Oxidation of alkenes catalysed by molybdenum(VI)–oxodiperoxo complex anchored on the surface of magnetic nanoparticles under solvent-free conditions

Article abstract of DOI:10.1002/aoc.3611

A new epoxidation catalyst has been prepared by grafting a molybdenum(VI)–oxodiperoxo complex containing an oxazine ligand, [MoO(O₂)₂(phox)], on chloro-functionalized Fe₃O₄ nanoparticles. The synthesized heterogeneous catalyst (MoO(O₂)₂(phox)/Fe₃O₄ was characterized using powder X-ray diffraction, scanning and transmission electron microscopies, vibrating sample magnetometry, energy-dispersive X-ray analysis, Fourier transform infrared spectroscopy and inductively coupled plasma atomic emission spectroscopy. The immobilized complex gave high product yields and high selectivity for epoxide compared to the corresponding homogeneous one in the epoxidation of various olefins in the presence of tert-butyl hydroperoxide at 95°C without any co-solvent. Also, the heterogeneous catalyst can be recycled without a noticeable change in activity and selectivity.

Full text of DOI:10.1002/aoc.3611

Received: 27 April 2016
DOI 10.1002/aoc.3611
Revised: 2 August 2016
Accepted: 16 August 2016
F U L L PA P E R
Oxidation of alkenes catalysed by molybdenum(VI)–oxodiperoxo
complex anchored on the surface of magnetic nanoparticles under
solvent‐free conditions
1
Maryam Zare | Zeinab Moradi‐Shoeili2
*
1 Department of Basic Sciences, Golpayegan
A new epoxidation catalyst has been prepared by grafting a molybdenum(VI)–
oxodiperoxo complex containing an oxazine ligand, [MoO(O2)2(phox)], on chloro‐
functionalized Fe3O4 nanoparticles. The synthesized heterogeneous catalyst (MoO
(O2)2(phox)/Fe3O4 was characterized using powder X‐ray diffraction, scanning
and transmission electron microscopies, vibrating sample magnetometry, energy‐
dispersive X‐ray analysis, Fourier transform infrared spectroscopy and inductively
University of Technology, PO Box 8771765651,
Golpayegan, Iran
2 Department of Chemistry, Faculty of Sciences,
University of Guilan, PO Box 41335‐1914, Rasht,
Iran
Correspondence
Maryam Zare, Department of Basic Sciences,
Golpayegan University of Technology, PO Box
8771765651, Golpayegan, Iran.
Email: m_zare@gut.ac.ir
coupled plasma atomic emission spectroscopy. The immobilized complex gave high
product yields and high selectivity for epoxide compared to the corresponding
homogeneous one in the epoxidation of various olefins in the presence of tert‐butyl
hydroperoxide at 95°C without any co‐solvent. Also, the heterogeneous catalyst can
be recycled without a noticeable change in activity and selectivity.
KEYWORDS
epoxidation, heterogenization, molybdenum, nanoparticles, solvent‐free
1
|
INTRODUCTION
magnetic resonance imaging,[17] bioseparation,[18] drug
delivery,[19] immobilization of biomolecules,[20] etc.
