Highly efficient oxidative cleavage of alkenes and cyanosilylation of aldehydes catalysed by magnetically recoverable MIL-101

Article abstract of DOI:10.1002/aoc.3957

The catalytic activity of magnetically recoverable MIL-101 was investigated in the oxidation of alkenes to carboxylic acids and cyanosilylation of aldehydes. MIL-101 was treated with Fe₃O₄ and the prepared catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, N₂ adsorption measurements, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and inductively coupled plasma analysis. The catalytic active sites in this heterogeneous catalyst are Cr³⁺ nodes of the MIL-101 framework. This heterogeneous catalyst has the advantages of excellent yields, short reaction times and reusability several times without significant decrease in its initial activity and stability in both oxidation and cyanosilylation reactions. Its magnetic property allows its easy separation using an external magnetic field.

Full text of DOI:10.1002/aoc.3957

Received: 6 March 2017
DOI: 10.1002/aoc.3957
Revised: 15 May 2017
Accepted: 17 June 2017
F U L L P A P E R
Highly efficient oxidative cleavage of alkenes and
cyanosilylation of aldehydes catalysed by magnetically
recoverable MIL‐101
Maryam Nourian | Farnaz Zadehahmadi | Reihaneh Kardanpour |
Shahram Tangestaninejad
| Majid Moghadam
| Valiollah Mirkhani |
Iraj Mohammadpoor‐Baltork
Department of Chemistry, Catalysis
The catalytic activity of magnetically recoverable MIL‐101 was investigated in
the oxidation of alkenes to carboxylic acids and cyanosilylation of aldehydes.
MIL‐101 was treated with Fe O and the prepared catalyst was characterized
Division, University of Isfahan, Isfahan,
81746‐73441, Iran
3
4
Correspondence
Shahram Tangestaninejad, Majid
Moghadam and Valiollah Mirkhani,
Department of Chemistry, Catalysis
Division, University of Isfahan, Isfahan
using Fourier transform infrared spectroscopy, X‐ray diffraction, N adsorption
2
measurements, field emission scanning electron microscopy, energy‐dispersive
X‐ray spectroscopy and inductively coupled plasma analysis. The catalytic
3+
81746‐73441, Iran.
active sites in this heterogeneous catalyst are Cr nodes of the MIL‐101
framework. This heterogeneous catalyst has the advantages of excellent yields,
short reaction times and reusability several times without significant decrease
in its initial activity and stability in both oxidation and cyanosilylation reactions.
Its magnetic property allows its easy separation using an external magnetic field.
Email: stanges@sci.ui.ac.ir;
moghadamm@sci.ui.ac.ir; mirkhani@sci.
ui.ac.ir
KEYWORDS
cyanosilylation, magnetization, metal–organic frameworks, MIL‐101, oxidation
1
| INTRODUCTION
hierarchical pore structure, mesoporous cages, numerous
unsaturated chromium(III) sites and high hydrothermal
Metal–organic frameworks (MOFs) are a new class of
hybrid materials that possesses crystalline lattices
consisting of metal ions coordinated by organic ligands.
These porous solids have high surface area, good thermal
and chemical stability which make it a promising material
for a wide range of applications. Especially, the pores of
MIL‐101 and chromium nodes lead to specific catalytic
applications such as in the production of carboxylic acids
[1–3]
[21]
stability and modifiable pores and tunnels.
and ketones by catalytic oxidation of alkenes,
[
22]
These materials have received much attention because
of their unique characteristics which make them an ideal
class of materials for various applications in analytical
cyanosilylation of aldehydes,
tetralin,
benzylic oxidation of
[
23,24]
[25]
sulfoxidation of thioethers with H O
2 2
and allylic oxidation of alkenes with tert‐butyl
[
4]
[5]
[26]
chemistry, gas adsorption and separation processes,
hydroperoxide.
