Synthesis and characterization of mangenese(III) porphyrin supported on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for oxidation of hydrocarbons with sodium periodate

Article abstract of DOI:10.1016/j.jssc.2014.05.016

In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101, was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was characterized by UV-vis, FT-IR, X-ray diffraction (XRD), N ₂ adsorption, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in the alkene epoxidation and alkane hydroxylation using NaIO ₄ as an oxidant in CH₃CN/H₂O at room temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of hydrocarbons.

Full text of DOI:10.1016/j.jssc.2014.05.016

Author's Accepted Manuscript
Synthesis and characterization of mangenese
(III) porphyrin supported on imidazole mod-
ified chloromethylated MIL-101(Cr): A hetero-
geneous and reusable catalyst for oxidation of
hydrocarbons with sodium periodate
Farnaz Zadehahmadi, Shahram Tangestanine-
jad, Majid Moghadam, Valiollah Mirkhani, Iraj
Mohammadpoor-Baltork,
Khosropour, Reihaneh Kardanpour
Ahmad
R.
www.elsevier.com/locate/jssc
PII:
S0022-4596(14)00224-2
http://dx.doi.org/10.1016/j.jssc.2014.05.016
YJSSC18480
DOI:
Reference:
To appear in: Journal of Solid State Chemistry
Received date: 6 February 2014
Revised date: 12 May 2014
Accepted date: 19 May 2014
Cite this article as: Farnaz Zadehahmadi, Shahram Tangestaninejad, Majid
Moghadam, Valiollah Mirkhani, Iraj Mohammadpoor-Baltork, Ahmad R.
Khosropour, Reihaneh Kardanpour, Synthesis and characterization of
mangenese(III)
porphyrin
supported
on
imidazole
modified
chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for
oxidation of hydrocarbons with sodium periodate, Journal of Solid State
Chemistry, http://dx.doi.org/10.1016/j.jssc.2014.05.016
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Synthesis and characterization of mangenese(III) porphyrin supported
on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous
and reusable catalyst for oxidation of hydrocarbons with sodium
periodate
Farnaz Zadehahmadi, Shahram Tangestaninejad,∗Majid Moghadam,* Valiollah Mirkhani,* Iraj
Mohammadpoor-Baltork, Ahmad R. Khosropour, Reihaneh Kardanpour
Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan 81746-73441, Iran
Abstract- In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101,
was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The
imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese
porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was
characterized by UV-Vis, FT-IR, X-ray diffraction (XRD), N2 adsorption, field emission scanning
electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively
coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in
the alkene epoxidation and alkane hydroxylation using NaIO4 as an oxidant in CH3CN/H2O at room
temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of
hydrocarbons.
Keywords: Metal-organic framework; Manganese porphyrin; MIL-101(Cr); Axial ligand; Oxidation.
1. Introduction
The cytochrome P-450 is a natural monooxygenase enzyme which catalyzes a wide variety of reactions
in the body. The active site of this enzymeis an iron porphyrin surrounded by special proteins which
can be imitated by synthetic metalloporphyrins [1, 2]. These metalloporphyrins are highly efficient
homogeneous catalysts for oxidation of wide range of substrates in the presence of some single oxygen
∗Corresponding authors: Tel: +98-311-7932705; fax: +98-311-6689732: E-mails: stanges@sci.ui.ac.ir (S. Tangestaninejad);
moghadamm@sci.ui.ac.ir (M. Moghadam); mirkhani@sci.ui.ac.ir (V. Mirkhani).
1

