Synthesis and characterization of a Mn-Schiff base complex anchored on modified MCM-41 as a novel and recyclable catalyst for oxidation of olefins

Article abstract of DOI:10.1002/aoc.4593

Mn-Schiff base complex has been covalently attached to the surface of Mobil Composite Material No. 41 (MCM-41) using a 1,4-diisocyanatobutane (DIC-4) as a binder. The prepared heterogeneous catalyst was characterized by X-ray diffraction pattern (XRD), Brunauer–Emmett–Teller (BET), Fourier transform infrared (FT-IR) spectroscopy, X-ray fluorescence analysis (XRF), inductively coupled plasma (ICP) spectrometry and Transmission Electron Microscopy (TEM). The BET results indicated that the surface area and pore size of MCM-41 were decreased after modification. The obtained catalyst was used as a highly efficient, heterogeneous and recyclable catalyst for the oxidation of a wide range of alkenes with hydrogen peroxide (H₂O₂) as a green oxidant. The effect of various parameters such as catalyst and imidazole (co-catalyst) concentration, tempreture, and reaction time on the conversion effecincy and selectivity of the reaction have been studied. The catalyst was used in five consecutive experiment without any loss of activity, confirming the success of the anchoring process and the catalyst stability.

Full text of DOI:10.1002/aoc.4593

Received: 30 June 2018
DOI: 10.1002/aoc.4593
Revised: 15 August 2018
Accepted: 17 August 2018
C O M M U N I C A T I O N
Synthesis and characterization of a Mn‐Schiff base complex
anchored on modified MCM‐41 as a novel and recyclable
catalyst for oxidation of olefins
Hassan Zakeri1 | Saeed Rayati2
| Goldasteh Zarei1
1 Department of Chemistry, College of
Science, Yadegar‐e‐Imam Khomeini
(RAH), Shahre Rey Branch, Islamic Azad
University, Tehran, Iran
2 Department of Chemistry, K.N. Toosi
University of Technology, Tehran, PO Box
16315‐1618, Tehran 15418, Iran
Mn‐Schiff base complex has been covalently attached to the surface of Mobil
Composite Material No. 41 (MCM‐41) using a 1,4‐diisocyanatobutane (DIC‐4)
as a binder. The prepared heterogeneous catalyst was characterized by X‐ray
diffraction pattern (XRD), Brunauer–Emmett–Teller (BET), Fourier transform
infrared (FT‐IR) spectroscopy, X‐ray fluorescence analysis (XRF), inductively
coupled plasma (ICP) spectrometry and Transmission Electron Microscopy
(TEM). The BET results indicated that the surface area and pore size of
MCM‐41 were decreased after modification. The obtained catalyst was used
as a highly efficient, heterogeneous and recyclable catalyst for the oxidation
of a wide range of alkenes with hydrogen peroxide (H2O2) as a green oxidant.
The effect of various parameters such as catalyst and imidazole (co‐catalyst)
concentration, tempreture, and reaction time on the conversion effecincy and
selectivity of the reaction have been studied. The catalyst was used in five con-
secutive experiment without any loss of activity, confirming the success of the
anchoring process and the catalyst stability.
Correspondence
Saeed Rayati, Department of Chemistry,
K.N. Toosi University of Technology,
Tehran, PO Box 16315‐1618, Tehran
15418, Iran.
Email: rayati@kntu.ac.ir; srayati@yahoo.
com
KEYWORDS
heterogeneous catalyst, manganese schiff base, MCM‐41, olefins, oxidation
1 | INTRODUCTION
To overcome this problem and recycling of valuable cata-
lysts by filtration or other easy separation methods,
Catalytic oxidation is one of the important process which
has attracted great attention in the various field of chem-
ical industry.[1–4] Transition metal complexes in either
supported or not supported and stabilized forms play an
important role in common oxidation processes as catalyst.
Among the catalysts, Schiff base complexes show good
catalytic properties for oxygen transfer reactions.[5–10]
The Schiff base complex catalysts can be synthesized eas-
ily and their electronic and steric effects can be finely
tuned by introducing suitable groups in the phenolic
and/or in the diamine bridge. Unfortunately, the ligand
oxidation and dimers/polymer formation limit activation
of these catalysts in homogeneous liquid solution.[11,12]
heterogenization of the homogeneous catalysts could be
performed. Immobilization of catalyst on an appropriate
solid material with high surface area such as zeolite,
active carbon, polymer etc. is an effective way for
heterogenization of homogeneous catalyst. In the current
work the inorganic MCM‐41 was selected as appropriate
solid support for heterogenization process. The MCM‐41
has advantages such as high surface area, low affinity
for swelling and shrinking in various media (due to its
rigid structure). Also the MCM‐41 has mesoporous
ordered structure (ordered array of hexagonal channels)
which reduce diffusional resistance of the reactant mole-
cules to access the metal active sites located within the
Appl Organometal Chem. 2018;e4593.
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© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4593