[6–13]
[14]
heterogeneous catalysis,
delivery systems
optoelectronics,
drug
Catalyst recovery and reuse are very important fea-
tures in many catalytic processes. Nowadays, magnetic
nanoparticles (MNPs) have received much attention in
catalytic systems because they provide much easier and
faster separation of a catalyst from reaction media using
an external magnetic field instead of performing tedious
[15,16]
[17–19]
and sensor technology.
In 2005 Férey et al. reported a porous chromium tere-
phthalate MOF, MIL‐101 (Cr X(H O) O(bdc) ; X = F,
3
2
2
3
OH; bdc
pores.
=
benzene‐1,4‐dicarboxylate), with large
[
20]
MIL‐101 has outstanding features including
Appl Organometal Chem. 2017;e3957.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
1 of 9
https://doi.org/10.1002/aoc.3957

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NOURIAN ET AL.
[
27,28]
centrifugation and filtration steps.
The use of MNPs
Fluka. FT‐IR spectra were obtained using potassium
−
1
for enhancing the separation of MOFs from reaction
media has been reported by various research groups.
bromide pellets in the range 400–4000 cm
with a
[
29–
JASCO 6300 spectrophotometer. Field emission scanning
electron microscopy (FE‐SEM) images were obtained
with a Hitachi S‐4700 instrument. X‐ray diffraction
(XRD) patterns were recorded using a Bruker D8
Advance X‐ray diffractometer equipped with nickel
monochromatized Cu Kα radiation (λ = 1.5406 Å).
Specific surface area was determined using N2 gas
adsorption–desorption measurements at 77 K with a
Micromeritics ASAP 2000 instrument. Inductively
coupled plasma (ICP) analyses were carried out with a
PerkinElmer Optima 7300 DV spectrometer. GC ex-
periments were performed with a Shimadzu GC‐16A
instrument using a 2 m column packed with silicon
DC‐200 or Carbowax 20 M. In the GC experiments,
n‐decane was used as the internal standard. The
MNPs (Fe O ) were synthesized and coated with silica
33]
Magnetite (Fe O ) is one of the main representatives
3
4
of MNPs that is synthesized using three different path-
ways: physical, wet chemical and microbial methods.
Also, the use of surface coating materials during the syn-
thesis of MNPs stabilizes the newly formed surfaces and
prevents aggregation of the particles.
on the outside surface of Fe O MNPs can be effective in
[34–36]
A silica coating
3
4
preventing the magnetite particles from aggregation, oxi-
dation, corrosion, chemical degradation and leaching
[37,38]
under harsh conditions.
Zhang et al. reported a facile method for the synthesis
of MIL‐100(Fe) at low temperatures and atmospheric
pressure from the reaction of trimesic acid and ferric
[39]
nitrate under HF‐free conditions.
The synthesized
MIL‐100(Fe) was utilized as a catalyst in the liquid‐phase
acetalization of various aldehydes with diols. Recently Hu
et al. synthesized a magnetic MIL‐100(Fe)@SiO @Fe O
catalyst with a novel core–shell structure via a facile in
situ self‐assembly method and applied it in the liquid‐
3
4
[
42]
as reported in the literature.
MIL‐101 was syn-
thesized according to the procedure reported
2
3 4
[
20,43]
previously.
[40]
phase acetalization of benzaldehyde and glycol.
In this paper, we report the preparation of magneti-
2
.2 | Magnetization of MIL‐101 (Fe O –
cally recoverable MIL‐101 (Fe O @SiO –MIL‐101) by
3 4
3
4
2
SiO @MIL‐101)
mixing silica‐coated iron nanoparticles and MIL‐101
2
under sonication using a slight modification of the method
Fe O –SiO @MIL‐101 was prepared according to the
3
4
2
[41]
reported by Huo and Yan. The resulting heterogeneous
catalyst was characterized using various methods. The
catalytic activity of this hybrid material was investigated
in the direct oxidation of alkenes to carboxylic acids in
the presence of H O and cyanosilylation of aldehydes in
[41]
method of Huo and Yan
with some modification.