Transition metal‐based homogeneous catalysts have shown
potential in performing selective catalytic transformations of
molecules.[1,2] Among them, molybdenum complexes are
able to promote catalytic reactions such as epoxidation of
olefins,[3,4] oxidation of saturated hydrocarbons[5] and oxida-
tion of sulfides.[6] However, homogeneous catalysts, whilst
very effective, are not recoverable and degrade in the reaction
media and therefore contaminate the products. Therefore,
attention is now being directed towards the heterogenization
of these complexes onto various solid supports such as
polymers,[7] boehmite nanoparticles,[8] mesoporous mate-
rials[9,10] and magnetic nanoparticles.[11]
Magnetic nanoparticles have attracted great interest for
immobilizing homogeneous transition metal catalysts since
they can be efficiently isolated from the product solution
through a simple magnetic separation process after comple-
tion of reactions.[12,13] The selective modification of the
external surface of magnetic nanoparticles by a wide variety
of chemical groups can give rise to materials presenting a
variety of potential applications such as catalysis,[14–16]
According to the importance of epoxides as building
blocks for the synthesis of a wide variety of fine chemicals,
e.g. epoxy resins, paints and surfactants, a number of
epoxidations based on homogeneous and heterogeneous
molybdenum complex catalysts with tert‐butyl hydropero-
xide (TBHP) have been reported.[21–26] Molybdenum
oxidoperoxido complexes are an important class of catalysts
for this type of reaction. Recent studies showed that these
complexes can be used both as an oxidation catalyst and as
a stoichiometric reactant. Due to high activity and selectivity
of oxidoperoxido molybdenum(VI) complexes, much effort
has been made to develop homogeneous or heterogeneous
catalysts based on these complexes. For instance, Schurig
and co‐workers found the oxido‐bisperoxido Mo(VI) com-
plex containing
a (S)‐N,N‐dimethyl lactamide ligand
catalysed the epoxidation of olefins in nitromethane solvent
at room temperature.[21] Monoperoxido complexes of the
general formula MoO(O2)L2Cl2 (L = DMF, HMPT) and
MoO(O2)Cl(O‐N)(HMPT) (O‐N = Pic, Quin) were reported
as catalysts in epoxidation of alkenes.[22] Thiel et al.
Appl. Organometal. Chem. 2016; 1–7
wileyonlinelibrary.com/journal/aoc
Copyright © 2016 John Wiley & Sons, Ltd.
1

2
ZARE AND MORADI‐SHOEILI
synthesized oxido‐bisperoxido molybdenum complexes
containing bidentate ligands. The catalytic activity of these
catalysts was evaluated for the cyclooctene epoxidation
reaction in presence of TBHP as an oxidant and CHCl3 as a
solvent at 65°C for 3 h.[23]. Oxodiperoxo molybdenum
complexes of the type (L–L)MoO(O)2 with bidentate
2‐(1‐alkyl‐3‐pyrazolyl)pyridine ligands were grafted on
MCM‐41 and used as catalysts for the oxidation of
cyclooctene with TBHP in refluxing chloroform.[24,25]
The oxidoperoxido molybdenum(VI) moiety was also
immobilized on polystyrene crossed‐linked with 5%
divinylbenzene through the chelating ligands 2‐(2‐pyridyl)
benzimidazole and 2‐(3‐pyridyl)benzimidazole. They were
applied as catalysts in the oxidation of styrene using H2O2
as an oxidant in refluxing acetonitrile.[26] Epoxidation of
olefins is mostly performed in an organic solvent. According
to the increasing demand for cleaner and environmentally
friendlier processes, attention has been drawn to the design
and development of new oxidation catalysts which can elim-
inate the need for volatile organic solvents in chemical
manufacturing processes. For this purpose, we have prepared
a new catalytic system and evaluated its catalytic activity for
epoxidation reaction using TBHP under solvent‐free
conditions.
In the work presented here, the molybdenum(VI)–
oxodiperoxo complex [MoO(O2)2(phox)] (Hphox =2‐(2′‐
hydroxyphenyl)‐5,6‐dihydro‐1,3‐oxazine), previously syn-
thesized by Amini et al.,[27] was grafted on Fe3O4
nanoparticles modified with 3‐chloropropyltrimethoxysilane.
The catalytic behaviour of the epoxidation of alkenes over the
heterogeneous catalyst was compared with the homogeneous
counterpart under solvent‐free experimental conditions. The
heterogenized catalyst shows an activity comparable to that
of the corresponding homogeneous one. The heterogeneous
catalyst is easily recovered and reused nine times before a
decrease is observed in both activity and selectivity.
spectrophotometer. Scanning electron microscopy (SEM)
images were obtained with a KYKY‐EM3200 scanning
electron microscope. Transmission electron microscopy
(TEM) analysis was carried out using a JEOL‐2010 micro-
scope operating at 200 kV. Vibrating sample magnetometry
(VSM) was used to measure the magnetic properties of the
samples at room temperature, whereby Ni was used as
standard. Elemental analysis was conducted with an
energy‐dispersive X‐ray (EDX) analyser (KEVEX Delta
series) mounted on a Hitachi S‐800. GC analyses were
performed with an Agilent Technologies 6890 N, equipped
with a 19019 J‐413 HP‐5, 5% phenyl methyl siloxane and
a capillary column (60.0 m × 250 μm × 1.00 μm).