–
atom donors such as PhIO, ClO–, KHSO5, H2O2, ROOH or IO4 [3-5]. Among the metalloporphyrins,
manganese porphyrins have been used as good catalysts for oxidation of hydrocarbons [6-8].
Unfortunately, irreversible dimerization, oxidative self-destruction in an intermolecular process and
impossible recovery of the catalyst at the end of reaction, are three major drawbacks which limit the
usage of metalloporphyrins. One way to overcome these problems is to anchor them onto solid supports
[9-15]. This leads to catalysts which are easier to handle, more cost-effective and simple to recover. On
the other hands, steric and electronic effects provided by solid supports can mimic the vestige of
protein matrix of hemoprotein. One of the main approaches for immobilization of metalloporphyrins is
coordinative binding between support and the porphyrin metal center [16, 17].
Metal-organic frameworks (MOFs) are a subfamily of porous coordination polymers (PCPs) which
have outstanding potential for a wide range of applications in gas separation/storage [18-20], sensing
[21-23], magnetism [24, 25], drug delivery systems [26] and catalysis [27-30]. The use of MOFs for
heterogeneous catalysis is nearly a new methodology which deserves more investigations. They have
prominent properties such as high surface area, large and accessible cages, tunable pores and facile
functionalizing possibility which make them suitable supports for immobilization of active catalytic
species such as metal nanoparticles [31-35] or molecular complex species [36-40]. But low thermal and
chemical stability of MOFs are limiting factors for their practical applications. In 2005, Ferey et al.
[41] reported a 3D hybrid material, MIL-101(Cr) [(Cr3X(H2O)2O(bdc)3; X=F, OH; bdc=benzene-1,4-
dicarboxylate)] which possesses high chemical, thermal and hydrothermal stability. Also, MIL-101(Cr)
has large cavities which can be functionalized by two main methods, the first one is grafting electron
rich ligands onto the unsaturated Cr(III) sites [42] and the second one is direct reaction of aromatic
rings of linker, benzene-1,4-dicarboxylate, in MIL-101 with strong reagents [43]. Recently, Goesten et
al. [44] reported attachment of chloromethyl functional group into MIL-101(Cr) by post synthetic
modification of aromatic rings of MIL-101(Cr) using methoxyacetyl chloride. The chlorine atom in the
2

structure of chloromethylated MIL-101(Cr), CM-MIL-101(Cr), can be substituted with any
nucleophile.
In continuation our previous work in the oxidation of hydrocarbons catalyzed by MOF supported
metalloporphyrins [45], here; we report the preparation of modified MIL-101 by substitution of
chlorine atom of CM-MIL-101(Cr) with imidazole. This Im-MIL-101 was used as a support for
immobilization of Mn(TPP)Cl. The catalytic activity of Mn(TPP)Cl@Im-MIL-101 was investigated in
the alkene epoxidation and alkane hydroxylation as a recyclable and sustainable catalyst (Scheme 1).
Scheme 1.
2. Experimental
2.1. Reagents and methods
All materials were commercial reagent grade. Alkenes, alkanes and alkylaromatic compounds were
obtained from Merck or Fluka chemical companies. All of these compounds were passed through a
column containing active alumina to remove peroxidic impurities. Tetraphenylporphyrin was prepared
and metallated according to a literature procedure [46].
The diffuse reflectance UV–vis spectra were recorded by a JASCO V-670 UV–vis spectrophotometer.
Diffuse reflectance FT-IR spectra were obtained with potassium bromide pellets in the range of 400–
4000 cm-1 with a JASCO 6300 spectrophotometer. The XRD patterns were recorded using a Bruker D8
ADVANCE X-ray diffractometer equipped with nickel monochromatized Cu Kα radiation (λ = 1.5406
Ǻ). The scanning electron micrographs were taken on a Hitachi S-4700 field emission-scanning
electron microscope (FE-SEM). Specific surface area was measured by adsorption–desorption of N2
gas at 77 K with ASAP 2000 Micromeritics instrument. The ICP analyses were carried out by a Jarrell-
Ash 1100 spectrometer. Elemental analysis was performed on a LECO, CHNS-932 analyzer. Gas
chromatography experiments (GC) were performed with a Shimadzu GC-16A instrument using a 2 m
3

