Aerobic oxidation of olefins in the presence of a new amine functionalized core–shell magnetic nanocatalyst

Article abstract of DOI:10.1016/j.catcom.2019.01.019

In this study meso-tetrakis(4-carboxyphenyl)porphyrinatomanganese(III) acetate was immobilized onto the surface of amine functionalized Fe₃O₄ magnetic nanoparticles through covalent linkage. The new magnetic nanocatalyst [Fe₃

Full text of DOI:10.1016/j.catcom.2019.01.019

Accepted Manuscript
Aerobic oxidation of olefins in the presence of a new amine
functionalized core–shell magnetic nanocatalyst
Saeed Rayati, Fatemeh Nejabat, Fatemeh Panjiali
PII:
S1566-7367(19)30022-6
DOI:
Reference:
https://doi.org/10.1016/j.catcom.2019.01.019
CATCOM 5603
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
17 October 2018
13 December 2018
25 January 2019
Please cite this article as: S. Rayati, F. Nejabat and F. Panjiali, Aerobic oxidation of olefins
in the presence of a new amine functionalized core–shell magnetic nanocatalyst, Catalysis
Communications, https://doi.org/10.1016/j.catcom.2019.01.019
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ACCEPTED MANUSCRIPT
Aerobic oxidation of olefins in the presence of a new amine functionalized
core–shell magnetic nanocatalyst
Saeed Rayati,* Fatemeh Nejabat and Fatemeh Panjiali
Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran 15418, Iran
Abstract
In this study meso-tetrakis(4-carboxyphenyl)porphyrinatomanganese(III) acetate was
immobilized onto the surface of amine functionalized Fe3O4 magnetic nanoparticles through
covalent linkage. The new magnetic nanocatalyst [Fe3O4@SiO2@NH2@MnTCPP(OAc)] was
characterized using Fourier infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD),
electronic and atomic absorption spectroscopy, vibrating sample magnetometry (VSM),
thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The prepared
catalyst was used for the oxidation of alkenes with molecular oxygen as standard green oxidant
and
excellent
results
were
achieved.
The
new
heterogenized
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] oxidation catalyst could be readily reused at least five
times without significant decrease in the activity, which displays potential for practical
applications.
Keywords: Magnetic nanoparticles, Molecular oxygen, Aerobic oxidation, Heterogenized
catalyst, Metalloporphyrin.
* Corresponding author. Tel.: +98 21 22850266; Fax: +98 21 22853650.
E-mail addresses: rayati@kntu.ac.ir.
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1. Introduction
Oxidation of organic compounds is considered as a starting point for the synthesis of valuable
pharmaceutical chemicals in the presence of various catalytic systems. Epoxides as the most
important intermediate, which play a significant role in various chemical and biological reactions
such as preparation of glue, ethylene glycol, amino alcohols and resin, can usually produce by
oxidation of olefins [1-3].
Cytochrome P450 as a powerful enzyme for the oxidation of different types of substrates
consists of an iron porphyrin serving as an active catalytic site [4]. Considerable attentions has
been paid to the role of porphyrin-based complexes in the oxidation reaction as biomimetic
systems, especially for laboratory use [4-6]. In the past decades, due to an ever-increasing
environmental pollution, special attention was paid to the use of green oxidants in oxidation
reactions [7-9] and great attention has been devoted to the molecular oxygen because of its
important advantages such as high active oxygen content, low cost, fast kinetic and available
amount [10-12]. Moreover, use of heterogeneous catalyst in the oxidation reactions is another
way of approaching green chemistry. Beside the importance of green chemistry in process
research, heterogenization of metal complexes help to overcome the problems of oxidative
degradation of catalysts. In this aspect, various types of solid support such as mesoporous
materials, activated carbons, clays and zeolites were applied to produce hybrid catalysts. The
immobilization of transition metal complexes onto the surface of nanomaterials is of widespread
interest [13-15]. Large-scale application of Fe3O4 nanoparticle as solid support is due to their
super paramagnetic property, simple separation, large surface area to volume ratio and easy
functionalization [16-18].
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In this study, a highly efficient nanocatalyst for the aerobic oxidation of olefins was
introduced by immobilization of manganese porphyrin onto the surface of amine functionalized
magnetic nanoparticles via amide bond.
