"ship in a bottle" Porph@MOMs as highly efficient catalysts for selective controllable oxidation and insights into different mechanisms in heterogeneous and homogeneous environments

Article abstract of DOI:10.1039/c8nj00315g

In the present work, three "ship in a bottle" Porph@MOMs are reported as biomimetic oxidation catalysts for different reactions. These frameworks are constructed from trimesic acid and metal ions (M = Fe, Co and Mn) in which tetra(N-methyl-4-pyridyl)porphyrin (MTMPyP) is encapsulated within the cavities. Additionally, the catalytic activities of the corresponding homogeneous compounds, FeTMPyP, CoTMPyP and MnTMPyP, and the frameworks without porphyrins within the cavities were investigated in the foregoing oxidation reactions. The prepared 3D porous structures have the ability to control selectivity toward the desired product. Furthermore, they are capable of acting as effective peroxidase mimics, which successfully catalyze the oxidation of diverse olefins as well as hydrocarbons using TBHP as an oxidant. The heterogeneous catalysts significantly enhance conversion in contrast to their corresponding homogeneous systems. Remarkably, an insight into the catalyst behavior was gained from the proposed mechanism based on the reversal of selectivity. Investigation of the stability and reusability of the catalysts revealed the heterogeneity character of the catalyst with no desorption during the course of oxidation reactions. The high yields, clean reactions, high thermal stability and reusability of the catalysts make them good candidates for heterogeneous catalysts in various oxidation reactions.

Full text of DOI:10.1039/c8nj00315g

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ISSN 1144-0546
PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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“Ship in bottle” Porph@MOMs as highly efficient catalysts for
selective controllable oxidation and insights into different
mechanism in heterogeneous and homogeneous environment
Received 00th January 20xx,
Accepted 00th January 20xx
M. Saghian,a S. Dehghanpour*a and M. Sharbatdaranb
DOI: 10.1039/x0xx00000x
In the present work, three “ship in bottle” Porph@MOMs are reported as biomimetic oxidation catalysts for different
reactions. The frameworks are constructed from trimesic acid and metal ions (M= Fe, Co and Mn) in which tetra(N-methyl-
4-pyridyl) porphyrin (MTMPyP) is encapsulated within the cavities. Additionally, the catalytic activity of the corresponding
homogeneous compounds, FeTMPyP, CoTMPyP and MnTMPyP, and the frameworks without porphyrins within the
cavities were investigated in the foregoing oxidation reactions. The prepared 3D porous structures have the ability to
control selectivity toward the desired product. Furthermore, they are capable of acting as effective peroxidase mimics,
which successfully catalyze oxidation of diverse olefins as well as hydrocarbons using TBHP as oxidant. The heterogeneous
catalysts significantly enhance conversion in contrast to their corresponding homogeneous systems. Remarkably, an
insight into the catalyst behavior was gained from the proposed mechanism based on the reversal of selectivity.
Investigation of the stability and reusability of the catalysts revealed the heterogeneity character of the catalyst with no
desorption during the course of oxidation reactions. High yields, clean reactions, high thermal stability and reusability of
catalysts, make them good candidates for heterogeneous catalyst in various oxidation reactions.
www.rsc.org/
extensively explored as catalysts in various oxidation reactions
carried out with Cytochrome P450.9-11 Notwithstanding the
high catalytic activity of these compounds, they have also
Introduction
Nowadays, alkene oxidation is one of the most important
reactions in industry due to the importance and usefulness of
epoxy precursors in the manufacture of different commercial
products. However, epoxide selectivity is still a major challenge
because of the byproducts formation in these reactions.1-3 On
the other hand, another very important issue in organic
synthesis is the selective oxidation of saturated hydrocarbons
some
disadvantageous.
Overall,
homogenous
metalloporphyrin catalysts suffer from limited lifespan activity
due to deactivation or degradation in the reaction medium
which is caused by the formation of bridge μ-oxo dimers, self-
aggregation because of π-π stacking or self-oxidation of the
active centers.12, 13 One of the best ways to overcome these
major drawbacks is to stabilize metalloporphyrin onto
different solid supports such as zeolites, ion-exchange resins,
silica and polymers.14-19 These heterogeneous catalysts dispel
the defects of heterogeneous systems and subsequently can
be easily isolated from the reaction media and show higher
stability due to protection of their catalytic site.20 Among
different possible catalyst supports, metal-organic frameworks
(MOFs) have attracted the attention of many researchers in
under mild conditions.4 Because of the inactivity of C
ꟷ H
bonds, oxidation of alkanes requires strong catalysts with high
catalytic activity.5 Different catalysts have been used in these
fields such as Cytochrome P450.