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ZAKERI ET AL.
channel. In the other words the hexagonal channels with
a pore diameter increase availability of active sites for
reactant molecules.[13,14] In designing of catalyst support
with robust structure the homogeneous catalyst must be
attached to support masterly (in the correct direction) as
no destructive effect impose on reactive centers. Among
various catalyst immobilization techniques,[15] the attach-
ment of support to ligand by covalent band has attracted
more attention correspond with others. This attention is
in favor of chemical stability of catalyst and no reaching
of catalyst during catalytic reaction and catalyst recycling.
In this work the anchoring of Mn‐Schiff base complex
through its hydroxyl groups (phenolic moiety) onto
MCM‐41 by 1,4‐diisocyanatobutane as linking agent was
studied.[16] The obtained catalyst was used for oxidation
of alkenes in presence of H2O2.
sodium silicate solution was added dropwise under vigor-
ous magnetic stirring. The pH of the mixture was
adjusted to 10 using 2 M sulphuric acid solution. The
resulting gel was transferred to Teflon lined autoclave
and heated statically at 100 °C for 2 days. The obtained
solid material was filtered, washed with water and dried
at 60 °C. The sample was then calcined in flowing nitro-
gen at 550 °C (2 °C/min), then in air at the same temper-
ature for 5 hr. The formation of MCM‐41 was confirmed
by low angle X‐ray diffraction pattern.
2.2.2 | Preparation of 1,2‐bis
(phthalimidooxy)ethane
1,2‐Bis (phthalimidooxy) ethane (Scheme 1, I) was syn-
thesized according to the standard reported method.[18]
The method is as follows:
1 equivalent of 1,2‐
dibromoethane was alkylated with 2 equivalents of N‐
hydroxy phthalamide in dimethyl formamide (DMF) con-
taining 6 equivalents of triethylamine to produce white
needles solid. The recrystallization of product (white
solid) performed in DMF.
2 | EXPERIMENTAL SECTION
2.1 | Materials and characterization
Chemicals were purchased from Merck or Fluka and used
as received without further purification. The solid samples
were identified by X‐ray powder diffraction (XRD) using a
2.2.3 | Preparation of 1,2‐bis (aminooxy)
Siemens D500 diffractometer, Cu‐kα (λ = 4541 ̊A). The
ethane
morphology of the solid catalyst was investigated with
transmission electron microscopy (TEM, Phillips EM
085). Infrared spectra were recorded (KBr pellets) on a
For synthesis of 1,2‐bis (aminooxy) ethane (Scheme 1, II),
5.82 ml hydrazine (25%) was added drop‐wise into 1,2‐bis
(phthalimidooxy) ethane (0.0568 ml) suspension over a
period of a 10 min in 95% ethanol (20 ml) at room temper-
ature under N2. After the hydrazine addition, the reaction
was completed in 5 min and a white phthalhydrazine was
obtained. The precipitate was broken up with a spatula
and the mixture was stirred for 2 hr. Then 50 ml of ethanol
(95%) was added to the mixture and the resulting mixture
was subsequently filtered to collect the phthalhydrazide.
The collected product was washed with 95% ethanol and
its residual solvent was vaporized under reduced pressure.
In next, 100 ml of CH2Cl2 was added to the residue and
the solution was stored at 10 °C overnight hitting to the
dissolved phthalhydrazide to precipitate. Finally, the
solution was filtered and the precipitate was dried.[18]
VECTOR‐22 Bruker in the range of 400 to 4000 cm−1
.
The measurement of specific surface area for the prepared
samples was performed through measuring N2 adsorp-
tion–desorption isotherms at 77 K with a Quanta‐chrome
NOVA‐2200e system. Amount of loaded Mn (II)
was determined by inductively coupled plasma (ICP‐
OESJobinYvon) or X‐ray fluorescence using Oxford ED
2000. Gas chromatography (GC) analysis were conducted
on an Agilent chromatograph (model 7890B) equipped
with flame ionization detector (FID) and capillary column
HP‐5 (phenyl methyl siloxane 30 m × 0.32 mm × 0.25 μm).
2.2 | Catalysts preparation
2.2.1 | Preparation of MCM‐41
Mesoporous silica materials (MCM‐41) were successfully
prepared by the hydrothermal crystallization method
according to the procedure declared by Das et al.[17] The
Sodium silicate was considered as a silica source and
cethyltrimethylamonium bromide (CTAB) was consid-
ered as a template for crystal growth. In order to prepare
MCM‐41, the precursor ratio was as 1 (SiO2):0.33
(NaO2):0.5 (CTAB):74 (H2O). A determined value of
CTAB was dissolved in deionized water and then the
2.2.4 | Preparation of the Schiff base ligand
The condensing of the 1,2‐bis (aminooxy) ethane
(3.9 mmol) and 2,4‐dihydroxybenzadehyd (7.8 mmol)
have been developed in ethanol as a solvent for synthesis
of Schiff base ligand. A yellow‐orange precipitate began
to appear however, the reaction required more 1 hour
for completion. The obtained precipitates were filtrated
and dried under vacuum[19] (scheme 1, (III)).