2.2 | Fe3O4 magnetic nanoparticles
Magnetic nanoparticles of Fe3O4 were prepared as reported
previously.[28] Typically, FeCl2⋅4H2O (3.17 g, 16 mmol)
and FeCl3⋅6H2O (7.57 g, 28 mmol) were dissolved in
300 ml of degassed water. The solution was stirred vigo-
rously under nitrogen atmosphere at 80°C for 1 h. Then,
40 ml of NH3⋅H2O was rapidly added into the mixture. The
reaction system turned black quickly. After continuous
stirring by a mechanical stirrer for another 1 h under nitrogen,
the product was separated using a 1.2 T magnet and washed
several times with hot water. The magnetic nanoparticles
were dried at 80°C.
2.3 | Chloropropyltrimethoxysilane‐coated magnetite
nanoparticles (SiCl/Fe3O4)
Fe3O4 (2 g) was added to 100 ml of ethanol and the pH of
the solution was adjusted to 10 by the addition of 25%
ammonium hydroxide solution (2 ml). The mixture was son-
icated for 30 min to achieve a uniform dispersion. After-
wards, 3‐chloropropyltriethoxysilane (5 ml) was added
dropwise over a period of 10 min, and the reaction mixture
was stirred at 50°C for 48 h. The particles were washed
several times with ethanol and magnetically separated to
remove any excess reagent and salts. The final product was
dried at 70°C for 8 h.
2
| EXPERIMENTAL
2.1 | Materials and methods
2.4 | Immobilization of MoO(O2)2(phox) on the surface
of magnetic nanoparticles (MoO(O2)2(phox)/Fe3O4)
Starting reagents were purchased from Merck or Aldrich.
All solvents were of reagent grade and dried and distilled
before use according to standard procedures. MoO(O2)2
(phox) was synthesized according to a published proce-
dure.[27] Powder X‐ray diffraction (XRD) data were
collected with a Philips X'Pert MPD diffractometer (Cu
Kα X‐radiation, λ = 1.54056 Å). The metal loading of the
host materials and leaching of molybdenum into the solution
were determined using inductively coupled plasma atomic
emission spectroscopy (ICP‐AES) with a PerkinElmer
AA‐300 spectrophotometer. Fourier transform infrared
(FT‐IR) spectra of samples in the form of KBr pellets were
recorded using an ABB Bomem MB‐100 FT‐IR
To a solution of MoO(O2)2(phox) in methanol (100 ml) was
added 1 g of SiCl/Fe3O4 and the mixture was vigorously
stirred at 50°C for 72 h. At the end of the reaction, the
mixture was cooled to room temperature; the solid material
was magnetically separated, washed with methanol and then
dried at 60°C for 48 h.
2.5 | Catalytic reactions
To a solution of alkene (1 mmol), MoO(O2)2(phox)/Fe3O4 or
MoO(O2)2(phox) (0.0005 mmol Mo complex) and

ZARE AND MORADI‐SHOEILI
3
SCHEME 1 Synthesis of MoO(O2)2(phox)/Fe3O4.
chlorobenzene (1 mmol) as internal standard was added
1 mmol of TBHP as oxidant. The system was stirred for
20–60 min at 95°C. The progress of the reaction was moni-
tored using GC. All reactions were performed at least two
times and the products were compared with standard
samples.
2.6 | Catalyst recycling
In a typical procedure, the MoO(O2)2(phox)/Fe3O4 catalyst
was magnetically separated after each cycle, washed with
methanol and dried at 50°C. Then, the recovered catalyst
was added to fresh substrates under similar conditions to
those of the first cycle.
3
| RESULTS AND DISCUSSION
The supported material MoO(O2)2(phox)/Fe3O4 was pre-
pared by immobilization of the complex on the surface of
magnetic nanoparticles containing chloropropyl groups,
FIGURE 1 FT‐IR spectra of (a) [MoO(O2)2(phox)], (b) MoO(O2)2(phox)/
Fe3O4 and (c) Fe3O4 nanoparticles.
FIGURE 3 EDX analysis of MoO(O2)2(phox)/Fe3O4.
