Manganese porphines-NH2@SBA-15 as heterogeneous catalytic systems with homogeneous behavior: Effect of length of linker in immobilized manganese porphine catalysts in oxidation of olefins

Article abstract of DOI:10.1016/j.molcata.2016.06.012

Two types of SBA-15 mesoporous silica were functionalized with different nitrogen-carbon chain lengths (long and short-chain) and then used as solid supports for immobilization of manganese(III) complex of meso-tetrakis(4-carboxyphenyl)porphine, [SBA-15-short-chain-NH₂@Mn(TCPP)OAc] and [SBA-15-long-chain-NH₂@Mn(TCPP)OAc]. The prepared catalysts were characterized by powder X-ray diffraction (XRD), FT-IR and UV–vis spectroscopy. The loading of catalyst onto porous materials was determined by atomic absorption spectroscopy. Thermal analysis also demonstrated that the immobilized catalysts are thermally stable up to almost 400?°C. A comparative study based on the difference in chain length of the functional groups of SBA-15 in the oxidation of olefins was carried out in the presence of urea hydrogen peroxide (UHP) as oxidant and acetic anhydride as an activator. The novel long-chain catalyst was designed to improve performance of the catalytic activity.

Full text of DOI:10.1016/j.molcata.2016.06.012

Accepted Manuscript
Title: Manganese porphines-NH @SBA-15 as heterogeneous
2
catalytic systems with homogeneous behavior: Effect of
length of linker in immobilized manganese porphine catalysts
in oxidation of olefins
Author: Saeed Rayati Zahra Sheybanifard Mostafa M. Amini
Azam Aliakbari
PII:
S1381-1169(16)30225-4
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.molcata.2016.06.012
MOLCAA 9918
To appear in:
Journal of Molecular Catalysis A: Chemical
Received date:
Revised date:
Accepted date:
8-5-2016
12-6-2016
14-6-2016
Please cite this article as: Saeed Rayati, Zahra Sheybanifard, Mostafa M.Amini, Azam
Aliakbari, Manganese porphines-NH2@SBA-15 as heterogeneous catalytic systems
with homogeneous behavior: Effect of length of linker in immobilized manganese
porphine catalysts in oxidation of olefins, Journal of Molecular Catalysis A: Chemical
http://dx.doi.org/10.1016/j.molcata.2016.06.012
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Manganese porphines-NH @SBA-15 as heterogeneous catalytic systems
2
with homogeneous behavior: Effect of length of linker in immobilized
manganese porphine catalysts in oxidation of olefins
a
a
b
b
Saeed Rayati , Zahra Sheybanifard , Mostafa M. Amini and Azam Aliakbari
a
Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, 15418 Tehran, Iran
bDepartment of Chemistry, Shahid Behesti University, Tehran, Iran
*Corresponding Author:Saeed Rayati
Associate Professor
Department of Chemistry
K.N. Toosi University of Technology
P.O. Box 16315-1618
Tehran, Iran
Tel.: +98 21 228 50266
Fax: +98 21 228 53650
E-mail : rayati@kntu.ac.ir, srayati@yahoo.com.

Graphical abstract
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Highlights




Preparation of a novel long chain immobilized catalyst
Effect of length of linker in immobilized manganese porphyrin
Catalytic oxidation of olefins with urea hydrogen peroxide
Heterogenized catalyst with homogenous behavior
Abstract
Two types of SBA-15 mesoporous silica were functionalized with different nitrogen-carbon
chain lengths (long and short-chain) and then used as solid supports for immobilization of
manganese(III) complex of meso-tetrakis(4-carboxyphenyl)porphine, [SBA-15-short-chain-
NH
2
@Mn(TCPP)OAc] and [SBA-15-long-chain-NH @Mn(TCPP)OAc]. The prepared
2
catalysts were characterized by powder X-ray diffraction (XRD), FT-IR and UV-Vis
spectroscopy. The loading of catalyst onto porous materials was determined by atomic
absorption spectroscopy. Thermal analysis also demonstrated that the immobilized catalysts
are thermally stable up to almost 400 ˚C. A comparative study based on the difference in
chain length of the functional groups of SBA-15 in the oxidation of olefins was carried out in
the presence of urea hydrogen peroxide (UHP) as oxidant and acetic anhydride as an
activator. The novel long-chain catalyst was designed to improve performance of the catalytic
activity.
Keywords: Long-chain catalyst, Heterogeneous catalytic system, Mn-porphine, Oxidation,
Olefins