Cytochrome P450 is one of the most important
monooxygenase enzymes which catalyze oxygenation
reactions in the chemical and biological communities via
formation of high-valent metal-oxo species. Researchers are
trying to mimic this enzyme because of the high cost, difficult
sequestration and limitations found while working in the
laboratory.6-8 Metalloporphyrins are one of the best models
introduced to the Cytochrome P450 enzyme. They have been
recent years because of their various applications and
properties.21,
22
These compounds, which are composed of
inorganic clusters/metal ions connecting to organic linkers,
have emerged as new particular subset of porous
a
coordination polymers (PCPs).23 They are widely used for
diverse applications owing to their unique and remarkable
attributes such as high surface areas, tuneable pore structure,
high stability and structural diversity. Porphyrins can take part
in the structure of MOFs and are therefore stabilized in two
ways: they are placed as struts in MOFs via the functional
group at their peripheries (PorphMOMs)24, 25 or encapsulated
in the pore of the structure with regard to the proportion of
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their diameter to the volume of the cavity (Porph@MOMs)26, 27 flask. The reaction was started by adding TBHP (3 mmol, 0.4
and subsequently can be used as efficient catalysts. Among ml, 70% in H2O). The mixture obtained was then refluxed for 6
various porphyrins assembled in porphyrinic frameworks, h. The catalyst was filtered and the filtrate was subjected to GC
carboxy and pyridyl derivatives have been widely used. and GC–MS analyses. The, Fe, Co and Mn contents of the
Carboxy-based porphyrin ligands are used only as bridging recycled catalyst were measured using ICP-OES techniques.
ligands in MOFs whereas pyridyl derivatives can be either used
as struts or encapsulated within the cavities of the structure.
Results and discussion
In spite of many attempts in using carboxy porphyrinic
frameworks as catalysts,28-30 there are few reports on
Characterization of catalysts
utilization of porphyrins with pyridyl functional groups and
Synthesis and description of catalysts. Porphyrins and
their derivatives.
metalloporphyrins were synthesized through little method32,
Herein, the preparation and structural analysis of three
metalloporphyrinic MOFs constructed by meso-Tetra(N-
1
33. Their structures were characterized using UV-Vis, H NMR
and FT-IR spectroscopy. H2TMPyP and Trimesic acid with
methyl-4-pyridyl) porphyrin and metal ions such as Fe, Co and
FeCl2.4H2O, CoCl2.6H2O and MnCl2.4H2O were applied in the
Mn are reported. These structures are used as heterogeneous
solvothermal synthesis of Porph@MOM-4, Porph@MOM-5
catalysts in the selective oxidation of diverse alkenes and
and Porph@MOM-6, respectively (Scheme 1)31. FT-IR
alkanes with tert-Butyl hydroperoxide (TBHP) as the oxidant.
spectroscopy, PXRD, XPS, TGA, SEM and ICP techniques were
For further investigation, the catalytic activities of relevant
used for characterization of these MOFs.
metalloporphyrins were evaluated in homogeneous
environment. Furthermore, the mechanism of reactions in
Characterization of Porph@MOMs. Upon encapsulation of
both heterogeneous and homogeneous environment was also
porphyrin within the MOFs, some changes occur in the
investigated. The details of activity, selectivity, stability and
structure and properties of these compounds.
reusability of the catalyst will also be discussed.
As can be seen in FT-IR spectrum of Porph@MOM-4 (Fig.
S1c), the bands appearing at 1382 and 1639 cm-1 correspond
Experimental
to the symmetric and asymmetric COO stretching vibrations,
respectively.34 Furthermore, the out-of-plane deformation
Materials and instrumentation
vibrations of the C H groups in the benzene ring become
Material and instrumentation are explained in supporting
manifest at 715 and 769 cm-1. The band attributed to the
information.
stretching vibration of C N pyridyl ring overlaps with the
asymmetric stretching vibration band of carboxylic acid
Synthesis of catalysts
functional group. FT-IR spectra of Porph@MOM-4,
Porph@MOM-5 and Porph@MOM-6 before and after being
used as catalyst are exhibited in Fig. S2, S3 and S4,
The synthesis procedure for 5, 10, 15, 20- Tetra(4-pyridyl)
porphyrin (H2TPyP) and meso-Tetra(N-methyl-4-pyridyl) porphyrin
(H2TMPyP) were explained in supporting information.
respectively. They all show the same pattern
.
XRD patterns of the as-synthesized compounds before and
after being used as catalysts (after 5 cycles) are presented in
Fig. S5. As shown in this Figure, in each picture the main
diffraction peaks of the as-synthesized compounds are
thoroughly in accommodation with those of the simulated
Porph@MOMs,31 confirming the construction of the desired
crystalline structures. Furthermore, it can be observed that
after using the aforementioned catalysts in oxidation reactions
for 5 cycles, the crystal structure of these compounds has been
Synthesis and purification of Porph@MOM-4. Porph@MOM-4
was synthesized according to the previously reported
method31. In a typical synthesis, FeCl2.4H2O (238.8 mg, 1.20
mmol), Trimesic acid (126 mg, 0.60 mmol), H2TMPyP (8.4 mg,
0.0063 mmol), N, N-dimethylformamide (16.5 ml), H2O (3 ml)
were mixed and homogenized by stirring at room
temperature. The resulting dark red solution was transferred
to Teflon-lined steel autoclave and heated at 85 °C for 12 h.