MIL‐101 (60 mg) and Fe O –SiO (100 mg) were placed
3
4
2
in a 25 ml glass vial, and dispersed in methanol under
ultrasonic irradiation for 1.5 to form Fe O –
h
3
4
2
2
SiO @MIL‐101. The magnetic MIL‐101 was separated
2
the presence of trimethylsilylcyanide (Scheme 1).
using an external magnet from methanol and dried over-
night in an oven at 75 °C.
2
2
| EXPERIMENTAL
2
2
.3 | Catalytic experiments
.1 | Reagents and methods
.3.1 | General procedure for direct oxida-
All materials were of commercial reagent grade. The
alkenes and aldehydes were obtained from Merck or
tion of alkenes to carboxylic acids catalysed
by Fe O –SiO @MIL‐101
3
4
2
Alkene (0.5 mmol), Fe O @SiO –MIL‐101 (20 mg),
3
4
2
H O (30%, 500 μl, 5 mmol) and CH CN (3 ml) were
2
2
3
mixed in a 25 ml round‐bottom flask and refluxed.
The progress of the reaction was monitored by GC. At
the end of the reaction, the catalyst was separated using
an external magnet and washed with CH CN (10 ml).
3
The solvent was evaporated and the pure products were
obtained by chromatography using a short silica gel
1
column. All the products were characterized using H
2 2
SCHEME 1 Oxidation of alkenes with H O and cyanosilylation
of aldehydes with trimethylsilylcyanide catalysed by Fe
3
O
4
@SiO
2
–
NMR, FT‐IR and mass spectral analyses (supporting
MIL‐101
information).

NOURIAN ET AL.
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2
.3.2 | General procedure for
cyanosilylation of aldehydes catalysed by
Fe O –SiO @MIL‐101
3
4
2
Aldehyde (1 mmol), trimethylsilylcyanide (TMSCN;
1
0
98.5 mg, 2 mmol) and Fe O –SiO @MIL‐101 (20 mg,
.0053 mmol) were mixed in heptane (5 ml). The reaction
3
4
2
mixture was stirred at room temperature and the progress
of the reaction was monitored by GC. Purification of the
products was as described above. The products were char-
1
13
acterized using H NMR, FT‐IR and C NMR spectral
analyses (supporting information).
2.4 | Recycling tests
The oxidation of cyclooctene was chosen as a model sub-
strate for investigating the reusability of Fe O –
3
4
SiO @MIL‐101. After each run the catalyst was separated
2
FIGURE 1 XRD patterns of: (a) MIL‐101, (b) Fe
Fe –SiO @MIL‐101 and (d) recovered catalyst
3 4 2
O @SiO , (c)
from the reaction mixture, washed with acetonitrile and
dried before being used in the next run. The same proce-
dure was repeated for other runs. After the reaction was
completed, the catalyst was filtered and the filtrate was
3
O
4
2
dissolved in strong acidic solution (HNO –HCl, 1:3).
3
Then, the amount of Cr leached was determined using
ICP analysis.
The reusability of the catalyst was also investigated in
the cyanosilylation of benzaldehyde using the same proce-
dure. After each run, the catalyst was separated easily
using an external magnet, washed with heptane and dried
before being used in subsequent runs.
3
3
| RESULTS AND DISCUSSION
.1 | Characterization of Fe O –
3
4
SiO @MIL‐101 catalyst
2
The XRD pattern (Figure 1a) and FT‐IR spectrum
(
Figure 2b) of synthesized MIL‐101 match well with those
[20,44]
reported previously.
The main diffraction peaks at 2θ
(
°) = 5.1, 8.4, 9.0, 16.5 were as same as the standard data
[20,45]
for MIL‐101.
As it is obvious from Figure 1c that
FIGURE 2 FT‐IR spectra of (a) Fe
3 4 2
O –SiO , (b) MIL‐101, (c)
Fe –SiO @MIL‐101 and (d) recovered catalyst
3
O
4
2
the crystallinity of MIL‐101 is maintained after magneti-
zation with Fe O –SiO . The additional peak in Figure 1
3
4
2
(
c) corresponds to Fe O –SiO as shown in Figure 1(b).