FIGURE
4
SEM images of Fe3O4 and MoO(O2)2(phox)/Fe3O4
FIGURE 2 XRD patterns of Fe3O4 and MoO(O2)2(phox)/Fe3O4.
nanoparticles.

4
ZARE AND MORADI‐SHOEILI
through covalent bonding between chloropropyl group and
oxazine ring nitrogen atom of the ligand (Scheme 1).
The successful synthesis of the supported catalyst was
confirmed using FT‐IR spectroscopy. The FT‐IR spectra of
Fe3O4 nanoparticles and MoO(O2)2(phox)/Fe3O4 were
recorded between 400 and 4000 cm−1 as shown in
Figure 1. The spectrum of Fe3O4 shows absorption bands
at 587, 1635 and 3474 cm−1 which are related to the
stretching of Fe─O, the O─H bending vibration of absorbed
water and the stretching vibration of O─H bonds, respec-
tively.[29] The absorption band observed at 1097 cm−1 in
the spectrum of MoO(O2)2(phox)/Fe3O4 is assigned to
Si─O─Si stretching.[30] In spectrum of MoO(O2)2(phox)/
Fe3O4, the characteristic bands due to the stretching vibra-
tion of Mo═O and O─O groups are observed at 966 and
860 cm−1, respectively,[27] confirming the immobilization
of the complex on the surface of the nanoparticles. The band
at 1635 cm−1 appearing in the spectrum of MoO(O2)2
(phox)/Fe3O4 nanoparticles is mainly related to the overlap
of C═N stretching (from the ligand group) and O─H bend-
ing of adsorbed water. Bands in the region 1280–1635 cm−1
are mainly due to the vibrational frequencies of the
complex.[27]
FIGURE 5 TEM images of MoO(O2)2(phox)/Fe3O4 nanoparticles.
The powder XRD pattern of the magnetite sample in
Figure
2
clearly shows six diffraction peaks at
2θ = 30.1°, 35.5°, 43.2°, 53.5°, 57.8° and 62.8°, corre-
sponding to (220), (311), (400), (422), (551) and (440)
diffraction planes of Fe3O4 magnetic nanoparticles, respec-
tively, which are in good agreement with the standard data
(44–1485 IC DD; JCPDS).[31] The XRD pattern of the
catalyst demonstrates that almost no change occurs upon
immobilization of the complex on the surface of the
magnetic nanoparticles.
EDX analysis of MoO(O2)2(phox)/Fe3O4 (Figure 3)
proves the presence of N, C and Mo, which confirms the
successful anchoring of the molybdenum complex on the
surface of the magnetic nanoparticles. It is found from EDX
analysis that 4.21 wt% (0.044 mol%) of the molybdenum is
FIGURE 6 VSM magnetization curves of Fe3O4 and MoO(O2)2(phox)/
Fe3O4.
TABLE 1 Screening of reaction conditions for the oxidation of cyclooctenea
Entry
Catalyst
MoO5Lb
Amount of catalyst (mmol)
Solvent
Temperature (°C)
Conversion (%)
1
—
C2H4Cl2
C2H4Cl2
—
95
95
24
21
2
MoO5L
—
3
MoO5L
0.005
0.005
0.005
0.005
0.001
0.0005
0.0002
0.0005
0.0005
0.0005
0.0005
0.0002
0.005
0.005
80
45
4
MoO5L
—
85
69
5
MoO5L
—
90
89
6
MoO5L
—
95
>99
>99
97
7
MoO5L
—
95
8
MoO5L
—
95
9
MoO5L
—
95
91
10
11
12
13
14
15
16
MoO5L
C2H4Cl2
CH2Cl2
—
95
98
MoO5L
Reflux
95
43
c
MoO5L/Fe3O4
MoO5L/Fe3O4
MoO5L/Fe3O4
MoO5L/Fe3O4
MoO5L/Fe3O4
100
99
C2H4Cl2
—
95
95
93
—
90
91
—
85
70
aReaction conditions: 1 mmol cyclooctene, 1 mmol TBHP. The reactions were run for 20 min.
bCatalyst: MoO(O2)2(phox).
cCatalyst: MoO(O2)2(phox)/Fe3O4.