2. Experimental
2.1. Preparation of nanocatalyst
A
multistep procedure was applied to prepare the magnetic nanocatalyst
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] as illustrated in scheme 1.
Scheme 1. Schematic preparation of magnetic nanocatalyst.
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Fe3O4 nanoparticles, Fe3O4@SiO2 and Fe3O4@SiO2@NH2 were prepared and characterized
using precipitation method as reported previously [18-22] (see supporting information).
Meso-tetrakis(4-carboxyphenyl)porphyrin (H2TCPP) and MnTCPP(OAc) were prepared and
characterized by Adler’s method (see supporting information, S1).
MnTCPP(OAc) was anchored onto the surface of amine-functionalized magnetic
nanoparticles (Fe3O4@SiO2@NH2) through covalent linkage. The carboxyl group of the
MnTCPP(OAc) was attached to the -NH2 group of magnetic nanoparticles (Fe3O4@SiO2@NH2)
using 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium tetraflouroborate (TBTU) as a
highly effective uranium salt in the presence of N,N′-diisopropylamine (DIPEA) [23-24] (see
supporting information, S1).
2.2. Catalytic test
In a typical procedure, catalytic experiments were carried out in a 5 mL test tube containing
1.06 10-3 mmol of nanocatalyst, 0.19 mmol of alkene and 0.96 mmol isobutyraldehyde (IBA) in
˟
acetone (1mL). The oxidation reaction initiated under O2 atmosphere (oxygen balloon) and
allowed to stir for 30 min at room temperature. After completion of the reaction, the
heterogeneous nanocatalyst was magnetically recovered, organic phase was analyzed by GC-FID
and the oxidation product was identified by comparison with authentic samples.
3. Results and Discussion
3.1. Catalyst preparation
Chemical formation of amide bond is one of the most challenging organic transformations,
especially for the activity of many peptide hormones. In this aspect, carboxylic acid usually
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activated by a coupling reagent and subsequently, the activated form of carboxylic acid react
with amine group to produce amide bond.
The surface of amine functionalized silica coated magnetic nanoparticles
(Fe3O4@SiO2@NH2) were modified via the attachment of Mn-porphyrin to prepare porphyrin
based magnetic nanocatalyst (Scheme 1). To promote formation of amide bonds between
carboxyl group of metalloporphyrin and the amine group of Fe3O4@SiO2@NH2, basic coupling
reagents (TBTU/DIPEA) were used as reported previously [25-27]. The resultant catalyst
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] were fully characterized by different standard methods.
3.2. Catalyst characterization
The amount of loaded manganese porphyrins center onto the surface of amine-functionalized
magnetic nanoparticles was determined by atomic absorption spectroscopy (AAS) revealed that
each gram of the magnetic nanocatalyst contains 500 µmol of manganese porphyrin.
Immobilization of MnTCPP(OAc) on the surface of amine functionalized magnetic
nanoparticles was evaluated with FT-IR spectra. The FT-IR spectrum of
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] (see supporting information, Figure S4) showed a
detectable absorption band at around 1650 cm-1 which confirmed the formation of amide bond
between –COOH groups of Mn-porphyrins and –NH2 groups of the support. In addition, other
-1
signals at about 1392, 1540 and 1595 cm corresponding to the vibrations of metalloporphyrin
-1
are present in the FT-IR spectra. The absorption band at 2854-2923 cm ascribed to the C-H
stretching of the propyl group in the pendent APTS can be clearly observed in the FT-IR
spectrum of Fe3O4@SiO2@NH2, which confirms that APTS has been successfully bonded to the
silica coated magnetic nanoparticles. The wide absorption peak at about 3400 cm−1 is due to
hydroxyls (OH) present in water and the amine groups are obscured [28-29].
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Fig. 1 shows the XRD pattern of [Fe3O4@SiO2@NH2@MnTCPP(OAc)] to investigate the
crystalline structure of the prepared magnetic nanocatalyst. In the XRD pattern of
[Fe3O4@SiO2@NH2@MnTCPP(OAc)], some characteristic peaks centered on the 2θ values of
30.6, 35.7, 43.8, 54.2, 57.3, 63.6, 71.5 and 74.8 correspond to (220), (311), (400), (422), (511),
(440), (620) and (533) plans of cubic inverse spinel Fe3O4. These diffraction peaks are in good
agreement with the database in JCPDS file (PCPDFWIv.2.02, PDF no. 85-1436) and shows that
Fe3O4 nanoparticles were synthesized without impurity phases and also indicated that the
crystalline structure of Fe3O4 did not changed after coating with silica shell [30]. Based on the
Scherrer’s equation, the average particle size of [Fe3O4@SiO2@NH2@MnTCPP(OAc)] were 22
nm.