The resulting solid powder was decanted and washed with
methanol in order to remove unreacted porphyrins from
solution. FT-IR (KBr, cm-1): 3435 (m), 1639 (s), 1581 (m), 1452
(m), 1382 (s), 1122(w), 954 (w), 769 (m), 715 (s), 632 (w).
The synthesis procedure for Porph@MOM-5 and Porph@MOM-6
were explained in supporting information.
Catalytic studies
The catalytic reactions were carried out in a sealed round
bottomed flask equipped with
a magnetic stirrer and
condenser. In atypical procedure, the alkenes/alkanes (2
mmol), catalyst (5 mg) and CH3CN (5 ml) were added into the
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MnIII2p1/2 and MnIII2p3/2 of the corresponding manganese
porphyrin, respectively. In retrospect, the appearance of
maintained. Besides, the structures of CoBTC, FeBTC and
MnBTC frameworks without porphyrin molecules within their
cavities are represented in Fig. S6, S7 and S8, respectively. satellite peaks at higher binding energy is owing to the
electron-withdrawing effect of porphyrin ligand. The N1s
These results agree with the structures previously reported.35-
37
region for Porph@MoM-6 (Fig. 1f) can be divided into two
peaks with identical contributions at 399.2 and 401.3 eV,
XPS analysis was carried out for Porph@MOM-4,
assigned to the pyrrolic N and quaternary N of manganese
Porph@MOM-5 and Porph@MOM-6 in order to gain
porphyrin, respectively.40, 41 Also, the XPS spectrum of the O1s
information about surface compositions, bonding states and
indicates only a broad single peak at 531 eV which is attributed
alternation in chemical environment of the elements. The
to the oxygen atom of carboxylic acid ligand in the
results are shown in Fig. 1a-f. XPS spectra of Porph@MOM-4
Porph@MOMs (Fig. S9b, d and f). Inspired by these results, the
are shown in Fig. 1a-b and Fig. S9a-b. From the survey
metal ions and N1s signals confirm the presence of related
spectrum in Fig. S9a remarkable signals corresponding to C, O,
matalloporphyrins in the framework. The ratio of FeII: FeIII is
Fe and N can be observed. As shown in Fig. 1a, the peaks at
95.64: 4.36%. The ratio of CoII: CoIII is 80.38: 19.62% and the ratio of
MnII: MnIII is 75.16: 24.84 %. The results show that the ratio of
components is in accordance with the amount of loading. Overall, in
XPS spectra, a small change in the position of peaks observed due
to the difference in the chemical environment and oxidation state.
Scanning electron microscopy (SEM) was accomplished to
specify the morphology of the samples. Therefore, MnBTC
framework without porphyrin molecules in the cavities shows
rod shaped particles with an average diameter of around 4
micrometers (Fig. 2a and b). However, upon encapsulation of
porphyrin into the framework, the representative SEM image
indicates well-defined octahedral morphology with an average
particle diameter of 2.2 micrometers (Fig. 2c and d). Such a
change in morphology was also observed for CoBTC and FeBTC
(Fig. S10 and Fig. S11, respectively). Consequently,
encapsulation triggers reduced particle size and morphology
change clearly observed in these micrographs.
725.7 and 711.9 eV can be attributed to the FeII2p1/2 and
FeII2p3/2 of the framework, respectively which are in
39
agreement the values reported before.38,
Interestingly,
beside the main peak of Fe2p, a feeble satellite peak with
lower intensity and at higher binding energy can be observed
at 717.3 and 730.9 eV. These peaks are attributed to the
FeIII2p3/2 and FeIII2p1/2 of metalloporphyrin existing in the
framework. The low intensity of these peaks represents the
lower contribution of related iron porphyrin in the framework
to iron nodes. Hence, due to the different environment of the
metal ions, two kinds of peaks related to the Fe2p can be seen.
Since Porphyrins are strong π-acceptor ligands, the related
peaks become apparent at higher binding energies.