1. Introduction
In order to achieve useful and practical intermediates and products, metal complexes
have been considered as catalysts for the oxidation of various compounds. Meanwhile,
the development of approaches for designing efficient catalytic systems has attracted
much interest in recent years [1]. Even though the homogeneous catalytic systems are
often more effective than the heterogeneous analogues, the difficulties in separation of
the catalyst is the disadvantage of them and therefore the researchers are interested to
design and construct more effective heterogeneous catalytic systems. Synthetic
metalloporphines as model catalysts for cytochrome P450 have been extensively
studied for oxidation of variety compounds using various oxidizing agents [2-8].
However, the oxidative degradation of these valuable macromolecules is often
encountered in the oxidation reactions [9]. Therefore, immobilization of the
metalloporphine complexes onto solid supports such as mesoporous materials with
high specific surface area, make them stable toward degradation [10-18]. The
supporting of the large metal complexes such as metalloporphines through an organic
spacer onto the mesoporous materials is often preferred and also, the solidity of the
attachment to the support is an important factor that should be considered during
immobilization process [10, 19]. Among different mesoporous silica, Santa Barbara
Amorphous (SBA-15) due to its unique properties such as thick walls (4-6 nm),
thermal and mechanical stability, highly ordered mesostructure, large specific surface
2
area (above 1000 m /g) and regular 2D hexagonal array of channels with a narrow
pore-size distribution of 1.5–300 Å has attracted more attentions as solid support [17,
2
0-23]. The functionalization and modification of SBA-15 could enhance its capability
as a support for supporting the large metal complexes such as metalloporphines. On
the other hand, covalent immobilization of the catalyst, decrease catalyst leaching
during catalytic reactions [24-29].
In the present study, we have utilized two types of functionalized SBA-15 with 3-
aminopropyltriethoxysilane and N-(3-trimethoxysilylpropyl)diethylenetriamine which
have short and long chain lengths relative to the surface of support and then a Mn-
complex of meso-tetrakis(4-carboxyphenyl)porphine (H
anchored onto them, [(SBA-15-short-chain-NH @Mn(TCPP)OAc] and [SBA-15-
long-chain-NH @Mn(TCPP)OAc)]. Hydrogen peroxide and its derivatives are well-
known as green oxidants which extensively used in the oxidation of various
2
TCPP) has been covalently
2
2

compounds [30, 31]. One of the methods for the activation of hydrogen peroxide and
its derivatives is the formation of peroxycarboxylic acids from the reaction of
carboxcylic acid anhydrides and H
2
2
O [30, 32].
2. Experimental section
2
.1. Materials and Physico-chemical characterization techniques
The chemicals, reagents and solvents were purchased from Aldrich, Merck or Fluka
chemical companies and were employed without further purification. The electronic
absorption spectra were recorded on PerkinElmer Lambda 25 UV-Vis
spectrophotometer. The mesoporous materials and heterogenous catalytic systems
were identified by X-ray powder diffraction (XRD) using a STOE diffractometer with
Cu-K radiation (λ = 0.15418 nm) at 40 kV and 40 mA. The diffraction patterns were
α
recorded in the Bragg angle (theta) range from 0.5° to 10° for small angle XRD with a
position sensitive detector using a step size of 0.06°. Infrared spectra were recorded
−
1
(
KBr pellets) on an ABB Bomem: FTLA 2000-100 in the range of 400 to 4000 cm .
Thermal analysis (TGA/DTA) was carried out on a Bahr STA-503 instrument in air at
−
1
a heating rate of 10 °C min . Gas chromatography experiments (GC) were performed
with a Shimadzu GC-14B equipped with a flame ionization detector (FID) with a
SAB-5 capillary column (phenyl methyl siloxane 30 m × 320 mm × 0.25 mm). A
Varian AA 240 atomic absorption spectrometer was used for manganese
determination.
2.2.General procedure for the preparation of porphine and metalloporphine
H
2
TCPP was prepared by refluxing 4-carboxybenzaldehyde (300 mg, 2 mmol) and
pyrrole (0.12 mL, 1.8 mmol) in propionic acid as described by Adler et al. [33] and
then, Mn(TCPP)OAc was prepared according to the literature [34].
2
.3.General procedure for the preparation of 3- aminopropyltriethoxysilane and N-(3
Trimethoxysilylpropyl)diethylenetriamine functionalized SBA-15 (SBA-15-short-
chain-NH2 and SBA-15-long-chain-NH2)
SBA-15 nanoporous silica was prepared according to previous reports [35]. The SBA-
5 nanoporous was functionalized using general procedure used for functionalization
1
of silica using silane coupling agent [36]. In a typical reaction, 1.0 g of SBA-15 was
suspended in 50 mL toluene and the mixture was stirred for 1 h, then 2.0 mL of 3-
aminopropyltriethoxysilane[(C
2
H
5
O)
3
Si-(CH
2
)
3
NH
2
,
Aldrich,
USA]or
N-(3-