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SCHEME 1 Anchoring of catalyst on
MCM‐41 support
room temperature, the Mn (II) complex was added to it
and refluxed for 6 hr under N2 atmosphere. Then the
resulting product was extracted through soxhlet mode[16]
by ethanol for 24 hr and dried under vacuum. The
resulting materials denoted as Mn‐Salen‐DIC@MCM‐
41(Scheme 1, VI).
2.2.5 | Preparation of manganese Schiff
base complex
Preparation of Mn (II) Schiff base complex (Scheme 1, IV)
has been done according to reported method.[11] To a
solution of Schiff base ligand (3 mmol) in ethanol
(30 ml), a hot solution of manganese (II) acetate
tetrahydrate (3.3 mmol) in ethanol (10 ml) was added.
The reaction mixture was refluxed for 2 hr. The solution
color changes from yellow‐orange to dark brown during
reflux process. The crystallization of Mn (II)‐complex
was performed in a solution of ethanol: acetonitrile
(1:1). The obtained product was dried under vacuum.[20]
2.3 | General heterogeneous oxidation
procedure
The oxidation reactions of alkenes in the presence of syn-
thesized catalyst were performed in a batch mode, under
atmospheric pressure and gentle stirring condition. In a
typical procedure, to 1 ml of ethanol, 4.6 × 10−3 g of pre-
pared catalyst, 0.09 mmol of alkene and appropriate
amount of imidazole and H2O2 were added. The mixture
was stirred slowly by magnetic stirrer for determined time
at room temperature. After reaction completed, solid
phase was separated by centrifugation and the products
were characterized by GC.
2.2.6 | Immobilization of Mn‐complex on
MCM‐41
In order to anchoring of prepared catalyst, 1 g of the
MCM‐41 as support was refluxed with 3 mmol of DIC‐4
as binder, in dry toluene for 3 hr under N2 atmosphere
(Scheme 1, V). After cooling down the solution to the