Additionally, the high resolution of N1s spectrum of
Porph@MOM-4 exhibits two peaks at 398.8 and 401.3 eV
which are attributed to pyrrolic N and quaternary N of iron
porphyrin, respectively.40,
41
As observed in Fig. 1b,
Moreover, encapsulation of porphyrins into the framework
was confirmed by N2 adsorption-desorption isotherms. The N2
adsorption-desorption isotherms of (a) CoBTC and (b)
CoTMPyP are depicted in Fig. S12, indicating type IV isotherms,
and the textural parameters are presented in Table S1. Large
contribution of both signals are quite equal which is in
agreement with the number of nitrogen atoms in the
structure. Since the only nitrogen atom in the structure is
related to the corresponding metalloporphyrins, N signals
confirm the presence of porphyrin into the structure. Similarly,
for Porh@MOM-5 the full spectra regions were provided in
Fig. S9c which reveals the signals corresponding to C, O, Co
and N. As can be seen in Fig. 1c, the CoII2p1/2 and CoII2p3/2 of
the framework appear at binding energies of 796.7 and 781
43
The other
eV, as previously reported in the literature.42,
weak satellite peaks located at 801.7 and 785.6 eV can be
ascribed to the CoIII2p1/2 and CoIII2p3/2 of cobalt porphyrin
existent in the framework, respectively. These binding energy
increments of satellite peaks are because of the electron-
withdrawing effect of porphyrin. Fig. 1d shows N1s XPS spectra
of Porph@MOM-5 which indicates two peaks at 398.7 and
401.4 eV with equal contribution, corresponding to the
pyrrolic
N
and quaternary
N
of cobalt porphyrin,
respectively.40, 41 The XPS survey scan of Porph@MOM-6 in Fig.
S9e represents the existence of C, O, Mn and N elements.
Mn2p curve deconvolution yielded two pairs of peaks in
accordance with Mn2p and satellite peaks. Therefore, in the
high resolution spectra of Mn2p (Fig. 1e), two peaks located at
653.3 and 641.6 eV are associated with MnII2p1/2 and
MnII2p3/2
, respectively which are quite close to those
previously reported.44, 45 Moreover, the presence of two weak
satellite peaks at 657.9 and 645.8 eV are further indicative of
Fig. 1 XPS spectra of Porph@MOM-4 (a) Fe2p, (b) N 1s, Porph@MOM-5 (c) Co
2p, (d) N 1s, Porph@MOM-6 (e) Mn 2p, (f) N 1s.
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decrease in textural parameters is observed due to the
encapsulation of porphyrin in the framework.
The presence of porphyrin in the framework was also
confirmed by UV-Vis spectra. Afterwards, each sample of
Porph@MOMs was dissolved in water by adding a small
amount of HCl. The investigation of UV-Vis spectra clearly
affirmed the presence of metalloporphyrins into the
framework (Fig. S13). Moreover, to determine the presence of
porphyrin into the framework and the amount of framework
loading, ICP technique was performed. Based on the results,
the amount of porphyrin loading in the framework according
to the weight percent of iodine was obtained as 5, 24.5 and
32% for Porph@MOM-4, Porph@MOM-5 and Porph@MOM-6,
respectively. UV-Vis analysis calculation, using a calibration
curve, confirmed the aforementioned results about the
amount of loadings. Furthermore, CHN analysis was performed
in order to gain the amount of loading. But since solvent
molecules may get stuck into the cavities of the framework,
this analysis is not very efficient.
The effects of catalyst amounts are shown in Fig. S15,
reveal that increasing the amount of catalyst from 2 to 20 mg
enhances the conversion from 36 to 100, 60 to 100 and 44 to
Catalytic activity of catalysts
To evaluate the catalytic properties, Porph@MOMs were
prepared for the oxidation reaction of various alkenes/alkanes.
In order to evaluate the catalytic properties of porphyrins as
the active site of reactions, oxidation reactions were also
performed in the presence of the corresponding framework
100% for catalyst 1, 2 and 3, respectively with 85 to 95%
selectivity towards ketone product. Since the main product of
cyclohexene oxidation is ketone and epoxidation reactions
have been investigated, optimizing of another substrate which
without porphyrin molecules into the cavities. In addition, the has yielding epoxy upon oxidation was also performed and
similar results were obtained. With regards to the optimized
conversion and selectivity obtained using 5 mg of catalyst, all
alkene oxidation reactions were carried out using this amount.
In order to choose a suitable solvent, the oxidation of
cyclohexene was carried out in acetonitrile, dichloromethane,
chloroform and methanol (Fig. S16). The results indicate that
among different solvents, polar aprotic solvent acts better
than polar protic solvents and cause to increase the efficiency
of the catalysts. On the other hand, high conversion and
selectivity toward ketone was achieved in polar aprotic solvent
in the order of CHCl3< CH2Cl2 < C2H5OH < CH3CN. Therefore
acetonitrile shows the best catalytic activity due to its higher
dielectric constant. Consequently, based on the results,
increasing solvent polarity causes higher conversion in
cyclohexene oxidation.
catalytic activity of the corresponding homogeneous systems
(FeTMPyP, CoTMPyP and MnTMPyP) was also investigated in
order to compare the oxidation reactions and mechanism in
heterogeneous and homogeneous environment. Therefore,
the Porphyrinic frameworks which are porph@MOM-4,
porph@MOM-5 and porph@MOM-6 were used as catalysts
1,
2
and 3 and the corresponding metalloporphyrins (FeTMPyP,
CoTMPyP and MnTMPyP) were used as catalysts
the oxidation reactions, respectively.