column packed with silicon DC-200 or Carbowax 20M. In the GC experiments, n-decane was used as
the internal standard.
2.2. Preparation of the catalyst
MIL-101(Cr) and chloromethylated MIL-101were synthesized based on the procedure reported by
Férey et al. [41] and Goesten et al. [44], respectively. The resulting CM-MIL-101(Cr) was modified
with imidazole through the same method described by Alvarez-Builla et al. [47]. In a typical procedure,
imidazole (0.68 g) and NaI (0.01 g) were added to a mixture of CM-MIL-101 (1 g) in CH3CN (20 ml)
and refluxed for 48 h. Then, the solid was filtered off, washed with CH3CN, K2CO3/H2O,
methanol/H2O and methanol/diethyl ether and dried in vacuum for several hours. The prepared Im-
MIL-101was used as support for immobilization of Mn(TPP)Cl via axial ligation. For this purpose, to a
solution of 0.25 g (0.32 mmol) manganese(III) tetraphenylporphyrin in toluene (25 mL), Im-MIL-101
(2 g) was added and the mixture was vigorously stirred at 80oC for 48 h. After cooling, the dark green
powder was collected by filtration, washed thoroughly with toluene, dichloromethane and acetone,
respectively, and dried at room temperature. The manganese content of the heterogenized catalyst was
determined by ICP.
2.4. Catalytic experiments
All of the reactions were carried out at room temperature with magnetic stirring. To a mixture of alkene
or alkane (1 mmol), Mn(TPP)Cl@Im-MIL-101(100 mg) in CH3CN (10 mL), a solution of NaIO4 (2
mmol) in H2O (10 mL) was added. The reaction mixture was stirred at room temperature. The progress
of the reaction was monitored by GC. At the end of the reaction, the mixture was diluted with Et2O (20
ml) and filtered. The catalyst was thoroughly washed with Et2O and the combined washings and
filtrates were purified on a silica gel plates or a silica gel column to afford the product.
The reusability of the Mn(TPP)Cl@Im-MIL-101 was investigated in the multiple sequential
epoxidation of cyclooctene as described above. At the end of each reaction, the catalyst was separated
4

from the reaction mixture by filtration, washed with acetonitrile and Et2O and dried before reusing. The
catalyst was consecutively reused four times without a detectable catalyst leaching or a significant loss
of its activity. The catalyst stability was followed by XRD, FT-IR and solid state UV-vis.
3. Results and discussion
3.1. Preparation and characterization of the catalyst, Mn(TPP)Cl@Im-MIL-101
Scheme 2 shows the preparation procedure for immobilization of Mn(TPP)Cl on imidazole modified
CM-MIL-101. First, the Im-MIL-101 was prepared by the reaction of imidazole with –CH2Cl group. In
the next step, the Mn(TPP)Cl was reacted with Im-MIL-101 via axial ligation to obtain the catalyst. In
biomimetic oxidations with NaIO4 catalyzed Mn(III) porphyrin as catalyst, imidazole has a co-catalytic
role [48-50]. In this catalytic system, the Im-MIL-101 not only used as support but also applied as a
heterogeneous axial base.
Scheme 2
During the conversion of MIL-101 to Mn(TPP)Cl@Im-MIL-101, the color changed clearly from green-
blue to green (Fig. 1).
Fig. 1
The synthesized hybrid catalyst was characterized by diffuse reflectance FT-IR and diffuses reflectance
UV-vis spectroscopic methods, inductively coupled plasma, elemental analysis, XRD, BET and SEM
methods. The nitrogen content of the support was determined by CHN analysis which showed a value
of about 2.98%. According to this value, the degree of imidazole which was introduced into the CM-
MIL-101 was 1.06 mmol/g of support. The Mn content of the catalyst, measured by ICP analysis, was
obtained 0.098 mmol/g of Mn(TPP)Cl@Im-MIL-101.
The most prominent spectroscopic data, which confirmed the anchoring of the Mn(TPP)Cl on the Im-
MIL-101, were obtained by comparison of the diffuse reflectance UV-vis spectra of Im-MIL-101 and
Mn(TPP)Cl@Im-MIL-101 (Fig. 2) with the UV-vis spectrum of homogeneous Mn(TPP)Cl (Fig. 3).
5

