Hydrosilylation of alkenes catalyzed by Fe powder

Article abstract of DOI:10.1080/10426507.2018.1506782

A novel iron-catalyzed hydrosilylation of alkenes process under solvent-free conditions has been reported. The influence of the amount of Fe catalyst, reaction temperature and various alkenes and silanes on the hydrosilylation were investigated. High yields of adduct were obtained in the hydrosilylation of octene with MeCl₂H, Me₂ClSiH and Ph₂SiH₂ by using 10 mol% iron powder as a signal catalyst.

Full text of DOI:10.1080/10426507.2018.1506782

Phosphorus, Sulfur, and Silicon and the Related Elements
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Hydrosilylation of alkenes catalyzed by Fe powder
Xiaoling Yang, Ying Bai, Jiayun Li, Zinan Dai & Jiajian Peng
To cite this article: Xiaoling Yang, Ying Bai, Jiayun Li, Zinan Dai & Jiajian Peng (2019):
Hydrosilylation of alkenes catalyzed by Fe powder, Phosphorus, Sulfur, and Silicon and the Related
Elements, DOI: 10.1080/10426507.2018.1506782
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PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
https://doi.org/10.1080/10426507.2018.1506782
Hydrosilylation of alkenes catalyzed by Fe powder
Xiaoling Yang, Ying Bai, Jiayun Li, Zinan Dai, and Jiajian Peng
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou, China
ABSTRACT
ARTICLE HISTORY
Received 26 March 2018
Accepted 27 July 2018
A novel iron-catalyzed hydrosilylation of alkenes process under solvent-free conditions has been
reported. The influence of the amount of Fe catalyst, reaction temperature and various alkenes
and silanes on the hydrosilylation were investigated. High yields of adduct were obtained in the
hydrosilylation of octene with MeCl2H, Me2ClSiH and Ph2SiH2 by using 10 mol% iron powder as a
signal catalyst.
KEYWORDS
Iron powder; catalysis;
hydrosilylation; alkenes
GRAPHICAL ABSTRACT
Introduction
pincer-type ligands also play an important role in the hydro-
silylation of alkenes as effective catalysts.[14,15] Nagashima
and coworkers reported that iron carboxylate and an iso-
cyanide ligand efficiently and selectively catalyzed the hydro-
silylation of alkenes with hydrosiloxaned.[16] Very recently,
Obora and coworkers reported that monodispersed N,N-
dimethylformamide (DMF)-stabilized Fe2O3 nanoparticles
exhibited efficient catalytic activity in hydrosilylation of
alkenes without further additives.[17]
However, these aforementioned iron-based catalysts are
all metal organic complexes and have some disadvantages
such as instability in air and complicated preparation pro-
cess. Herein, we developed an extremely simple experimental
procedure that hydrosilylation of alkenes could be con-
ducted by using iron powder as catalyst directly. The cata-
lytic system showed excellent catalytic performance and
good recyclability in the hydrosilylation of 1-octene
with Ph2SiH2.
Iron and iron compounds are intensively used in scientific
research and engineering application due to its rich resource
as the second most abundant metal reserve in the earth
crust (4.7%) and the low cost. The use of iron-based mater-
ial as a catalyst in the organic synthesis reaction has
attracted much attention up to now. Various iron-catalyzed
reaction systems have been developed, including substitution
reactions, addition reactions, elimination reactions, reduc-
tion of heteroatoms, domino reactions and cyclization
reactions.[1–4]
Iron-catalyzed hydrosilylation should be particularly
noticed owing to their superior atom economy compared
with precious metal compounds.[5–8] A number of Fe com-
plexes have also been developed for the alkene hydrosilyla-
tion reactions.[9] The study of iron-catalyzed hydrosilylation
can be dated back to the 1960s. In 1962, Mesmeyanoc and
coworkers reported hydrosilylation of olefins catalyzed by
pentacabonyl iron(0) or colloidal iron.[10] Subsequently,
Wrighton and coworkers found that Fe(CO)5 showed an
excellent catalytic performance in the hydrosilylation of ole-
fins.[11] Recently, iron-based materials have received much
attention again owing to their superior performance in the
catalytic hydrosilylation of alkenes. The catalytic hydrosilyla-
tions were selective in forming the anti-Markovnikov prod-
uct catalyzed by five-coordinate iron dinitrogen complexes
Results and discussion
Catalytic hydrosilylation of alkenes
Initially, the hydrosilylation of alkenes with Ph2SiH2 cata-
lyzed by Fe-powder were tested and the results were listed
in Table 1. The results indicate that the Fe-powder catalyst
shows excellent catalytic performance for the hydrosilylation
of linear alkenes. The conversion of 1-hexene reaches up to
(
iPrPDI)Fe(N2)2.[12] Lu’s group also reported that iron com-
plexes showed high activity in the asymmetric hydrosilyla- 92.6% with a higher than 99% b-adduct selectivity (entry 1,
tion of alkenes with Ph2SiH2.[13] In addition, Huang and Table 1). Meanwhile, 73.8% conversion of 1-octene with
Walter reported that new iron complexes containing PNN 98.1% selectivity for the b-adduct was obtained under
CONTACT Ying Bai
baiying0912@163.com; Jiajian Peng
jjpeng@hznu.edu.cn
Key Laboratory of Organosilicon Chemistry and Material Technology of
Ministry of Education, Hangzhou Normal University, Yuhangtang Road 2318, Hangzhou 311121, China.
Supplemental data for this article can be accessed on the publisher’s website at https://doi.org/10.1080/10426507.2018.1506782.
ß 2019 Taylor & Francis Group, LLC