4, 5 and 6 in
Oxidation of alkenes by Porph@MOMs
The catalyst performance of catalysts
1, 2 and 3 were
evaluated in the oxidation of aforementioned alkenes in terms
of activity, selectivity and recyclability. Cyclohexene was
selected as the representative substrate for the early
exploration of oxidation reactions. In order to study the effect
of time on product distribution, reaction times of 2, 4, 6,
8 and 10 h were examined in the presence of 5 mg of
The effect of catalysts on the oxidation reactions of other
alkenes is presented in Table 1. According to these results,
cyclohexene oxidation leads to the formation of ketone
product for all three catalysts. In contrast to other cases,
cyclohexene undergoes just allylic site oxidation. As indicated
in Table 1, cyclohexene was oxidized to the corresponding
ketones with 87, 90 and 94% selectivities under the effect of
catalyst
1, 2 and 3, and TBHP as oxidant (Fig. S14). Based on
the obtained results, the catalytic activity of the prepared
catalysts are strongly influenced by the reaction time. As seen,
cyclohexene is oxidized to the corresponding ketone with
catalysts 1, 2 and 3, respectively (entry 4, Table 1). Whereas
oxidation of norbornene and trans-stilbene were carried only
on double bond site and the corresponding epoxides were
selectively formed. Therefore, epoxide is the sole product of
these reactions and quantitative conversions and selectivities
are notable (entries 1 and 2, Table 1). In the cases of α-
methylstyrene, styrene and cyclooctene, oxidation reactions
100% conversion. The optimum time was 6 h for catalysts
1
and 2 and 10 h for catalyst 3. According to the results, after
the optimal time, the selectivity increases up to 98% towards
the ketone product for all catalysts.
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Table 1 Oxidation results of various alkenes in the presence of used catalysts.
Entry Substrate Catalyst
Conversiona
(%)
98
Selectivity (%)
ketone
TONb
epoxide
100
100
100
100
100
100
100
58
alcohol
1
4
0
0
0
0
0
0
0
0
10140
480
94
99
2
0
2069
502
1
5
98
98
0
3
6
1
4
0
1557
488
97
90
0
0
42c
0
0
9312
61
12
0
2
100
87
100
89
0
2090
446
11c
0
2
5
0
3
6
1
4
95
40
100
80
0
1509
201
20c
0
64
51
93
97
7d
0
6622
260
3d
0
33d
1d
2
90
82
67
99
0
1881
420
3
5
0
43d
3
6
1
4
68
43
57
97
0
1080
216
3d
0
100
97
0
87e
80e
90e
94e
94e
83e
21c
83c
29c
55c
17c
80c
13f
20f
10f
6f
6f
17f
0
10140
491
0
2
100
81
0
2069
397
4
5
0
3
6
1
4
100
84
0
1573
413
0
79
57
39
5798
199
17
71
0
2
81
65
0
1693
333
5
5
45
83
0
3
6
1
4
71
32
0
1128
161
20
0
100
22
72
28g
29g
16g
28g
35g
39g
0
17h
0
0
10347
113
54i
84
0
2
100
87
0
2090
445
6
5
67j
65
5h
0
0
3
6
100
80
0
1589
402
50k
11h
0
aReaction conditions: catalyst, 5 mg, alkenes (2 mmol) except for trans-stillbene (0.2 mmol), TBHP (3 mmol), solvent (acetonitrile, 5 ml,
reflux at 80 °C), time (6 h). bTON is the mmol of product to mmol of porphyrin present in catalyst. Byproducts: cBenzaldehyde,
dAcetophenone, e2-Cyclohexene-1-one, f2-Cyclohexene-1-ol, g2-Cyclooctene-1-one, hCyclooctanone.
were carried out on both double bond and allylic site. In each The appropriate obtained results prompted us to exert these
case, the respective epoxide was the major product and the catalytic systems in the oxidation of hydrocarbons. For this
corresponding ketone was the byproduct (entries 3, 5 and 6, purpose, the catalytic behavior of catalysts
1, 2 and 3 in
respectively, Table 1). Although both cyclohexene and oxidation of different alkanes were investigated. Similar the
cyclooctene substrates have allylic site, they yield different reactions of alkene oxidation were carried out, the effects of
products upon oxidation. Since the allylic site is more reactive reaction time and amount of the catalysts were investigated
than the double bond site in cyclohexene,46 the corresponding and the results are shown in Fig. S17 and Fig. S18, respectively.
ketone is the main product of this substrate. Whereas, in the According to the result in Fig. S17, time strongly affects the
case of cyclooctene, the reaction proceeds via concerted catalytic activity of the catalysts. Therefore, with increasing the
mechanism and epoxide is the major product. Moreover, reaction time, the conversion increased up to 100%. The
according to the results, high conversion (100%) was obtained optimum time was 6 h for catalyst
2 and 10 h for catalysts 1
for oxidation of norbornene, trans-stilbene, cyclohexene and and 3. The effects of the catalyst amount with respect to Fig.
cyclooctene (entries 1, 2, 4 and 6, respectively, Table 1).