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ZAKERI ET AL.
Finally, the products of oxidation process were identi-
fied by comparison of the obtained results with valid sam-
ples (retention times stability and reuse test were carried
out by running five consecutive in GC) experiment.
3 | RESULTS AND DISCUSSION
3.1 | Characterization of the heterogenized
catalyst
The XRD patterns of the MCM‐41 and the catalyst loaded
MCM‐41 are shown in Figure 1. The XRD pattern showed
the characteristic reflection peaks at Bragg angle
(2θ) = 2°‐6° range. The characteristic peaks at 2θ =2.8°
(intensive peak), 4.6°, and 5.5° (weak peaks) correspond
to (100), (110) and (200) planes of MCM‐41 structure
respectively. The sharp peak at 2.8 corresponds to 100
plane and is due to the hexagonal pore structure of
MCM‐41. The mentioned peaks corresponding to (100),
(110) and (200) reflection plane were kept in catalyst
loaded MCM‐41 sample, however their intensity was
decreased which indicates disordering of plane arrange-
ment during catalyst loading in MCM‐41 structure.[21,22]
The position of (100) reflection was preserved suggesting
that basic hexagonal pore arrangement was kept.
Figure 2 shows the FT‐IR spectra of the binder
(DIC‐4), unmodified MCM‐41, DIC‐4‐MCM‐41 and the
catalyst (Mn‐Salen‐DIC@MCM‐41). The catalyst spectra
(final product) confirms that the MCM‐41 framework
was not changed during the modification. The broad
band in the range of 3770–3300 cm−1 are attributed to
the surface hydroxyl groups and the strong band in the
range of 1300–750 cm−1 are for lattice vibrations.[20] The
bands observed at 1215,1085, 807 and 480 cm−1 can be
assigned to the asymmetric and symmetric stretching
(Si─O─Si) and (Si─O─Si)) of the MCM‐41framework.
The band seen at about 970 cm−1 is attributed to ν
FIGURE 2 FTIR spectra of 1,4‐diisocyanate, MCM‐41, 1,4‐
diisocyanate bonded to MCM‐41 and heterogeneous catalyst
(Si─OH) vibrations. The observed peak at 1690 cm−1 in
final product is assigned to carbamate amide group. As
can be seen the intensity of 970 cm−1peak in
heterogenized catalyst spectra has decreased which is
indicative of functionalization of the silanol groups. The
observed peak in 1580–1600 cm−1 range is attributed to
stretching vibration of the C═N bonds. Disappearing
the‐NCO characteristic peak, at about 2275 cm−1, indi-
cates the reaction of both functional groups of 1,4‐
diisocyanatobutane. The peak observed at t 2955 cm−1
has more intensity and also a new peak was observed at
1443 cm−1 which can be attributed to the ─CH2
bending.[23,24]
Figure 3 shows the TEM images of MCM‐41 and cat-
alyst loaded MCM‐41 materials. As can be seen the
MCM‐41 has a rectangular shape with an average width
about 200 nm. The loading of catalyst on MCM‐41 didn't
change the original morphology of MCM‐41. The catalyst
image shows typical octahedral shape with an average
size of about 300 nm. Apparently the catalyst particles
are adsorbed onto the channels of mesoporous system,
therefore the MCM‐41 structure didn't show serious
change. The TEM images of MCM‐41 and Mn‐Salen‐
DIC@MCM‐41 samples were taken in different views.
The specific surface area of MCM‐41 and catalyst
loaded MCM‐41 (estimated from the BET method) were
1441.31 and 445.02 m2/g respectively. The results indicate
that surface area of MCM‐41 decreased significantly after
catalyst modification. The decreased in surface area can
be attributed to dispersion and deposition of catalyst par-
ticles into MCM‐41 pore channels.[25–27]
Nitrogen adsorption isotherms of the MCM‐41 and
catalyst loaded MCM‐41 are shown in Figure 4. The iso-
therms have a typical type IV form with a type H4 hyster-
etic loop, typical of mesoporous materials based on to
FIGURE 1 XRD pattern of MCM‐41 and catalyst loaded
MCM‐41