Trimethoxysilylpropyl)diethylenetriamine
[(CH
3
O) Si-
3
(
CH NH(CH NH(CH NH , Aldrich, USA] was added to the mixture and refluxed
2
)
3
2
)
2
2
)
2
2
for 24 h. The white solid was then removed from the solvent by filtration and washed
with ethanol and then dried at room temperature.
2.4.General procedure for the preparation of heterogeneous catalytic systems [SBA-15-
short-chain-NH @Mn(TCPP)OAc],[SBA-15-long-chain-NH @Mn(TCPP)OAc]
2
2
Synthesis of heterogenized catalysts was carried out according to the method described in the
literature [9, 19 and 30]. 2-(1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium
tetrafluoroborate (TBTU) (400 mg) and N,N’-diisopropylamine(DIPEA) (300 mg) were
added to a mixture of short or/and long chain functionalized SBA-15 (400 mg) and
Mn(TCPP)OAc (100 mg) in 25 mL dichloromethane and then this mixturewas stirred for 48
hours at room temperature. In order to remove the weakly adsorbed metalloporphines on the
mesoporous surface, the solid residue was finally washed with dichloromethane until the
filtrate became colorless and then, dried at room temperature.
2.5. General procedure for catalytic oxidation of olefins
In a typical procedure, catalytic experiments were carried out in a 5 mL test tube containing
.39×10−4 mmol of catalyst (7.07×10 g of Mn(TCPP)OAc per 1g catalyst), 0.16mmol of
−7
6
imidazole as co-catalyst and 0.064mmol of olefins in a mixture of dichloromethane and
methanol (1mL, 1:1) as solvent. The oxidation reaction was initiated by adding the UHP
(0.089 mmol) and then acetic anhydride (0.3mmol), under magnetic stirring at room
temperature. The heterogenized catalyst was then filtered, and the organic phase was
analyzed by gas chromatography and the oxidation products were identified by comparison
with authentic samples. The reusability of heterogeneous catalytic systems was checked in
the multiple consecutive oxidation of 4-methyl styrene as described above. At the end of each
reaction, the catalyst was separated and washed with methanol and dichloromethane and then,
dried at 60⁰C for 24hours before reuse.
3. Results and Discussion
3.1.Characterizationof the heterogeneous catalytic systems[(SBA-15-short-chain-
NH
The heterogenized catalysts were synthesized using TBTU (2-(1H-benzotriazole-1-yl)-
,1,3,3-tetramethyluronium tetrafluoroborate) as a highly effective uronium salt that
2
@Mn(TCPP)OAc] and [SBA-15-long-chain-NH
2
@Mn(TCPP)OAc)]
1