S18, revealed that with increasing the catalyst amount from 2
to 20 mg, the conversion enhanced up to 100%. Based on the
obtained conversion and selectivity, the optimum amounts of
Oxidation of alkanes by Porph@MOMs
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the catalysts were achieved 10, 4 and 5 mg for catalysts
1,
2
product, respectively (entries 5 and 6, Table 2).
and 3, respectively. In these cases, the model substrate was
selectively converted to ketone, except for catalyst
showed 70% selectivity toward the ketone product.
2
which Comparison of oxidation reactions in homogeneous and
heterogeneous environment
The oxidation results of various alkanes under optimized
reaction conditions are given in Table 2. According to the
results, obtaining 100% conversion and selectivity for
It is interesting to note that there are remarkable differences
between substrate conversions in homogeneous and
heterogeneous systems in both cases of oxidation of alkenes
and alkanes. In spite of the fact that the catalysts in
homogeneous systems showed better activity,47 opposite
results were obtained in this research. Contrary to the
expectation, the encapsulated metalloporphyrins showed
better catalytic activity than the corresponding unsupported
analogs. This can be because heterogeneous systems prevent
the formation of bridge μ-oxo dimers which can deactivate the
catalyst active centers in the reaction medium and thereby
stabilize the intermediate species48 (Fig. 3). The μ-oxo dimers
cyclohexane, and fluorene using catalysts
1, 2 and 3 is
promising (entries 1 and 2, Table 2). In oxidation of
cyclooctane, high conversion (100%) was achieved for all
catalysts and the relevant ketone was the sole product for
catalysts
1 and 3. But in the case of catalyst 2, the
corresponding ketone was the main product (entry 3, Table 2).
Moreover, diphenylmethane oxidation also led to the
corresponding ketone as the major product (94%) (entry 4,
Table 2). In the oxidation of ethyl benzene and adamantane,
the relevant ketone and alcohol were obtained as the major
Table 2 Oxidation results of various alkanes in the presence of used catalysts.
Entry
Substrate
Catalyst Conversiona (%)
Selectivity (%)
ketone alcohol
TONb
1
4
2
5
3
6
1
4
2
5
3
6
1
4
2
5
3
6
1
4
2
5
3
6
1
4
2
5
3
6
1
4
2
5
3
6
100
100
100
100
100
100
100
35
100
100
100
100
100
100
100
100
100
100
100
100
100
76
0
0
5714
568
0
2898
569
1
0
0
1765
567
0
0
5714
199
0
100
85
0
2898
484
2
3
4
5
6
0
100
73
0
1765
414
0
100
25
0
5714
142
0c
0d
0e
0
100
42
70
81
2898
239
100
42
100
73
1765
238
0f
0g
0
0h
0i
0j
0
0k
0l
0m
0n
0o
0p
70
68
71
72
69
70
76
31
94
4343
176
100
94
81
52
2348
296
91
94
73
16
1289
91
100
64
67
35
3829
199
95
77
87
49
2522
279
85
61
51
42
900
238
90
30
66
42
3771
238
32
29
76
47
2203
267
28
31
78
36
1377
204
30
aReaction conditions: catalyst (10,
4 and 5 mg), alkanes (2 mmol), (flourene, diphenyl methane and
adamantane: 0.2 mmol)TBHP (3 mmol), solvent (acetonitrile, 5 ml, reflux at 80 °C). time (10 h). bTON is the
mmol of product to mmol of porphyrins present in catalyst. Byproducts: 1, 4-cyclooctane dione and
cycloheptane carboxylic acid c(19%) and (5%), d(19%) and (11%), e(11%) and (8%), (25%) and (11%). There is a
byproduct which can’t identify g(6%), h(6%), i(9%), j(6%). Benzaldehyde k(36%), l(5%), m(23%), n(15%), o(39%),
f
6 | J. Name., 2012, 00, 1-3
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species is not formed due to the steric hindrance and rigidity. revealed that the reaction proceeds via a radical mechanism
In fact, this causes catalysts and to show greater (Scheme 2). In the proposed mechanism, initially the oxo
efficiency than the corresponding homogeneous catalysts in intermediate was formed in the presence of the oxidant.
the oxidation of alkenes and alkanes. Henceforth, the substrate approached the intermediate and
1,
2
3
It is noteworthy that in some cases, selectivity is different formed a charge transfer complex with the MV(O)P active
in oxidation of alkenes in heterogeneous and homogeneous species (Scheme 2, route A). Afterwards, the charge transfer
systems (entries 2 and 5, Table 1). According to the results, complex procreated a solvent caged alkyl radical by electron
styrene can be oxidized on both double bond and allylic site. transfer between the substrate and the active species (Scheme
With this regard, it can be seen that using catalysts
1
,
2
and
3
2, route B).49 The alkyl radical tended to transfer electron from
as heterogeneous catalysts gave the respective epoxide and the alkene to the MIV(O)P+. active species and subsequently
ketone as the major product and byproduct, repectively. afforded a carbocation intermediate. Eventually, with the
Whereas, when the related homogeneous catalysts (catalysts withdrawal of epoxy product, the active species returned to its
2, 4 and 6) were used, the results were completely reversed. principal state. Alkene epoxidation could occur via either the
Therefore in homogeneous systems the corresponding ketone aforementioned mechanism or concerted mechanism (Scheme
was the major product and the epoxide was the byproduct 2, route C)49 and the epoxy product was generated.