ZAKERI ET AL.
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TABLE 1 The effect of the catalyst concentration on the
epoxidition of cyclooctene
No.
Catalyst Amount
Conversion (%)
1
2
3
4
0
0
3 mg, 0.002 mmol
4.5 mg, 0.003 mmol
6 mg, 0.004 mmol
40
65
63
Reaction condition: H2O2 (30%) 1 ml, 8 h, 25 °C
average pore diameters decreased from 2.7 nm for
MCM‐41 to 2.18 nm for catalyst loaded MCM‐41, which
is in line with BET and amount of adsorbed nitrogen
results and confirm successful modification of MCM‐41.
The Mn (II) value of the catalyst was determined by
ICP and XRF techniques. The results indicated that both
techniques give approximately same Mn (II) value, about
3.6%(W/W) in catalyst.
3.2 | Catalytic oxidation of olefins
Cyclooctene oxidation was selected to investigate the cat-
alytic performance of the synthezied catalyst. Cyclooctene
oxidation was investigated in presence Mn‐Salen‐
DIC@MCM‐41 as catalyst, hydrogen peroxideas as oxy-
gen donor and imidazol as co‐catalyst. The effect of vari-
ous factors such as catalyst concentration, imidazole
concentration, tempreture, and time on the conversion
efficiency and selectivity of the catalyst have been stud-
ied. In order to optimize the concentration of catalyst, dif-
ferent amounts of catalyst were used in the epoxidation of
cyclooctene (Table 1). As can be seen the presence of cat-
alyst is essential for cyclooctene oxidation the maximum
FIGURE 3 TEM image of (a) MCM‐41 and (b) catalyst‐MCM‐41
samples
IUPAC classification.[25–27] The plot of the pore‐size dis-
tribution (Figure 4 inset) was determined from the
desorption branch of the isotherm using the Barrett–
Joyner–Halenda (BJH) method. As can be seen modifica-
tion of MCM‐41 by catalyst, decreased amount of
physisorbed nitrogen and average pore diameter. The
FIGURE 4 N2 adsorption–desorption
isotherms of MCM‐41 and heterogeneous
catalyst. (Inset) BJH pore‐size distribution
curves of the of MCM‐41 and Catalyst‐
MCM‐41

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ZAKERI ET AL.
FIGURE 5 Effect of reaction time on
catalyst performance
conversation was obtained when 4.5 mg catalyst was used
in oxidation process.
The Mn‐Salen‐DIC@MCM‐41 was used for the oxida-
tion of various olefins and the results are given in Table 3.
As can be seen, the catalyst has the most effect on trans‐
stilbene oxidation (100% conversion).
Measuring of conversion value at different reaction
time (2, 8, 24 and 48 hr) clarified that the conversion effi-
ciency increased faster with increasing time, and reaching
a maximum of 88% during 24 hr. Therefore, the best time
for this reaction was found to be 24 hr (Figure 5).
Temperature plays a key role in the chemical reac-
tions. The effect of temperature on oxidation of
cyclooctene in the presence of Mn‐Salen‐DIC@MCM‐41
was investigated at different temperature (25, 50 and
80 °C). The result indicates that the cyclooctene oxidation
process was not occurred at higher than room tempera-
ture (Table 2). This result can be attributed to the destruc-
tion of the catalyst structure at the higher temperature.
The catalyst performance can be improved by addi-
tion of nitrogenous bases as co‐catalyst in the system. In
this work imidazole was selected as co‐catalyst, and the
cyclooctene epoxidation efficiency was determined in
absence and presence of co‐catalyst (Figure 6). The results
indicated that the oxidation reaction improved signifi-
cantly in presence of co‐catalyst and increasing of co‐cat-
alyst concentration in solution led to an increase in the
conversion efficiency. However, more increase of co‐cata-
lyst concentration led to a decrease of conversion effi-
ciency due to inactivation of catalyst surface by
imidazole.[28]
3.3 | Proposed mechanism
A mechanism for these reactions is proposed in scheme 2.
In the catalytic cycle for oxidation reactions with hydrogen
peroxide, two common intermediate species have been
suggested in the literature. In this mechanism, hydrogen
peroxide is activated by coordination to the manganese
center (Scheme 2, I) followed by the generation of high
valent Mn‐oxido species (Scheme 2, II).[29–31] Both inter-
mediates are able to produce epoxide products.
3.4 | Catalyst reuse and stability
The reusability of heterogeneous catalyst can remarkably
reduce the production costs and improve its economy. A suit-
able heterogeneous catalyst retains its catalytic activity and
can be separated from solution. The stability of the catalyst
TABLE 2 The effect of temperature on the epoxidation of
cyclooctene
No
Temperature (°C)
Conversion (%)
1
2
3
25
50
80
65
0
0
FIGURE 6 Effect of imidazole concentration on the oxidation of
Catalyst:Imidazole:Cyclooctene ratio is 1:100:30, H2O2 (30%) 1 ml, 8 h
cyclooctene