has been used as an coupling reagent in the presence of DIPEA (N,N´-
diisopropylamine) for the preparation of amidic bonds (Scheme 1).
The manganese content of the heterogenized catalysts was determined by atomic
absorption spectroscopy which showed loadings of 0.24 and 0.46 mmol/g of the
−
4
catalyst for the long-chain (2.6×10 g of Mn(TCPP)OAc per 1 g catalyst) and short-
−
4
chain (5.09×10 g of Mn(TCPP)OAc per 1g catalyst) catalysts, respectively.
The immobilization of manganese porphine onto mesoporous materials was evaluated
using FT-IR spectra (Fig. 1).
The FT-IR spectra of functionalized porous materials (short and long-chain) shows
-
1
two bands at 1064 and 1090cm , which are attributed to the stretching vibrations of
-
1
Si-O-Si and also the bands at 796 and 784 cm are assigned to the stretching
-
1
vibrations of Si-OH. The strong bands at 3444 and 3460 cm confirmed the presence
of amine groups (Fig. 1 a and b). In the FT-IR spectra of [SBA-15-short-chain-
NH
2
@Mn(TCPP)OAc] and [SBA-15-long-chain-NH @Mn(TCPP)OAc] a broad band
2
at 3470 and 3446cm-1 are attributed to the amidic bond constructed between
functionalized porous materials and Mn-porphine (Fig. 1 c and d) [37]. The similarity
between FT-IR spectra of functionalized porous materials and heterogenized catalysts
indicates that the porous nature of the amine-SBA-15 has been kept after immobilizing
the metalloporphine complexes onto them.
Existence of the porphine in the mesoporous materials was confirmed by comparison
of the UV-Vis spectra of functionalized amine-SBA-15, [SBA-15-long-chain-
NH
UV-Vis spectra of functionalized porous materials (long and short-chain) were similar
Fig. 2 c and d). The absorption spectrum of Mn(TCPP)OAc in DMF exhibits a sharp
2
@Mn(TCPP)OAc] and [SBA-15-short-chain-NH
2
@Mn(TCPP)OAc] (Fig. 2). The
(
band at 470 nm (Soret band) and two weak absorptions at 566 nm and 601 nm (Q
bands) [19]. These bands were remaining when the Mn-porphine was anchored onto
the functionalized porous materials (Fig. 2 a and b).
The low-angle X-ray diffraction pattern of functionalized amine-SBA-15 showed that the
nanoporous structure of silica after functionalization remains intact (Fig. 3). The
characteristic diffraction peak (d100) of mesoporous materials is at about 1.41⁰ (Fig. 3 c and d)

[38]. This diffraction peak was also observed after anchoring of Mn-porphine onto
functinalized amine-SBA-15. A slight shift to a lower angle and lower intensity is due to a
decrease in the mesoscopic order of the materials and mainly due to the contrast matching
between the silicate framework and organic moieties located inside the porous materials
channels (Fig. 3 a and b) [17, 39 ].
The thermal behavior of long-chain and short-chain catalysts is also illustrated in Fig.
4
which shows thermal stability of heterogenized catalysts up to 400
⁰C. According to
the results, the degradation of catalyst has been occurred between 400-500
⁰C.
3
.2. Catalytic oxidation of olefins
The catalytic efficiency of [SBA-15-short-chain-NH
chain-NH @Mn(TCPP)OAc] as heterogenized catalysts was compared in the oxidation of
2
@Mn(TCPP)OAc] and [SBA-15-long-
2
cyclooctene as a model substrate with urea hydrogen peroxide (UHP) as oxygen donor and
acetic anhydride as activator and the influence of various parameters such as nature of
solvent, amount of co-catalyst, activator and oxidant has been evaluated. In order to
investigate the catalytic performance of the prepared catalysts, a blank experiment was also
performed and the result showed that the presence of catalyst is indispensable for an efficient
catalytic reaction and in the absence of the heterogenized catalysts only 20% cyclooctene
oxide was obtained after 3 hours. Also, in the presence of funectinalized-SBA-15-NH
catalyst no significant conversion was observed (13%).
2
as
In reactions catalyzed by metalloporphines, the conversion values and product yields are
usually influenced by the nature of solvent [40]. Methanol and dichloromethane were chosen
as the reaction media for oxidation of cyclooctene with UHP and acetic anhydride in the
presence of [SBA-15-long-chain-NH
2
@Mn(TCPP)OAc] as heterogenized catalysts and a
mixture of MeOH and CH Cl (1:1) was found to be the best one (Table 1). At this mixture of
2
2
solvent, short-chain catalyst showed lower reactivity toward oxidation of cyclooctene in
comparison with long-chain catalyst (Table 1, entries 3 and 4).