2
X. YANG ET AL.
Table 1. Hydrosilylation of alkenes catalyzed by Fe powder.
Entry
Alkenes
1-Hexene
1-Hexene
1-Octene
1-Octene
3,3-Dimethyl-1-butene
1-Tetradecene
Iso-butyl vinyl ether
Butyl vinyl ether
Styrene
Silanes
Tem. (ꢀC)
Time (h)
Conversion (%)
Select. (%)a
1
2b
3
4
5
6
7
8
9
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
Ph2SiH2
90
90
90
90
90
120
120
120
120
12
12
12
24
12
22
22
22
22
92.6
/
73.8
96.5
>99
/
98.1
98.3
64.6
98.6
/
/
/
/
/
/
/
/
Reaction condition: alkenes 4.0 mmol, silanes 4.8 mmol, Fe powder 10 mol% based on alkene.
aThe selectivity of b-adduct, the byproduct are a-adduct and alkane.
bThe blank catalytic reaction without Fe catalyst.
Table 2. Effect of amount of Fe on hydrosilylation of 1-octene.
Seclect. (%)
Entry
Catalyst (mol%)
Conversion (%)
b-Adduct
a-Adduct
Octane
Dehydrogenative silylation
1
2
3
4
2.5
5
10
54.8
65.8
73.8
85.9
100
100
98.1
98.7
/
/
/
/
/
/
1.9
1.3
/
/
/
/
20
Reaction condition: 1-octene 4.0 mmol, Ph2SiH2 4.8 mmol, 90 ꢀC, 12 h.
similar conditions (entry 3, Table 1). The conversion of 1-
octene is increased to 96.5% when prolonging reaction time
to 24 h. The conversion of 3,3-dimethyl-1-butene reaches up
to 64.6% with 98.6% b-adduct selectivity (entry 5, Table 1).
Unfortunately, almost no adducts were detected when using
tetradecene, iso-butyl vinyl ether, butyl vinyl ether and styr-
ene as substrates. The alkenes of starting materials almost
have no changes. The reactivity of these olefins is low for Fe
catalyst due to the steric effect.
Table 3. Effect of temperature on the hydrosilylaiton of 1-octene
with Ph2SiH2.
Select. (%)
Temp. Conv.
Dehydrogenative
silylation
Entries
(ꢀC)
(%)
b-Adduct a-Adduct Octane
1
2
3
4
5
6
50
70
90
100
110
120
7.4
16.6
73.8
84.9
97.1
98.3
100
100
98.1
98.7
99.7
99.9
/
/
/
/
/
/
/
/
1.9
1.3
0.3
0.1
/
/
/
/
/
/
Reaction condition: 1-octene 4.0 mmol, Ph2SiH2 4.4 mmol, Fe powder 10 mol%
based on 1-octene, 12 h.
Effect of the amount of Fe-powder on the reaction
The effect of the amount of Fe on the conversion of 1-
octene is illustrated in Table 2. It can be seen that higher
conversion is obtained when a greater amount of Fe catalyst
was used during the same reaction time. 85.9% conversion
with 98.7% selectivity of b-adduct is obtained by using
20 mol% catalyst based on 1-octene, however, the better
selectivity is attained by using lower amount of Fe powder.
The more Fe catalyst leaded to generating octane through
hydrogenation of 1-octene.
indicates that the activity of the Fe powder increases along
with the increase of reaction temperature. Using the same
amount of Fe powder as catalyst, the conversion of the sub-
strate is 16.6% at 70 ꢀC after 12 h. When the temperature is
90 ꢀC, the conversion of octene is 73.8% within 12 h. At
110 ꢀC, the conversion of 1-octene reaches 97.1%
within 12 h.
Hydrosilylation of 1-octene with various silanes
Under similar conditions, different silanes were used (Table
4). The conversion of octene is 85.7% and 72.9% when
Effect of reaction temperature on the hydrosilylation
The effect of reaction temperature on the catalytic activity Me2ClSiH and MeCl2SiH were used, respectively. The corre-
was investigated and the results are illustrated in Table 3. It sponding selectivity of b-adduct is 80.5% and 74.8%,