3
4
2
−
1
−1
−1
According to these patterns, the synthesis of Fe O –
SiO @MIL‐101 was successful.
As shown in Figure 2(c), the structure of the frame-
work is preserved after magnetization and the characteris-
tic vibrational bands of the framework ─(O─C─O)─
580 cm (Fe─O), 950 cm (Si─OH) and 1091 cm
(Si─O─Si), added to the MIL‐101 spectrum (Figure 2b)
after magnetization, which prove the synthesis of
3
4
2
Fe
O
–SiO
The FE‐SEM images in Figure 3 show that MIL‐
101 retains its nature and is not altered during
modification and magnetization. Also, Fe @SiO
MNPs were found to be homogeneously assembled
@MIL‐101.
3
4
2
−
1
groups around 1550 and 1400 cm
confirm this
[46,47]
point
708 and 1628 cm . Also, the FT‐IR spectrum of
Fe O –SiO (Figure 2a) exhibits characteristic bands at
and the catalyst C═O vibrations appear at
3
O
4
2
−
1
1
[
41,48]
onto the external surface of MIL‐101 crystals.
3
4
2

4
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NOURIAN ET AL.
The energy dispersive X‐ray (EDX) results, obtained
from SEM analysis, for the magnetic MIL‐101 in
Figure 4 clearly show the presence of Fe, Si and Cr in
Fe O –SiO @MIL‐101.
3
4
2
The specific surface area and pore volume of MIL‐101
and Fe O –SiO @MIL‐101 were determined using
3
4
2
nitrogen physisorption measurements at low temperature.
There is a predictable decrease in pore volume from 1.35
3
−1
to 0.602 cm g . The BET surface area decreased from
2
−1
2
729 to 886 m g (Figure 5).
FIGURE 3 FE‐SEM images of (a) MIL‐101 and (b) Fe
3 4
O –
SiO @MIL‐101
2
FIGURE 5
and (b) Fe
circles, desorption)
N
2
adsorption–desorption isotherms of (a) MIL‐101
3
O
4
–SiO @MIL‐101 (open circles, adsorption; filled
2
3 4 2
FIGURE 4 SEM–EDX spectrum of Fe O –SiO @MIL‐101

NOURIAN ET AL.
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The magnetization curves of Fe O , Fe O –SiO and
TABLE 1 Effect of Fe
cyclooctene at 70°C
3
O
4
–SiO
2
@MIL‐101 amount on oxidation of
3
4
3
4
2
a
Fe O –SiO @MIL‐101 are shown in Figure 6. The
3
4
2
−
1
saturation magnetization value of 10 emu g for Fe O –
b
3
4
Entry
Amount of catalyst (mg)
Yield (%) after 4 h
SiO @MIL‐101 makes it susceptible to magnetic fields
and easy to isolate from reaction media.
2
1
Without catalyst
0
2
3
4
5
6
Fe
10
20
25
30
3
O
4
–SiO
2
15
80
95
95
95
3.2 | Catalytic experiments
The catalytic activity of the Fe O –SiO @MIL‐101 was
3
4
2
evaluated in both the oxidation of alkenes with H O2
2
and cyanosilylation of aldehydes with TMSCN.
a
Reaction conditions: cyclooctene (0.5 mmol), H
3 ml).
2 2
O (5 mmol), acetonitrile
(
b
3
.2.1 | Catalytic activity of Fe O –
GC yield based on starting alkene.