311
250
200
150
100
50
440
511
220
400
422
533
620
0
10
20
30
40
50
2 Theta ( ° )
60
70
80
90
Fig. 1. XRD pattern of [Fe3O4@SiO2@NH2@MnTCPP(OAc)].
The
SEM
images
of
Fe3O4@SiO2
and
the
prepared
nanocatalyst
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] clearly show uniformity and the smooth spherical
morphology of magnetic nanoparticles (see supporting information, Figure S5). After porphyrin
incorporation, magnetic nanoparticles slightly aggregated and average particle sizes increased,
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suggesting immobilization of a huge amount of Mn-porphyrins onto the surface of amine
functionalized solid support (Fe3O4@SiO2@NH2).
The magnetic properties of amine functionalized solid support (Fe3O4@SiO2@NH2), and the
prepared nano-catalyst [Fe3O4@SiO2@NH2@Mn(TCPP)OAc] were characterized by a vibrating
sample magnetometer (VSM) under an applied field of -10000 to 10000 Oe at room temperature
and the results are illustrated in Fig. 2. A ferromagnetic behavior evidenced through the S-
Shaped hysteresis loop and the prepared magnetic nano-catalyst shows strong magnetization,
which can be easily separated by an external magnet. According to the magnetization curves, the
reduced saturation magnetization values observed for the prepared nanocatalyst in comparison
with Fe3O4@SiO2@NH2 nanoparticles, which was predictable and were due to the diamagnetic
surface coating and surface functionalization of Fe3O4 nanoparticles [31-32].
60
40
20
0
-20
-40
-60
Catalyst
-20000 -10000
0
10000
20000
Fe3O4@SiO2@NH2
Applied field (Oe)
Fig. 2. Magnetization curves of Fe3O4@SiO2@NH2 (Red line) and catalyst (blue line).
The UV-Vis spectrum of magnetic nanocatalyst confirmed the presence of metalloporphyrin
on the surface of the synthesized magnetic solid support (Fe3O4@SiO2@NH2) (see supporting
information, Figure S6). According to the literature, manganese porphyrins show a characteristic
peak at about 475 nm (Soret band) which is clearly detectable in the UV-Vis spectrum of
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MnTCPP(OAc) in ethanol (see supporting information, Figure S6, a). No absorption peak was
observed in this region in the UV-Vis spectrum of dispersed Fe3O4@SiO2@NH2 in ethanol
(Figure S6, b). After deposition of MnTCPP(OAc) onto the surface of magnetic solid support,
the UV-Vis spectrum of [Fe3O4@SiO2@NH2@MnTCPP(OAc)] which has been dispersed in
ethanol (by using an ultrasonic bath) shows the typical Soret band of Mn-porphyrins at 481 nm
(see supporting information, Figure S5, c). Based on the results, the UV-Vis spectrum of
magnetic nanocatalyst exhibited a slight red shift compared to the spectrum of pure
MnTCPP(OAc), which could be because of the coordination and aggregation of
metalloporphyrins onto the surface of Fe3O4@SiO2@NH2. Moreover, these data confirmed that
the structure of Mn-porphyrin remain unchanged after deposition onto the surface of magnetic
solid support.
Thermal behavior of Fe3O4@SiO2@NH2 and [Fe3O4@SiO2@NH2@Mn(TCPP)OAc] were
analyzed by thermo-gravimetric analysis (TGA) under N2 atmosphere (100 mL/min) at a heating
rate of 10 °C/min (see supporting information, Figure S7). The TGA curves showed high thermal
stability of both Mn-porphyrin coated and uncoated magnetic nano-spheres and no significant
degradation of support and separation of the catalyst from the surface of support was observed.