The appearance of Soret and Q bands of homogeneous manganese tetraphenylporphyrin with a slight
shift in the supported catalyst clearly indicated the presence of the metalloporphyrin on the support.
Fig. 2 and 3
The FT-IR spectrum (Fig. 4A) and XRD pattern (Fig. 5A) of MIL-101 match well with the literature
[30, 51]. The characteristic vibrational bands of the framework, -(O-C-O)- groups, around 1550 and
1400 cm−1 in the FT-IR spectra (Fig. 4) are preserved and confirm the stability of framework during
modification process and attachment of the metalloporphyrin. In the FT-IR spectrum of Im-MIL-
101(Fig. 4C), the C=N vibrational band of imidazole group appears in 1549 cm-1 which confirmed the
anchoring of imidazole to CM-MIL-101. This characteristic band showed a slight shift to 1560 cm-1
after attachment of Mn(TPP)Cl to Im-MIL-101 (Fig. 4D). Comparison of this spectrum with the FT-IR
spectrum of metalloporphyrin (Fig. 4F) showed the characteristic bands of pure metalloporphyrin in the
supported catalyst at 1091 and 1256 cm-1 which proved the coordination of Mn(TPP)Cl to the support.
Fig. 4
It is obvious from the XRD patterns (Fig. 5B and 5C) that the crystallinity of MIL-101 is maintained
after chloromethylation and imidazole modification, respectively. The additional peak in Fig. 5D,
corresponding to Mn(TPP)Cl (Fig. 5F), is a strong evidence for the synthesis of Mn(TPP)Cl@Im-MIL-
101.
Fig. 5
The FE-SEM images of the catalyst, Im-MIL-101, CM-MIL-101 and MIL-101 are shown in Fig. 6.
These images show that the morphology of MIL-101 are octahedral and maintain during modification
and attachment of metalloporphyrin.
The energy dispersive X-ray (EDX) results, obtained from SEM analysis for the catalyst in Fig. 6E
clearly show the presence of Mn in Mn(TPP)Cl@Im-MIL-101.
Fig. 6
6

The specific surface area of Mn(TPP)Cl@Im-MIL-101, determined using nitrogen physisorption
measurements at low temperature (Fig. 7), shows a predictable decrease in pore volume compared to
MIL-101. The BET surface area decreased from 2125 to 1117 m2g−1.
Fig. 7
The TEM images showed that the Mn(TPP)Cl was homogeneously dispersed on the MIL-101 support
(Fig. 8B) and after reusing the catalyst in the epoxidation of cyclooctene, no obvious change which
represent the aggregation was observed (Fig. 8C).
Fig. 8
3. 2. Catalytic experiments
At first, the catalyst amount was optimized in the epoxidation of cyclooctene (0.5 mmol) with NaIO4 (1
mmol). The best results were obtained with 100 mg (0.0098 mmol) of the catalyst (Fig. 9).
A blank experiment in the presence of oxidant and pure MIL-101 under the same reaction conditions
was also investigated. The obtained results showed that only 8% cyclooctene oxide was detected in the
reaction mixture by GC. Also in the presence of sole oxidant and in the absence of catalyst, only 5% of
the desired product was produced. Recently, we reported the catalytic activity of MIL-101 in the
oxidation of alkenes with H2O2 under reflux conditions in which the alkenes were converted directly to
diacids. In those experiments, the catalytic active site is Cr [51]. But in the present work, the pure MIL-
101 is inactive using NaIO4 as oxidant, and only 8% of the cyclooctene oxide was produced in the
presence of pure MIL-101. These observations prove that the catalytic active site is Mn species.
Fig. 9
The effect of different oxidants on the epoxidation of cyclooctene catalyzed by Mn(TPP)Cl@Im-MIL-
101 was investigated. The results obtained at room temperature are summarized in Table 1. The results
7