3
4
SiO @MIL‐101 in direct oxidation of
alkenes to carboxylic acids
2
TABLE 2 Optimization of H
cyclooctene catalysed by Fe –SiO @MIL‐101 at 70°C
2 2
O amount in oxidation of
At first, the effect of amount of catalyst on the oxida-
tion of cyclooctene was investigated using various
amounts of Fe O –SiO @MIL‐101 in acetonitrile under
reflux condition. As evident from Table 1, the best
result was obtained with 20 mg (0.0053 mmol) of the
catalyst; no corresponding diacid was obtained in the
absence of the catalyst. It is noteworthy that in the
presence of Fe O –SiO a yield of only 15% of suberic
a
3
O
4
2
b
Entry
H
2
O
2
(mmol)
Yield (%) after 4 h
3
4
2
1
4
90
2
3
5
95
95
10
a
Reaction conditions: cyclooctene (0.5 mmol), catalyst (20 mg), acetonitrile
3 ml).
3
4
2
(
acid was obtained.
b
GC yield based on starting alkene.
The effect of amount of oxidant (H O ) on the
2
2
oxidation of cyclooctene catalysed by Fe O –SiO @MIL‐
3
4
2
The kind of solvent was also optimized for this reac-
1
01 was investigated. The results, obtained under reflux
conditions, are summarized in Table 2 and show that
mmol of H O is the best amount.
tion. Among various solvents such as methanol, dichloro-
methane and 1,2‐dichloroethane, acetonitrile was selected
as best solvent (Table 3).
5
2
2
The optimized reaction parameters used for the
oxidation of cyclooctene were catalyst, oxidant and
substrate in a molar ratio of 0.0053:5:0.5. Under these
conditions, various alkenes were oxidized with H O
2
2
(
Table 4). In this catalytic system, cyclooctene was
cleaved readily under the reaction conditions and pro-
duced suberic acid in 95% yield. In the case of cyclo-
hexene, the major product was adipic acid (89%) and
cyclohexene oxide was obtained as a minor product
(
11%). Both adipic and suberic acids are industrially
TABLE 3 Effect of solvent on oxidation of cyclooctene catalysed
a
by Fe
3
O
4
–SiO
2
@MIL‐101 at 70°C
b
Entry
Solvent
Yield (%) after 4 h
1
CH
CH
CH
3
2
3
OH
Cl
CN
Cl
36
2
2
3
4
2
95
1
C
2
H
4
2
a
2 2
Reaction conditions: cyclooctene (0.5 mmol), catalyst (20 mg), H O
FIGURE 6 Magnetic hysteresis curves of (a) Fe
SiO and (c) Fe –SiO @MIL‐101
3
O
4
, (b) Fe
3
O
4
–
(5 mmol), solvent (3 ml).
b
2
3
O
4
2
GC yield based on starting alkene.

6
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NOURIAN ET AL.
TABLE 4 Oxidation of alkenes with H
2
O
2
catalysed by Fe
3
O
4
–
TABLE 6 Effect of TMSCN amount on cyanosilylation of benz-
a
a
SiO
2
@MIL‐101 refluxing in acetonitrile
aldehyde catalysed by Fe
3
O
4
–SiO
2
@MIL‐101 at room temperature
b
−1
b
Entry
Alkene
Yield (%)
Time (h)
TOF (h
)
Entry
TMSCN (mmol)
Yield (%) after 4 h
1
Cyclooctene
95
4
22.40
1
1
94
2
3
4
5
6
Cyclohexene
Indene
89
90
80
77
80
8
3
8
8
5
10.49
28.30
9.43
2
3
2
4
100
98
a
1‐Octene
Reaction conditions: aldehyde (1 mmol), catalyst (20 mg), n‐heptane (5 ml).
b
1‐Decene
1‐Dodecene
9.08
GC yield based on starting aldehyde.
15.09
Also, the effect of solvent was investigated in the
a
2 2
Reaction conditions: alkene (0.5 mmol), H O (5 mmol), catalyst (20 mg),
model reaction and it is clear that n‐heptane was the best
solvent (Table 7).
3
CH CN (3 ml).
b
GC yield based on starting alkene.