ZAKERI ET AL.
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TABLE 3 Oxidation of alkenes with hydrogen peroxidea
No.
alkene
Conversion(%)
Selectivity (%) (Epoxide)
TONc (Total)
1
Cyclooctene
88
100
26.4
2
3
Cyclohexene
Indene
80
93
8b
24
100
27.9
4
5
Styrene
45
100
100
13.5
30
trans‐stilbene
100
6
1‐Octene
30
100
9
aCatalyst:Imidazole:olefine ratio is 1: 100: 30, H2O2 (30%)1 ml, 24 h.
b2‐cyclohexen‐1‐one is the other product.
cTON: (total turnover number) the ratio of the number of moles of product to the number of moles of catalyst.
SCHEME 2 Proposed catalytic cycle
was studied by sequential using of Mn‐Salen‐DIC@MCM‐
TABLE 4 The recovery and reuse of heterogenized catalyst in the
41in epoxidation reactions. After the completion of oxidation
process the catalyst was separated by filtration and washed
several time with ethanol and acetone. Then it was dried
and used as catalyst again. The catalyst was consecutively
reused five times without a detachable catalyst leaching or
a significant loss of its activity (Table 4).
For verifying the activity of Mn‐Salen‐DIC@MCM‐41,
the present study is compared with some of other litera-
ture for oxidation of olefins. The results are shown in
Table 5. It is worth noting that the conversion is higher
than other compared literature.
oxidation of cyclooctene
NO.
Conversion (%)
1
2
3
4
5
88
88
87
87
87
Catalyst:Imidazole:Cyclooctene ratio was:1:100:30. H2O2 (30%) 1 ml. reaction
time 24 h.

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ZAKERI ET AL.
TABLE 5 Comparison of the activity of different complexes in the oxidation reaction
Entry
Catalyst
Substrate
Oxidant
Conversion(%)
References
[32]
1
2
3
4
5
6
7
8
9
Al2O3
Cyclohexene
Cyclooctene
Cyclohexene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclohexene
Cyclooctene
H2O2
H2O2
H2O2
H2O2
TBHP
H2O2
H2O2
H2O2
H2O2
35
24
42
10
20
70
26
80
88
[33]
[34]
[35]
[36]
[37]
[37]
Fe (PCl8P)Cl
Na9[SbW9O33] + 9[MTCA] + Cl
Mn (Br8TPP)Cl‐PSI
FeTHPPCl‐MWCNT
Mn Schiff base‐Zeolit
VO Schiff base‐Zeolit
Mn (II)‐Complex‐MCM‐41
Mn (II)‐Complex‐MCM‐41
This work
This work
[7] L. Ma, F. Su, X. Zhang, D. Song, Y. Guo, J. Hu, Microporous.
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4 | CONCLUSION
[8] O. Pouralimardan, A. Chamayou, C. Janiak, H. Hosseini
Mn‐Salen‐DIC@MCM‐41was synthesized by attaching of
the Mn‐salen complex on MCM‐41 and characterized.
The oxidation of alkenes by synthesized catalyst were per-
formed in a batch mode, under atmospheric pressure.
Cyclooctene oxidation was investigated in presence of
MnSalen‐DIC@MCM‐41 as catalyst, hydrogen peroxideas
as oxygen donor and imidazole as cocatalyst. The maxi-
mum conversation (88%) was obtained when 4.5 mg cat-
alyst was used after 24 hr. Imidazole was selected in
this work to improve the catalyst performance. The cata-
lyst was consecutively reused five times without a detach-
able catalyst leaching or a significant loss of its activity.
Also the IR spectra of the catalyst remained intact during
the reaction. This observation show that the catalyst is
stable during the oxidation reaction.
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ORCID
Saeed Rayati http://orcid.org/0000-0003-2941-7216
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How to cite this article: Zakeri H, Rayati S,
Zarei G. Synthesis and characterization of a Mn‐
Schiff base complex anchored on modified MCM‐
41 as a novel and recyclable catalyst for oxidation
of olefins. Appl Organometal Chem. 2018;e4593.
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