show that NaIO4 is the best oxygen source because this oxidant, which is inert in the absence of
catalyst, can give good oxidation conversion in CH3CN/H2O mixture.
Table 1
Different alkenes and alkanes were oxidized with NaIO4 in the presence of the prepared catalyst
Mn(TPP)Cl@Im-MIL-101 at room temperature in a 1:1 mixture of acetonitrile/water as the reaction
medium. The optimized reaction parameters used for the epoxidation of cyclooctene was catalyst,
oxidant and substrate in a molar ratio of 0.0098: 1: 0.5 and Im-MIL-101 plays the role of support as
well as co-catalytic axial ligand in this catalytic system. The Mn(TPP)Cl@Im-MIL-101 was found as
an efficient catalyst for the epoxidation of alkenes with NaIO4 (Table 2). This heterogenized catalytic
system showed good activity in the oxidation of cyclooctene and afforded the cyclooctene oxide in
96%. In the case of cyclohexene, the major product was cyclohexene oxide (82%) and 2-cyclohexen-1-
one was produced as a minor product (10%). Epoxidation of styrene yielded styrene oxide as the major
product with only a small amount of benzaldehyde. The epoxidation of linear alkenes such as 1-octene
and 1-decene was also investigated which showed high yields with 100% selectivity.
Cyclic alkenes are more reactive than linear ones. In the case of linear alkenes, upon increasing the
alkene chain, its mobility toward catalyst active site decreases and therefore its reactivity reduces.
Table 2
The catalytic oxidation of alkanes is also one of the typical challenging problems in organic chemistry.
For this purpose the catalytic activity of Mn(TPP)Cl@Im-MIL-101 was investigated in biomimetic
oxidation of saturated hydrocarbons. This catalytic system converts different alkanes to their
corresponding alcohols and ketones. Cyclooctane, cyclohexane and tetralin were oxidized in high
yields to their corresponding alcohols and ketones. In contrast, ethylbenzene and propylbenzene only
produced the corresponding ketones (Table 3). As mentioned before in biomimetic systems using
manganese porphyrins as catalysts, addition of a п-donor base increases the stability of the metal oxo
8

complex and increase catalytic activity. Actually, imidazole coordinates to Mn and activates the
catalyst [48, 49]. In this case, by using Im-MIL-101, it is possible to immobilize Mn(TPP)Cl and obtain
a pentacoordinate Mn(III) complex which leaves a vacant position on the manganese for catalysis.
Table 3
Our research group, previously, reported the catalytic activity of Mn(TPP)Cl immobilized on silica
[15], polystyrene [16] and carbon nanotubes [7] in the oxidation of hydrocarbons. Comparison of this
new supported Mn(TPP)Cl catalytic system with these three systems show that Mn(TPP)Cl@Im-MIL-
101 is more efficient and have higher catalytic activity than other ones (Table 4). This can be related to
higher specific surface area of MIL-101 and isolation of catalytic active sites, which in turns increases
the catalytic activity.
Table 4
3.5. Catalyst reuse and stability
The stability and reusability of a heterogeneous catalyst is very significant for economical purposes. In
this manner, for completion of our study, the reusability of Mn(TPP)Cl@Im-MIL-101 was checked in
the multiple sequential epoxidation of cyclooctene with NaIO4. As shown in Table 5, the catalyst could
be reused for four consecutive times without significant loss of its catalytic activity. After each
reaction, the filtrates were collected for determination of the Mn leached. The amounts of Mn leached
after each run was determined by ICP. No remarkable manganese was detected in the filtrates.
Table 5
4. Conclusion
In conclusion, we reported Mn(TPP)Cl@Im-MIL-101 as a highly efficient and reusable heterogeneous
catalytic system in oxidation of alkenes and alkanes. This new heterogeneous catalyst was synthesized
by covalent attachment of manganese(III)tetraphenylporphyrin to chloromethylated MIL-101(Cr)
9

modified with imidazole by elimination of chlorine atom. The catalyst showed several unique features
such as excellent yields, noticeable reusability, mild reaction conditions and easy work up.
Acknowledgment
The support of this work by the Center of Excellence of Chemistry of the University of Isfahan
(CECUI) is acknowledged.
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[45] F. Zadehahmadi, S. Tangestaninejad, M. Moghadam, V. Mirkhani, I. Mohammadpoor-Baltork,
A.R. Khosropour, R. Kardanpour, Appl. Catal. A: Gen. 477 (2014) 34-41.
[46] A.D. Adler, F.R. Longo, F. Kampas, J. Kim, J. Inorg. Nucl. Chem. 32 (1970) 2443-2445.
[47] M.L. Linares, N. Sánchez, R. Alajarín, J.J. Vaquero, J. Alvarez-Builla, Synthesis 2001 (2001)
0382-0388.
[48] S. Tangestaninejad, M. Moghadam, J. Chem. Res. (S) (1998) 242-243.
[49] S. Tangestaninejad, M. Habibi, V. Mirkhani, M. Moghadam, Molecules 7 (2002) 264-270.
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(2004) 9-12.
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Commun. 17 (2012) 18-22.
13