ZARE AND MORADI‐SHOEILI
5
a
TABLE 2 Oxidation of various alkenes with TBHP catalysed by MoO(O2)2(phox) and MoO(O2)2(phox)/Fe3O4
Conversion (%)
MoO5L/Fe3O4
Time (min)
Selectivity (%)
MoO5L/Fe3O4
c
Entry
Substrate
MoO5Lb
MoO5L
MoO5L/Fe3O4
MoO5L
1
2
3
4
5
6
7
Cyclohexene
Cyclooctene
Styrene
100
97
83
89
74
77
70
100
100
90
20
20
20
20
20
20
20
20
20
60
20
20
60
60
83
100
24d
41
87
100
38d
43
α‐Methylstyrene
4‐Methylstyrene
1‐Heptene
75
64
53
25
71
86
88
1‐Octene
60
83
82
aReaction conditions: molar ratio for catalyst:alkene:TBHP is 1:2000:2000. The reactions were run at 95°C without co‐solvent.
bMoO(O2)2(phox).
cMoO(O2)2(phox)/Fe3O4.
dSelectivity of benzaldehyde was 70 and 57% for MoO5L and MoO5L/Fe3O4, respectively.
grafted on the surface of the magnetic nanoparticles. This
value is close to the molybdenum content of 4.32 wt%
(0.045 mol%) determined from ICP‐AES analysis.
The morphology and structure of the synthesized mate-
rials were examined using SEM (Figure 4). It can be seen that
the samples consist of monodispersed particles with spherical
morphology.[32]
and 1 mmol of cyclooctene, at 95°C and under solvent‐free
conditions. The turnover frequency of both homogeneous
and heterogeneous systems with a 1:2000:2000 catalyst:sub-
strate:oxidant ratio is about 6000 h−1 after 20 min. Then, the
catalytic activity of MoO(O2)2(phox) and MoO(O2)2(phox)/
Fe3O4 was further explored for the epoxidation of six other
olefins under optimized conditions.
TEM images of the prepared catalyst are shown in
Figure 5. As seen, each single‐phase primary particle is
spherical in shape with an average diameter of about
7–10 nm,[11] which is in good agreement with the average
crystallite size obtained using the Scherrer formula with the
full width at half maximum of the (311) diffraction peak.
Figure 6 shows plots of magnetization versus applied
magnetic field (hysteresis loops) of Fe3O4 nanoparticles and
MoO(O2)2(phox)/Fe3O4 measured using VSM at room
temperature in an applied magnetic field sweeping from −10
to 10 kOe. As shown in Figure 6, no hysteresis is observed
in the magnetization curves of the two materials, and the coer-
civity and remanence are nearly zero, exhibiting typical
superparamagnetic behaviour at room temperature.[33] The
saturation magnetizations for the Fe3O4 nanoparticles and
MoO(O2)2(phox)/Fe3O4 are 61.0 and 54.6 emu g−1, respec-
tively. Compared with the Fe3O4 nanoparticles, the decrease
in the saturation magnetization of MoO(O2)2(phox)/Fe3O4 is
due to the modification of the surface of the magnetic sup-
ports with chloropropyltrimethoxysilane and the anchored
MoO(O2)2(phox) complex.
SCHEME 2 Proposed mechanism for oxidation of styrene.
3.1 | Catalysis
To test the catalytic activity of the homogeneous and hetero-
geneous molybdenum complexes, we chose to examine the
oxidation of cyclooctene, used as a model substrate, with
TBHP as the oxygen donor for the survey of the reaction
parameters such as temperature, solvent and catalyst loading
(Table 1). The yield of cyclooctene increases with increasing
reaction temperature up to 95°C. The best results aere
obtained using 0.0005 mmol of catalyst, 1 mmol of TBHP
SCHEME 3 Proposed mechanism for oxidation of olefins with MoO(O2)2
(phox)/Fe3O4 in the presence of TBHP.

6
ZARE AND MORADI‐SHOEILI
TABLE 3 Reuse of MoO(O2)2(phox)/Fe3O4 in the selective oxidation of cyclooctenea
Run
1
2
3
4
5
6
7
8
9
Conversion (%)
Selectivity (%)
100
100
100
100
100
100
100
100
98
98
96
96
94
100
100
100
100
100
aReaction conditions: 0.0005 mmol catalyst, 1 mmol TBHP, 1 mmol cyclooctene. The reactions were run at 95°C for 20 min.