The results show that in the absence of an activator, the reaction do not proceed and acetic
anhydride was found to be an effective activator for both catalysts and also the effect of the
amount of acetic anhydride was inspected (Table 2). The results showed that the oxidation
reaction needs 0.3 mmol (3.5 equimolar amount of acetic anhydride with respect to the UHP)
acetic anhydride for the highest conversion in the presence of [SBA-15-long-chain-
NH
2
@Mn(TCPP)OAc] as catalyst. On the other hand, running the oxidation reaction by
@Mn(TCPP)OAc] as catalyst led to a conversion of 49% (Table 2,
[
SBA-15-short-chain-NH
2
entry 8). Therefore, long-chain catalyst has been found to show higher catalytic activity in the
oxidation of cyclooctene with 0.3 mmol acetic anhydride compared to short-chain catalyst.
The catalytic activity of the heterogenized catalysts was also evaluated with UHP and acetic
acid as activator (Table 2, entries 9 and 10). The results show that the reaction precedes only
6% and 3% with long-chain and short-chain catalysts, respectively.
In Fig. 5 the effect of UHP:cyclooctene molar ratio in the oxidation of cyclooctene in the
presence of long-chain catalyst is shown. Interestingly, cyclooctene conversion raised with
increasing the UHP:cyclooctene molar ratio to 1.4 and this increase in conversion turns into a
decrease beyond this ratio.
The influence of nitrogenous bases as co-catalyst in the oxidative reactions with
metalloporphines has been usually checked [41-43]. Here, the oxidation of cyclooctene was
−4
carried out using various amounts of imidazole as co-catalyst (Table 3) and 1.6×10 mol was
found to be optimized one in the presence of long-chain catalyst as catalyst (Table 3, entry 4).
In addition, the catalytic activity of short-chain catalyst was probed with and without
imidazole (Table 3, entries 6 and 7). The results showed when the imidazole was omitted
from the reaction mixture, 43% and 34% conversions were obtained for long-chain and short-
chain catalysts, respectively (Table 3 entries 1 and 6) and then upon addition of imidazole,
long-chain catalyst showed higher catalytic activity in comparison with short-chain one. On
−4
the other hand, addition of more imidazole to the reaction mixture (2.3×10 mol) led to no
change in conversion (Table 3 entry 5).
In order to compare homogeneous catalytic system (Mn(TCPP)OAc) with heterogeneous
catalytic systems, the oxidation of cyclooctene was also done in the same condition and the

formation of 73% cyclooctene oxide was observed (Fig. 6). According to these results, the
presence a long chain in the structure of long-chain catalyst led to the higher catalytic activity
as homogeneous one. Hence, using of long-chain catalyst leads to dual advantages: the high
catalytic activity as a homogeneous catalytic system and same time benefit of convenient
separation which the homogeneous complex cannot be recovered even once, the
heterogenized catalysts can be separated and reused for a similar reaction.
[SBA-15-long-chain-NH
2
@Mn(TCPP)OAc]
and
[SBA-15-short-chain-
NH @Mn(TCPP)OAc] are also efficient heterogenized catalysts for oxidation of various
2
olefins under the optimized reaction conditions and the results are presented in Fig. 7.
The long-chain catalyst has been found to show higher catalytic activity in oxidation of
various olefins compared to the short-chain one. In both catalytic systems, the oxidation of
cyclooctene (70% long-chain and 49% short-chain), cyclohexene (65% long-chain and 52%
short-chain), styrene (68% long-chain and 64% short-chain), 4-chloro styrene (57% long-
chain and 56% short-chain) and 4-methoxy styrene (96% long-chain and 94% short-chain)
give epoxide as the sole product at room temperature after 3 hours of reaction time but in the
oxidation of α-methyl styrene (79% long-chain and 74% short-chain) and 4-methyl styrene
(
86% long-chain and 81% short-chain), acetophenone and 4-methyl benzaldehyde are also
formed as the minor product, respectively.
Apparently, due to the steric hindrance of methyl substituent, α-methyl styrene is less reactive
than styrene towards epoxidation reaction. Indene was also oxidized in 73% and 56% yields
in the presence of long-chain and short-chain catalyst, respectively.
In the case of terminal olefins such as 1-octene (7% long-chain and 5% short-chain) the
corresponding epoxide was also detected as the sole product.
After 6 hours of reaction time, the catalytic activity of long-chain catalyst was also superior
in comparison with the Short-chain one.
The results show that about styrene and substituted styrenes, there is lower difference
between the catalytic activity of long-chain and short-chain one.
For studying catalyst reuse and stability, 4-methyl styrene was chosen as a model substrate
and the reactions were run as described in experimental section (Fig. 8). For each reaction,