The first weight loss step (3.9%) in the temperature range of 100 °C could be related to the loss
of physically adsorbed water molecules on the surface of the Fe3O4@SiO2@NH2, and the second
weight loss step of 4% between 170 °C and 280 °C is due to the loss of water molecules which
are either free-existent at the compound level or bonded to SiO2. The last weight loss observed in
the temperature range between 500 °C and 900 °C could be related to the loss of NH2 functional
groups attached to the surface of the Fe3O4@SiO2. The comparison of two thermograms showed
that the weight loss between temperature 260 °C and 470 °C is likely to be due to the separation
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of metalloporphyrins from the surface of solid support, which is a very modest reduction and
only 2% weight loss could be detectable in this step.
3.3. Catalytic experiments
In order to investigate the catalytic activity of the prepared magnetic nanocatalyst
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] for the aerobic oxidation of olefins, oxidation of styrene
(as a model substrate) has been studied under magnetic stirring and different parameters were
taken under consideration such as solvent, reaction time, amount of catalyst and reductant
(isobutyraldehyde).
In order to find an appropriate solvent for the oxidation of styrene with molecular oxygen and
isobutyraldehyde (IBA) in the presence of [Fe3O4@SiO2@NH2@MnTCPP(OAc)], different
solvents such as methanol, ethanol, dichloromethane, chloroform, acetonitrile and acetone were
applied and based on the results, the highest conversion in the relatively short time obtained in
acetone (Table 1). Epoxy styrene was the major product (acetophenone and benzaldehyde were
other products which are detected by GC) and no product was detectable by GC in the absence of
the catalyst.
Table 1. Effect of solvent on the oxidation of styrene with O2 in the presence of
a
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] at room temperature .
Entry
1
Solvent
CH2Cl2
Time (min)
Conversion%
Selectivity%
90
41
100
2
3
4
5
6
CH3CN
CHCl3
90
90
43
23
47
>99
0
78
68
65
76
-
CHCl3
120
60
CO(CH3)2
CH3OH
120
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7
EtOH
120
0
-
a The molar ratios for Catalyst:Styrene:IBA are (1:90:450) under an oxygen atmosphere.
Different catalyst concentrations were used in the range of 0.001 g to 0.003 g (see supporting
information, Figure S8). The obtained data showed superior catalytic efficiency for aerobic
oxidation of styrene in the presence of 0.002 g (0.55 mol%) of catalyst after 30 min (see
supporting information, Figure S8, b); however, more catalyst concentration applied caused less
efficiency in the same reaction time (see supporting information, Figure S8, c).
Previous reports have been shown that aerobic oxidation of hydrocarbons in the presence of
metallo-complexes for the best efficiency needs a reducing agent (such as light aldehydes) to
reduce dioxygen at the beginning of the reaction [33-34]. In this research, isobotylaldehyde
(IBA) was selected as effective reducing agent for the aerobic oxidation of styrene in the
presence of [Fe3O4@SiO2@NH2@MnTCPP(OAc)] and in order to achieve the highest product
yields, the effect of molar ratio of IBA/styrene was studied (see supporting information, Figure
S9). Based on the results, no product was observed in the absence of isobutyraldehyde and the
highest conversion (100%) was achieved at molar ratio 1:5 of IBA:styrene in acetone at room
temperature.
To prove the activity of [Fe3O4@SiO2@NH2@MnTCPP(OAc)] in the model reaction, aerobic
oxidation of a range of olefins under optimized condition were studied and the results have been
presented in Table 2.
Based on the results, excellent conversions and desired selectivity to epoxide were achieved
for all olefins. This catalytic system led to complete conversion of α-methyl styrene, trans-
stilbene and cyclohexene after 30 min and styrene, 4-methyl styrene and 4-chloro styrene in 1
hour. Cyclooctene was converted to its epoxide in 83% yield after 30 min, 4-methoxy styrene
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and indene converted to the corresponding epoxides by 96% and 80% respectively after 60 min.
Less activity was observed in the case of terminal olefins (1-octene, 48%).
Table
2.
Aerobic
oxidation
of
various
olefins
in
the
presence
of
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] at room temperature.a
Entry
1
Alkene
Product
Conversion%b Selectivity%b
83
87
80
O
2
100
O
3
4
100
100
85(100)b
97(90)b
O
56(100)b
(100)b
(96)b
57(80)b
70
O
5
6
7
Cl
Cl
O
Me
Me
O
98
MeO
Me
MeO
Me
8
O
100
67
9
80 b
85
O
O
10
21(48)b
100
5
5
a
Reaction conditions: the molar ratios for Catalyst:Olefin:IBA is 1: 180:900, reaction time:30 min
under an oxygen atmosphere, acetone: 1mL. b Reaction time: 60 min.