Fig. 1. The color change during the preparation of Mn(TPP)Cl@Im-MIL-101 from MIL-101
Fig. 2. Diffuse reflectance UV–vis spectrum of: (A) Im-MIL-101, (B) Mn(TPP)Cl@Im-MIL-101 and
(C) Recovered catalyst
Fig. 3. The UV–Vis spectrum of homogeneous [Mn(TPP)Cl]
Fig. 4. FT-IR spectrum of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-
MIL-101; (E) Recovered catalyst and (F) Mn(TPP)Cl
Fig. 5. XRD pattern of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-MIL-
101: (E) Recovered catalyst and (F) Mn(TPP)Cl
Fig. 6. FE-SEM image of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-
MIL-101 and (E) SEM-EDX spectrum of Mn(TPP)Cl@Im-MIL-101 (Al is for sample holder)
Fig. 7. N2 Adsorption/ desorption isotherm of: (A) MIL-101 and (B) Mn(TPP)Cl@Im-MIL-101 (■
Adsorption, □ Desorption)
Fig. 8. TEM image of: (A) MIL-101; (B) Mn(TPP)Cl@Im-MIL-101 and (C) Recovered catalyst
Fig. 9. Optimization of the catalyst amount in the epoxidation of cyclooctene with NaIO4 at room
temperature (Reaction conditions: cyclooctene (0.5 mmol), oxidant (1 mmol), catalyst, CH3CN/ H2O (5
ml/ 5 ml).
14

O
or
Mn(TPP)Cl@Im-MIL-101
NaIO4/ CH3CN/ H2O
or
OH
O
R1
R2
R1
R2
1
R2
+
R
Scheme 1. Epoxidation of alkenes and hydroxylation of alkanes with NaIO4 catalyzed by
Mn(TPP)Cl@Im-MIL-101
O
O
O
O
O
O
O
N
MeOAcCl
AlCl3
CH3CN/Imidazole
NaI/Reflux
Cl
N
MeNO2
N
O
O
O
O
O
Cl
N
N
N
O
O
N
N
N
N
N
Mn
Cl
O
O
N
Scheme 2. Preparation of Mn(TPP)Cl@Im-MIL-101
15

Fig. 1. The color change during the preparation of Mn(TPP)Cl@Im-MIL-101 from MIL-101
B
C
A
200
400
600
800
Fig. 2. Diffuse reflectance UV–vis spectrum of: (A) Im-MIL-101, (B) Mn(TPP)Cl@Im-MIL-101 and
(C) Recovered catalyst
16

Fig. 3. The UV–Vis spectrum of homogeneous [Mn(TPP)Cl]
17

3200 2800 2400 2000 1600 1200 800
400
A
B
C
D
E
F
Wavenumber (cm-1)
Fig. 4. FT-IR spectrum of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-
MIL-101; (E) Recovered catalyst and (F) Mn(TPP)Cl
18

F
E
D
C
B
A
1
2
3
4
5
6
7
8
9
10 11 12 13 14 15 16 17 18 19 20
2Θ (o)
Fig. 5. XRD pattern of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-MIL-
101: (E) Recovered catalyst and (F) Mn(TPP)Cl
19

Fig. 6. FE-SEM image of: (A) MIL-101; (B) CM-MIL-101; (C) Im-MIL-101; (D) Mn(TPP)Cl@Im-
MIL-101 and (E) SEM-EDX spectrum of Mn(TPP)Cl@Im-MIL-101 (Al is for sample holder).
20

Fig. 7. N2 Adsorption/ desorption isotherm of: (A) MIL-101 and (B) Mn(TPP)Cl@Im-MIL-101 (■
Adsorption, □ Desorption)
21

Fig. 8. TEM images of: (A) MIL-101; (B) Mn(TPP)Cl@Im-MIL-101 and (C) Recovered catalyst.
22