The optimized reaction parameters used for the
cyanosilylation of benzaldehyde were catalyst, TMSCN
and substrate in a molar ratio of 0.0053:2:1. Table 8 sum-
marizes the results obtained for cyanosilylation of various
aldehydes which were converted to their corresponding
cyanohydrin trimethylsilyl ethers. Using this catalytic sys-
tem, a variety of aromatic aldehydes such as benzalde-
hyde, 4‐methylbenzaldehyde, 2‐chlorobenzaldehyde,
very important. Linear alkenes, such as 1‐octene, 1‐
decene and 1‐dodecene, were easily converted into
their corresponding alkanoic acids in 77–80% yields
(
Table 4, entries 4–6). Also, indene (Table 4, entry 3)
was converted to 2‐(carboxymethyl)benzoic acid
homophthalic acid) in 90% yield.
(
2
,4‐dichlorobenzaldehyde,
nitrobenzaldehyde and 2‐nitrobenzaldehyde were easily
converted to their corresponding cyanohydrin
trimethylsilyl ethers in 75–100% yields (Table 8, entries
–7). Also, evident from Table 8, bulkier aromatic alde-
3‐nitrobenzaldehyde,
4‐
3
.2.2 | Catalytic activity of Fe O –
3
4
SiO @MIL‐101 in cyanosilylation of
aldehydes
2
1
As evident from Table 5, the effect of amount of catalyst
on the cyanosilylation of benzaldehyde was investigated
using various amounts of Fe O @SiO –MIL‐101 in
hyde (2‐naphthaldehyde) was converted to 2‐
trimethylsilyloxy‐2‐(2‐naphthyl)acetonitrile in 75% yield
3
4
2
(
entry 8).
n‐heptane at room temperature, the best result being
obtained with 20 mg (0.0053 mmol) of the catalyst. Also
a blank experiment in the absence of catalyst under the
same experimental conditions was carried out and the
corresponding product was obtained in a yield of only
3
.3 | Catalyst reuse and stability
For economical and synthetic purposes, the reusability of
a heterogeneous catalyst is very important. Thus, for com-
pletion of our study, the reusability of Fe O –SiO @MIL‐
5
%, while in the presence of Fe O –SiO the corresponding
3
4
2
3
4
2
silyl ether was produced in a yield of only 10%.
The effect of amount of TMSCN on the cyanosilylation
of benzaldehyde was also investigated. The results in
Table 6 show that 2 mmol of TMSCN was the optimum
amount.
101 was investigated in multiple sequential oxidation and
cyanosilylation reactions. The oxidation of cyclooctene
was chosen as a model substrate for investigating the
reusability of Fe O –SiO @MIL‐101. As evident from
Table 9, in the oxidation of cyclooctene the product yield
was 95% in the first run after 4 h. In the second, third and
fourth runs the product yield decreased to 92, 89 and 80%
3
4
2
TABLE 5 Effect of Fe
cyanosilylation of benzaldehyde at room temperature
3 4 2
O –SiO @MIL‐101 amount on
a
b
TABLE 7 Effect of solvent on cyanosilylation of benzaldehyde
Entry
Amount of catalyst (mg)
Yield (%) after 4 h
a
catalysed by Fe
3
O
4
–SiO
2
@MIL‐101 at room temperature
1
Without catalyst
5
b
Entry
Solvent
PhCH
n‐C
Yield (%) after 3 h
2
3
4
5
Fe
15
20
30
3
O
4
–SiO
2
(20)
10
93
1
3
17
2
3
6
H
14
35
28
100
100
3
CH CN
4
n‐C
7
H
16
100
a
Reaction conditions: aldehyde (1 mmol), TMSCN (2 mmol), n‐heptane
5 ml).
a
(
Reaction conditions: aldehyde (1 mmol), TMSCN (2 mmol), catalyst (20 mg).
b
b
GC yield based on starting aldehyde.
GC yield based on starting aldehyde.

NOURIAN ET AL.