A plausible mechanism for the oxidation of styrene with O2 in the presence of
[Fe3O4@SiO2@NH2@MnTCPP(OAc)] has been reported (Scheme 2). Isobutyraldehye used as a
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useful reducing agent for aerobic oxidations and based on the literature [33-36]; free radicals are
involved in the catalytic oxidation of olefins with molecular oxygen/IBA. In this mechanism,
two parallel pathways could be possible. In the first step, Mn-por reacts with IBA to generate an
acyl radical (Scheme 2, (a)). In the second one, the generated acyl radical reacts with dioxygen to
give an acylperoxy radical (Scheme 2, (b)) which can oxidize styrene directly (Scheme 2,
pathway (A)). Acylperoxy radical can also act with another aldehyde to give peroxyisobutyric
acid (Scheme 2, (c)), resulting the production of another acyl radical. Formation of epoxy styrene
is assumed by the presence of an active intermediate (high-valent Mn-porphyrin species) which
are formed by the reaction of the peroxyisobutyric acid with Mn(II) porphyrin (Scheme 2,
pathway (B)).
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Scheme 2. Proposed catalytic cycle of aerobic oxidation of alkenes in the presence of
[Fe3O4@SiO2@NH2@MnTCPP(OAc)].
The reusability of heterogeneous catalysts is one of the most important ability, which make
them useful for various applications. The magnetic property of core-shell magnetic nonocatalysts
can facilitate recovery and reusability of the heterogenized catalyst. The reusability of the
prepared porphyrin based nanocatalyst investigated in the multiple sequential oxidation of
styrene with O2 in acetone at room temperature. After each catalytic cycle, when the magnetic
stirring stopped, the catalyst easily separated from the reaction media by an external magnet (see
supporting information, Figure S10), washed with acetone (2 mL, 2×2 time), completely dried
and used in the subsequent run without further purification.
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[Fe3O4@SiO2@NH2@MnTCPP(OAc)] was reused for at least five consecutive cycle and the
amounts of Mn leached after each run were determined by AAS analysis as illustrated in Table 3.
The results show that after each catalytic cycle, trace amount of Mn was leached; only after more
reaction time, proper conversion and high selectivity was achieved (Table 3, column 3). AAS,
FTIR and UV-Vis spectra were employed to prove the stability of magnetic nano-catalyst after
five catalytic cycle; the results show that the structure of the recovered catalyst remain
unchanged (see supporting information, S4”.
Table 3. The result of the reusability of nano-catalyst for the oxidation of styrene with O2 at
room temperature.
Run
1
Time (min)
Conversion %a (Selectivity%) Mn-leaching%
60
100 (90)
97 (90)
86 (90)
86 (88)
80 (88)
0
2
3
4
5
60
80
80
90
0.04
0.15
0.21
0.47
a The molar ratios for Catalyst:Styrene:IBA are (1:180:900) under an oxygen atmosphere, acetone:1 mL.
To evaluate the catalytic efficiency of [Fe3O4@SiO2@NH2@MnTCPP(OAc)], the obtained
results of this catalytic system for the aerobic oxidation of styrene were compared with some
earlier reported studies and the results proved the efficiency of our proposed model especially in
the case of the reaction time and temperature ( see supporting information, Table S1).
4. Conclusions
In conclusion, manganese porphyrin was successfully immobilized onto the surface of amine
functionalized silica coated Fe3O4. The magnetically separable catalyst is highly efficient for
green oxidation of alkenes with O2 in the mild condition. This super magnetic nanoparticle can
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be used for several times without detectable leaching of the catalyst and decreasing the catalytic
activity and selectivity.
Acknowledgements
This work was supported by K.N. Toosi University of Technology research council and Iran
National Science Foundation (INSF) [grant No. 96011716].
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ACCEPTED MANUSCRIPT
 Preparation
of
a
new
porphyrin
based
magnetic
nanocatalyst
[Fe3O4@SiO2@NH2@MnTCPP(OAc)].
 Aerobic oxidation of olefins at room temparature and in the short reaction time.
 Excellent activity and high stability of magnetic nanocatalyst.
20