TABLE 4 Comparison of results obtained for oxidation of cyclooctene catalysed by MoO(O2)2(phox)/Fe3O4 with some of those reported in the literature
Entry
Catalyst
Molar ratio cat:sub:ox
Solvent
Time
Conversion (%)
Selectivity (%)
Ref.
1
2
3
4
5
6
MoO(O2)2(phox)/Fe3O4
MOO2sal/SBA‐15
1:2000:2000
1:588:588
1:100:120
1:100:154
1:147:155
1:156:311
Without co‐solvent
C2H4Cl2
20 min
1 h
100
95
100
98
This work
[38]
[11]
[39]
[40]
[8]
[(L–L)MoO(O2)2]/Fe3O4
PMO‐phMo(CO)3
CHCl3
6 h
96
100
100
100
96
Without co‐solvent
CHCl3
30 min
1.35 h
2 h
100
66
[(L–L)MoO(O2)2]/MCM‐41
Mo‐IFBNPs
CCl4
96
As evident from Table 2, excellent yields and selectiv-
ity towards epoxide are observed for cyclooctene and
cyclohexene. Also, the homogeneous and heterogeneous
complexes convert the aliphatic terminal alkenes to the
corresponding epoxides with good yield and high
selectivity in desired times. The reactions of styrene and
its derivatives are not selective to the corresponding
epoxide under the applied reaction conditions, giving a
wide spectrum of products including benzaldehyde
from styrene, acetophenone from methylstyrene and
4‐methylbenzaldehyde from 4‐methylstyrene. The high yield
of these products is obtained possibly due to further
oxidation of epoxide species which are formed in the first
step of the reaction[34–36] (Scheme 2).
A mechanism in which an eight‐coordinate species is
present as a responsible intermediate is suggested similar to
the mechanism proposed by Thiel. The epoxide product is
obtained by transfer of the oxygen atom of the ─OOR ligand,
which binds to the molybdenum centre, to the C═C double
bond. At the final stage, the release of a tert‐butanol molecule
from the metal centre leads to the formation of MoO(O2)2
(phox) (Scheme 3).[37]
The reusability of MoO(O2)2(phox)/Fe3O4 was also tested
in cyclooctene oxidation under reflux employing 1 mmol of
TBHP and 1 mmol of the substrate (Table 3). The catalyst
was separated using an external magnet after each cycle,
washed with methanol and dried at 50°C, and then redispersed
into a fresh reaction mixture. The yield and selectivity are
maintained at similar levels even after nine cycles. Also, anal-
ysis of the reaction media after each cycle using ICP‐AES
shows no molybdenum species detected in the filtrates. More-
over, after the catalyst was removed at about 40% conversion
of cyclooctene, no further reaction was detected in the filtrate
after 1 h. These results confirm that MoO(O2)2(phox)/Fe3O4
acts as a true heterogeneous catalyst.
and selectivity of our novel system are high in epoxidation
while no co‐solvent is used (Table 4).
4
| CONCLUSIONS
A new heterogeneous catalyst system was synthesized by
covalently anchoring a molybdenum(VI)–oxodiperoxo com-
plex containing an oxazine ligand onto the surface of Fe3O4
nanoparticles and was characterized using various tech-
niques. Both the homogeneous and also the corresponding
immobilized catalyst showed excellent catalytic capabilities
in the epoxidation of alkenes under solvent‐free conditions.
The catalytic systems presented showed high selectivity for
epoxide in the epoxidation of all examined olefinic
substrates with the exception of styrene and its derivatives.
In addition, the heterogenized catalyst could be easily
separated from the reaction mixture using an external
magnet and reused for up to nine successive cycles without
any significant decrease in catalytic activity and selectivity.
ACKNOWLEDGEMENTS
The authors are grateful to the Golpayegan University of
Technology and the University of Guilan. The authors thank
Dr Saim Ozkar of the Turkish Academy of Sciences for help
in the preparation of TEM images.
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How to cite this article: Zare, M., and Moradi‐
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