100
80
60
40
20
0
0
50
70
100
120
Amount of catalyst (mg)
Fig. 9. Optimization of the catalyst amount in the epoxidation of cyclooctene
with NaIO4 at room temperature (Reaction conditions: cyclooctene (0.5 mmol),
oxidant (1 mmol), catalyst, CH3CN/ H2O (5 ml/ 5 ml).
Table 1. The effect of oxidant on the epoxidation of cyclooctene catalyzed by [Mn(TPP)Cl@Im-
MIL-101] at room temperature.a
Entry
Oxidant
NaIO4 (1 mmol)
NaIO4 (0.5mmol)
H2O2
Solvent
CH3CN/H2O
CH3CN/H2O
CH3CN
Epoxide yield (%)b
1
2
3
4
5
96
44
40
29
18
Urea-H2O2 (UHP)
tert-BuOOH
CH3CN
CH3CN
aReaction conditions: cyclooctene (0.5 mmol), oxidant (1 mmol), catalyst (100 mg), CH3CN/ H2O (5
ml/ 5 ml).
bGC yield based on the starting alkene.
23

Table 2. Epoxidation of alkenes with NaIO4 catalyzed by Mn(TPP)/Im-MIL-101.a
Entry
1
Alkene
Conversion (%)b
96
Epoxide yield (%)b
96
Time (h)
2.5
TOF (h-1)
19.6
2
3
92c
94d
82
83
2.5
2.5
16.7
16.9
4
5
1-Octene
1-Decene
76
48
76
48
3.5
3.5
11.1
7.0
aReaction conditions: alkene (0.5 mmol), NaIO4 (1 mmol), catalyst (0.0098 mmol), CH3CN/H2O (5/5
ml).
bGC yield based on the starting alkene.
cThe by-product is allylic ketone.
dThe by product is benzaldehyde.
Table 3. Hydroxylation of alkanes with NaIO4 catalyzed by Mn(TPP)/Im-MIL-101.a
Entry Alkane
1
Conversion (%)b Ketone (%)b Alcohol (%)b
Time (h) TOF (h-1)
75
45
30
4
9.5
2
58
49
9
4
7.3
3
4
5
53c
50d
69e
53
50
48
-
-
4
4
4
6.8
6.4
8.8
21
24

aReaction conditions: alkane (0.5 mmol), NaIO4 (1 mmol), catalyst (0.0098 mmol), CH3CN/H2O (5/5
ml).
bGLC yield based on the starting alkane.
cThe product is acetophenone.
dThe product is ethyl phenyl ketone.
eOnly the α-position was oxidized.
Table 4. Comparison of the results obtained for the oxidation of cyclooctene with
NaIO4under magnetic stirring catalyzed by manganese porphyrins with those obtained
by the recently reported catalysts.
Row
Catalyst
TOF (h-1)
8.33
Ref
[15]
1
2
3
4
5
Mn(TPP)Cl-SiIm
Mn(TPP)-PSI
16.2
[16]
Mn(TPP)Cl-APy-MWCNT
Mn(TPP)Cl-AP-MWCNT
Mn(TPP)Cl/Im-MIL-101
10.26
7.59
[7]
[7]
19.6
Present work
25

Table 5. Recyclability of Mn(TPP)/Im-MIL-101 in the
epoxidation of cyclooctene.a
run
1
Yield (%)b
Mn leached (%)c
96
92
88
88
1.1
0.6
0
2
3
4
0
aReaction conditions: cyclooctene (0.5mmol), NaIO4 (1 mmol),
catalyst (100 mg), CH3CN/H2O (5/5 mL).
bGC yield based on the starting alkene.
cDetermined by ICP.
Graphical
O
O
O
O
N
N
O
N
N
N
Mn
Cl
N
or
+
or
O
OH
NaIO4 /CH3CN/ H2O
R1
R2
R1
R2
R1
R2
MIL‐101 was modified by covalent post synthetic modification ► Mn(TPP)Cl was anchored to imidazole
modified MIL‐101 by covalent attachment ► A heterogeneous catalyst was prepared ► The catalyst was used
for epoxidation of alkenes and hydroxylation of alkanes ► The catalyst was reusable
26