7 of 9
a
TABLE 8 Cyanosilylation of aldehydes catalysed by Fe
3
O
4
–SiO
2
@MIL‐101 with TMSCN at room temperature
b
−1
Entry
Aldehyde
Yield (%)
Time (h)
TOF (h
)
1
Benzaldehyde
100
3
62.89
40.09
44.81
38.16
41.51
36.9
2
3
4
5
6
7
8
4‐Methylbenzaldehyde
2‐Chlorobenzaldehyde
2,4‐Dichlorobenzaldehyde
3‐Nitrobenzaldehyde
4‐Nitrobenzaldehyde
2‐Nitrobenzaldehyde
2‐Naphthaldehyde
85
95
91
88
88
75
75
4
4
4.5
4
4.5
5
28.3
7
20.22
a
2 2 3
Reaction conditions: alkene (0.5 mmol), H O (5 mmol), catalyst (20 mg), CH CN (3 ml).
b
GC yield based on starting alkene.
a
3 4 2
TABLE 9 Recyclability of Fe O –SiO @MIL‐101 in oxidation of cyclooctene
b
b
c
Yield (%) before
activation
Cr leached
(%)
Yield (%)
Cr leached
(%)
Fe leached (%)
(both steps)
c
c
Run
after activation
1
95
92
89
80
—
—
5.8
4.5
4.1
3.9
—
97
2.2
1.5
0.89
0
0
0
0
0
0
0
2
3
4
5
6
95
92
92
90
90
0
—
0
a
2 2 3
Reaction conditions: cyclooctene (0.5 mmol), H O (5 mmol), catalyst (20 mg), CH CN (3 ml).
b
GC yield based on starting alkene.
c
Determined by ICP analysis.
TABLE 10 Recyclability of Fe
cyanosilylation of benzaldehyde
3
a
O
4
–SiO
2
@MIL‐101 in
of the framework. To decrease the catalyst leaching,
microwave irradiation was used before recycling tests.
[49]
b
c
c
As evident from Table 9, after activation of the catalyst,
the leaching of Cr decreased and the product yield and
the catalyst reusability improved.
Run
Yield (%)
Cr leached (%)
Fe leached (%)
1
100
4.3
0
2
3
4
97
94
84
2.1
3.1
1.8
0
0
0
Also the recyclability of the catalyst was investigated
in the cyanosilylation of benzaldehyde. The results are
summarized in Table 10. At the end of the reaction, the
catalyst was separated easily using an external magnet,
washed with heptane and dried before using in subse-
quent runs. The amount of Cr leached in the four runs
is about 11.3% of the initial Cr content, which is in accor-
dance to the decreasing of the product yield from 100% in
the first run to 84% in the fourth run.
a
Reaction conditions: benzaldehyde (1 mmol), TMSCN (2 mmol), catalyst
20 mg), n‐heptane (5 ml).
(
b
GC yield based on starting alkene.
c
Determined by ICP analysis.
respectively. The amount of Cr leached to the reaction
mixture was measured using the ICP method.
As XRD analysis confirms that the catalyst maintains
its stability even after the last run, it seems that the
leached Cr is not the Cr which is positioned in the nodes
of the framework. So this leaching is likely due to remain-
ing Cr in the pores, which is not removed during washing
4 | CONCLUSIONS
We have successfully synthesized and characterized a
magnetically recoverable heterogeneous catalyst (Fe O –
3
4
SiO @MIL‐101). The catalytic activity of this new catalyst
2

8
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NOURIAN ET AL.
was evaluated in oxidation of alkenes to carboxylic acids
and cyanosilylation of aldehydes, and showed excellent
yields and noticeable reusability in both reactions. Easy
workup, mild reaction conditions and separation of the
catalyst using an external magnetic field are other unique
features of this catalyst.
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Shahram Tangestaninejad
263-9795
Majid Moghadam http://orcid.org/0000-0001-8984-1225
Iraj Mohammadpoor‐Baltork http://orcid.org/0000-0001-
998-5401
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How to cite this article: Nourian M,
Zadehahmadi F, Kardanpour R, et al. Highly
efficient oxidative cleavage of alkenes and
cyanosilylation of aldehydes catalysed by
magnetically recoverable MIL‐101. Appl
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