(entry 5, Table 1). Moreover in oxidation of trans-stilbene, Remarkably, alkenes could undergo allylic site oxidation to
epoxide was the sole product of the reaction using catalysts
and . However, the corresponding homogeneous catalysts formation of the oxo intermediate, reactions proceeded
led to the formation of the byproduct (entry 2, Table 1). These through allylic oxidation. This means that the oxo intermediate
1,
form the corresponding products. In these cases, after
2
3
changes in selectivity will be discussed later.
abstracted an active hydrogen from allylic C H bond and
produced a caged cycloalkenyl radical and the MIV(OH)P π-
cation radical active species (Scheme 2, route D). In the next
step, the relative cycloalkenyl radical could evade from the
cage and subsequently the related ketone product was formed
by reacting with the oxidant.50, 51
Proposed mechanism for oxidation of alkenes and alkanes in
heterogeneous and homogeneous environment
To make insight into the reaction mechanism, oxidation of
cyclohexene was performed in the presence of diphenylamine
as a radical scavenger. Complete suppression of oxidation
Scheme 2 Proposed mechanism for epoxidation of alkenes in heterogeneous
environments.
Fig. 3 Lack of formation of μ-oxo dimer in heterogeneous environment.
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and separates. Therefore the corresponding metalloporphyrin
is attached in another way from pyrrolic nitrogen site to the
radical intermediate (Species B). A carbocation intermediate is
then formed by heterolytic cleavage53 and the obtained
intermediate can undergo hydrolysis due to the presence of
water caused by existence of aqueous solution of TBHP and
subsequently, the obtained diols (Species C) convert to the
corresponding byproduct (benzaldehyde) by C C cleavage.54
The aforementioned mechanism is more probable using the
homogeneous catalysts due to the less steric hindrance in
solution. Hence, benzaldehyde was the major product in
homogeneous environment whereas the major product in
heterogeneous environment was epoxy.
The mentioned mechanism can happen only for entries 2
and 5 of table 1. For other substrates, if these compounds
follow this mechanism, ultimately lead to ring opening
reaction and linear alcohol product is formed. In this case, they
lose their steady state, allylic oxidation. The choice of each of
these pathways depend on the substrate’s tendency toward
the desired pathway and intermediate stability.
As mentioned above, in some cases (entries 2 and 5, Table
In the case of alkanes as substrates, due to the absence of
double bod, this mechanism is not feasible and most
substrates converted to the corresponding ketone with regard
to the excessive activity of catalysts. Overall, selectivity can be
controlled in the case that it’s possible.
1) selectivity in homogeneous environment have some
interesting changes compared to heterogeneous environment.
The mentioned outcomes can be explained by the proposed
mechanism (Scheme 3). According to this mechanism, after
formation of oxo intermediate (MV(O)P) in the presence of
oxidant and translocation with the substrate in a cage,
electron transfer and substrate binding to the MV(O)P formed
The reaction pathway and identification of intermediate
species in oxidation reaction of alkanes was carried out by
oxidation of cyclooctane in the presence of diphenylamine as a
radical scavenger. Lack of reaction progress indicates that
oxidation reactions proceed through a radical mechanism
(Scheme S1). In these cases, alkane oxidation progressed via
“oxygen rebound mechanism”.55 In the proposed mechanism,
a radical intermediate with the MIV(O)P π-cation radical active
52
species (Species A).49,
In the next step, the approach of
another metalloporphyrin to substrate causes the M O bond
to break and the active species returns to its principal state
Table 3 The comparison of catalytic activity of the present work with some catalysts which previously reported.
