition: 1a (0.4 mmol), Ni(cod)2 (5%), 3,4,7,8-tetramethyl-1,10-
phenanthroline (6%), toluene (1 mL), 70 °C, under air (1 atm); b1a (0.4
mmol), Ni(COD)2 (10%), 3,4,7,8-tetramethyl-1,10-phenanthroline (12%),
toluene (1 mL), 90 °C, under air (1 atm); cIsolated yields.
N
N
Ni
H-SiR3
SiR3
C
Scheme 4: Plausible mechanism of the oxidative coupling
reaction

4
Tetrahedron
10. Minoru, T.; Toshio, S.; Yoshiaki, N. G.B. Patent 1,435, 465, 1976;
Chem. Abstr.1975, 82, 4411.
In summary, we reported an efficient zero valent nickel
catalyzed nonaqueous aerobic oxidation of wide range of
organosilanes to furnish disiloxanes. The methodology provided
high yield, simple experimental set-up, short reaction time which
are ideal for laboratory preparation.
11. Chojnowski, J.; Rubinsztajn, S.; Cella, J. A.; Fortuniak, W.;
Cypryk, M.; Kurjata, J.; Kaźmierski, K. Organometallics 2005,
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T.; Satsuma, A. Chem. Eur. J. 2012, 18, 2226. (d) Krüger, A.;
Albrecht, M. Chem. Eur. J. 2012, 18, 652. (e) Sawama, Y.;
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Acknowledgments
We gratefully thank the National Natural Science Foundation
of China (21572198), the Applied Basic Research Project of
Yunnan Province (2018FB021, 2017FA004) and Yunnan
Provincial Key Laboratory Construction Plan Funding of
Universities for financial support.
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18. General procedure for the synthesis 2a. Ni(COD)2 (5.5 mg, 0.02
mmol), 3,4,7,8-Tetramethyl-1,10-phenanthroline (5.7 mg, 0.024
mmol), 1.0 mL toluene were added to a Schlenk tube under argon
atmosphere. The resulting solution was stirred at room
temperature for 30 min, then the organosilane 1a (54.5 mg, 0.4
mmol) was added and the mixture was stirred at 70 °C under
atmosphere with GC monitoring until the complete consumption
of 1a. The residue was purified by silica gel column
chromatography to afford the corresponding disiloxane 2a (55.6
mg, 97% yield).
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Highlights
1) An efficient zero valent nickel catalyzed nonaqueous
aerobic oxidation of organosilanes was reported.
2) Various disiloxanes symmetrical disiloxanes were
prepared from their corresponding organosilanes.
3) The mechanism of the nickel catalyzed aerobic
oxidation of organosilane is proposed.