PHOSPHORUS, SULFUR, AND SILICON AND THE RELATED ELEMENTS
3
Table 4. Scope of silane for Fe powder catalyzed hydrosilylation of 1-octene.
signal catalyst. Although the active center for the iron pow-
der catalyst is still unclear, the simple and effective Fe cata-
lyst is attractive. At present, the further research work
including reaction mechanism is in process.
Select. (%)
Conv.
(%)
Dehydrogenative
silylation
Entry
Silanes
b-Adduct a-Adduct Octane
1
2
3
4
5
6
7a
8
Me2ClSiH
MeCl2SiH
Ph2SiH2
PhSiH3
PhMe2SiH
(MeO)3SiH
Et3SiH
85.7
72.9
73.8
73.1
/
/
/
80.5
74.8
98.1
96.6
/
/
/
/
/
/
/
/
/
/
/
3.2
15.2
1.9
1.6
/
/
/
16.3
10.0
/
1.8
/
/
/
Experimental
The 1-hexene (99%), 1-octene (98%), 3,3-dimethyl-1-buty-
lene (95%), iso-butyl vinyl ether (99%), butyl vinyl ether
(98%) were purchased from Aladdin Chemical Reagent Co.
Ltd. Tetradecene (96%) was purchased from Alfa Aesa
chemical reagent Co. LTD. The silanes were purchased from
Meryer Chemical Reagent Co. Ltd and Aladdin chemical
reagent Co. LTD. The iron powder (99%) was purchased
from Sinopharm Chemical Reagent Co. LTD (catalogue
No10197417-017). The other reagents were purchased from
Sinopharm Chemical Reagent Co. LTD. All reagents were
used without further purification.
Cl3SiH
12.5
65.2
23.1
11.7
Reaction condition: 1-octene 4.0 mmol, silanes 4.4 mmol, Fe powder 10 mol%
based on 1-octene, 90 ꢀC, 12 h.
aReaction temperature is 50 ꢀC.
General procedure for the catalytic hydrosilylation of ole-
fins is followed: iron powder (0.023 g, 0.4 mmol) was
charged into a 10 mL pressure glass tube with sealed cover.
Then olefin (4.0 mmol) and diphenylsilane (0.88 g, 4.8 mmol)
were charged into the flask, and the resulting mixture was
stirred at 90 ꢀC for desired time under the sealed condition.
The product was obtained by decantation separation. The
conversion of alkenes and selectivity were determined and
quantified by GC analysis on an Agilent 7890B. And the
structure of the products were determined by GC-MS ana-
lysis on an Agilent 7890B-5977B apparatus equipped with a
HP-5MS
Chromatography: Trace DSQ GC Column, split ¼ 50:1,
minꢂ1
constant flow, inlet
temperature ¼ 250 ꢀC, column temperature ¼ 55 ꢀC (held for
1 min) then 15 ꢀC minꢂ1 up to 1ꢂ210 ꢀC, then 20 ꢀC minꢂ1 up
to 200 ꢀC, and then 15 ꢀC min up to 280 ꢀC, (held for
5 min). 1 H NMR (400 MHz) and 13C NMR (100.6 MHz)
spectra were recorded on a Bruker Avance spectrometer.
column
(30 m ꢁ 0.25 mm ꢁ 0.25 lm).
Gas
Figure 1. Recyclability of Fe catalyst in the hydrosilylation of 1-octene. Reaction
condition: 1-octene 4.0 mmol, Ph2SiH2 4.4 mmol, Fe powder 10 mol% based on
1-octene, 90 ꢀC, 12 h.
flow ¼ 1.1 mL
respectively. H2SiPh2 and H3SiPh gave the conversion 73.8%
and 73.1% with high selectivity of b-adduct, is 98.1% and
96.6%, respectively. But HSiCl3 gave the conversion 12.5%
and the selectivity of b-adduct 65.2 with octane 23.1%.
However, almost no hydrosilylation products could be
detected by using PhMe2SiH, (MeO)3SiH or Et3SiH as
hydride under the same conditions. The catalytic activities
of tertiary silane were much lower in comparison to those
with primary and secondary silanes.[18]
Funding
We are grateful to the Natural Science Foundation of Zhejiang
Province (LY18B020012) and Zhejiang Provincial Technologies R&D
Program of China (2017C31105) for financial support.
Recyclability of Fe catalyst for hydrosilylation
References
In recycling experiments, the Fe catalyst was allowed to sep-
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The catalytic system without any further treatment was used
for the next cycle. The results are listed in Figure 1. Fe cata-
lyst can be recycled 6 times without significant loss
in activity.
€
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