Entry
Catalyst
Substrate
TON
Ref
Present work
(TON)
1573
1573
1557
1557
1557
1557
5181
1589
1128
1693
5798
1128
10347
1128
1128
1128
1128
1128
1128
1128
56
57
57
58
59
60
61
60
62
47
47
47
63
63
58
59
64
64
65
65
1
2
3
4
5
6
Azo-CMP-1
Cyclohexene
Cyclohexene
Cyclohexane
Cyclohexane
Cyclohexane
Cyclohexane
Cyclooctane
Cyclooctene
Styrene
199.2
232.5
137.5
30.5
33.6
29.2
2200
49
888
88.4
18
104
730
668
Fe3O4@SiO2-NH2@[MnTPFPP]
Fe3O4@SiO2-NH2@[MnTPFPP]
Mn(TPyP)/SiO2–Fe3O4
Mn(TPyP)OAc/CM-MIL-101
Mn(TPP)/Im-MIL-101
Fe(TMPyP)/NaX
Mn(TPP)/Im-MIL-101
Mn porphyrin MOF
CoTPPS/PANI
FeTPPS/PANI
MnTPPS/PANI
Fe3O4-AM-FeP
Fe3O4-AM-MnP
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Styrene
Styrene
Styrene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Cyclooctene
Mn(TPyP)/SiO2–Fe3O4
Mn(TPyP)OAc/CM-MIL-101
MnTDCSPP–SiNMe3
MnTF4TMAPP–SiSO3
Fe3O4@nSiO2@MCM-41-MnP
Fe3O4@nSiO2@MCM-41(E)-MnP
51.3
53.1
718
995
421
+
-
590
8 | J. Name., 2012, 00, 1-3
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the initial step after generation of oxo intermediate, appeared
to be the abstraction of hydrogen atom from the substrate to
form a substrate radical and the high-valent oxo MIV(OH)P π-
cation radical held together in a cage. The hydroxylated
product could be generated by transferring electron from
alkane to the MIV(O)P+. active species and incorporation of the
active species with the substrate radical (Scheme S1, route
A).55 However, in most cases, after formation of the MIV(OH)P
π-cation radical active species, the substrate radical gets away
from the cage and reacts directly with the oxidant to give the
related ketone product (Scheme S1, route B).50, 51
Conclusions
In summary, three 3D “ship in bottle” Porph@MOMs with
selectivity control capability and interesting catalytic property,
were prepared and designated as Porph@MOM-4,
Porph@MOM-5 and Porph@MOM-6. Evaluation of catalytic
performance of the prepared structures reveals that the
presence of metalloporphyrin into the cavities of the
framework enhances the catalytic activity of ultimate
compound and controls the selectivity of substrates toward
the desired product in the case that it’s possible. These
compounds were found to successfully catalyze the oxidation
of alkenes and alkanes in moderate to high yields. It was also
found that the selectivity and TON number of these
synthesized structures were higher than those of other
catalysts in which different metalloporphyrins were
immobilized on diverse supports.
Reusability of the catalysts and catalytic activity
The greatest advantage of heterogeneous catalysts is their
stability and reusability, which make them commercially
attractive. Therefore, the recycling experiments were carried
out in order to evaluate the reusability of the catalysts. For this
purpose, cyclohexene was selected as a model substrate.
Stability and reusability of the prepared catalysts were
examined via multiple sequential oxidation reactions under
the conditions defined in the tests. After each cycle, the
employed catalyst was isolated from the reaction mixture and
washed thoroughly with methanol and dried before using it in
the subsequent run. The results indicate that the catalysts
were consecutively reused five times without any substantial
loss of the initial catalytic activity and detectable leaching (Fig.
S19). The FT-IR spectra and XRD pattern indicate that there is
no remarkable change in the structure of the catalysts (Fig.
S2b, S3b, S4b and Fig. S5c, respectively).
Study of the catalysts reusability revealed that at least five
oxidation runs could be carried out without significant
reduction in catalytic activity.
Heterogeneous catalysts show better catalytic activity
compared to the related homogeneous catalysts due to the
formation of bridge μ-oxometalloporphyrin dimers in
homogeneous systems. In some cases, in the epoxidation of
alkenes, selectivity in heterogeneous and homogeneous
environment is completely reverse, which is due to differences
in the proposed mechanism, owing to the less steric hindrance
in homogeneous systems. High catalytic stability, high yield,
selectivity, reusability and mild reaction conditions are some
unique features of these catalysts. Compared to the reported
TONs in the conventional catalytic systems, the high TONs
obtained in this research are promising.
To check the presence of any leached catalyst, hot catalyst
filtration test was performed. In this manner, the catalyst was
removed from the reaction mixture after one hour and the
reaction was continued to the end. No significant changes in
conversion were observed and thus the system has no catalyst
leaching.
Acknowledgements
The authors would appreciate Alzahra University and Nuclear
Science and Technology Research Institute (NSTRI) for financial
support.
As
mentioned
above,
to
confirm
that
the
metalloporphyrins are the active species in the reactions and
the frameworks play no role, oxidation reactions were carried
out with the mentioned substrates in the presence of FeBTC,
CoBTC and MnBTC frameworks. The results show no significant
progress in the presence of these catalysts due to the
saturated coordination sites and inaccessible metal sites. The
saturated metal sites are shown in Fig. S20. Therefore, the
frameworks without porphyrin molecules within the cavities
do not interfere and participate in the oxidation reaction.
In order to evaluate the activity of the synthesized catalysts
with the other ones, a comparison is made between our
prepared catalysts and other catalyst in which different
porphyrins were immobilized on different supports. As the
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New Journal of Chemistry
Page 12 of 12
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DOI: 10.1039/C8NJ00315G
3D “ship in bottle” Porph@MOMs with selectivity control capability and interesting catalytic property
were used as biomimetic oxidation catalysts for different reactions.