the catalyst was separated, washed with MeOH and CH
2
Cl three times and dried before
2
being used. The results showed that the yield of the catalytic activity reach to 48% and 46%
for long-chain and short-chain catalyst, respectively after using the catalysts for five
consecutive times. As it can be seen, the short-chain catalyst in comparison with long-chain
catalyst showed a rapid decrease in the first cycle while such reduction was observed in the
second cycle for long-chain catalyst. Nevertheless, both catalysts can be use for several times
and this is a good result for a heterogeneous catalytic system.
3.3.Proposed catalytic mechanism
In the absence of acetic anhydride, the oxidation of olefins with UHP and heterogenized
catalysts did not proceed (Table 2, entry 1) but as mentioned above, in the presence of acetic
anhydride and UHP without catalysts (blank experiment) a conversion of ca. 20% was
obtained.These observations suggest a catalytic cycle containing peracetic acid formed by the
reaction of UHP and acetic anhydride (Scheme 2, I) [30, 32 and 44]. In the presence of
catalysts, addition of acetic anhydride resulted in an increase in the catalytic activity. It seems
that formed peracetic acid (I) can be coordinate to the Mn-center (Scheme 2, II) and then
oxygen transfer to the olefins will occur. Also, the intermediate II could produce a
manganese-oxo intermediate (Scheme 2, III) afterwards, olefins as a nucleophile will attack
to the oxygen atom and epoxide product will be formed [45-47].
In the absence of acetic anhydride, the oxidation of olefins with UHP and heterogeneous
catalytic systems did not proceed (Table 2, entry 1) but as mentioned above, in the presence
of acetic anhydride and UHP without catalysts (blank experiment) a conversion of ca. 20%
was obtained. These observations suggest a catalytic cycle containing peracetic acid formed
by the reaction of UHP and acetic anhydride (Scheme 2, I) [30, 32 and 44]. In the presence of
catalysts, addition of acetic anhydride resulted in an increase in the catalytic activity. It seems
that formed peracetic acid (I) can be coordinate to the Mn-center (Scheme 2, II) and then
oxygen transfer to the olefins will occur. This intermediate (Scheme 2, II) can either undergo
heterolytic and/or hemolytic cleavage of O-O band and could produce a manganese-oxo
intermediate (Scheme 2, III) as a result of homolytic cleavage of O-O band and afterwards,
olefins as a nucleophile will attack to the oxygen atom and epoxide product will be formed by
direct oxygenation [45-49]. On the other hand, this intermediate could produce another

manganese-oxo intermediate (Scheme 2, IV) as a result of heterolytic cleavage of O-O band
and a radical mechanism can be occurred through H abstraction from olefins or water.
However, both intermediates can be active oxidant.
4
. Conclusions
The catalytic activity of Mn(TCPP)OAc complexes immobilized onto the two types of
functionalized SBA-15(NH ) was investigated in the oxidation of olefins. The results
2
showed that the catalytic activity of the long-chain catalyst is higher than the short-
chain one and also its catalytic performance is similar with homogeneous catalytic
system. In this study, a mixture of CH
2
Cl :MeOH(0.5:0.5) has been found to be the
2
best solvent system. The results show that about styrene and substituted styrenes, there
is lower difference between the catalytic activity of long-chain and short-chain one.
However, in all these cases, the long-chain catalyst shows higher activity in
comparison with short-chain one. Also, both catalysts can be reused and recovered at
least four times.
Acknowledgements
The authors are thankful to Research Council of K.N. Toosi University of Technology
for their support during this work.

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Fig. 1. FT-IR spectra of (a) SBA-15-long-chain-NH
2
2
, (b) SBA-15-short-chain-NH , (c) catalyst [SBA-15-long-
chain-NH @Mn(TCPP)OAc] and (c) catalyst [SBA-15-short-chain-NH
2
2
@Mn(TCPP)OAc].

Fig. 2. UV-Vis spectra of (a) [SBA-15-short-chain-NH
chain-NH @Mn(TCPP)OAc] (c) SBA-15-short-chain-NH
2
@Mn(TCPP)OAc] and (b) [SBA-15-long-
2
2
(d) SBA-15-long-chain-NH
2
.

Fig. 3 XRD pattern of (a) [SBA-15-long-chain-NH
2
@Mn(TCPP)OAc] and (b) [SBA-15-short-chain-
NH @Mn(TCPP)OAc] (c) SBA-15-long-chain-NH (d) SBA-15-short-chain-NH .
2
2
2
Fig. 4. TGA/DTA curves of (a) long-chain catalyst and (b) short-chain catalyst.

Fig. 5. Effect of UHP to cyclooctene molar ratio in the oxidation of cyclooctene. The reaction conditions are as
follows:1:250:X:X:490, Cat.: co-catalyst: olefin:UHP:acetic anhydride and reactions were run at room
2 2
temperature for 3hours, CH Cl :MeOH(0.5:0.5) as solvent.

Fig. 6. Comparing between homogeneous and heterogeneous systems. The reaction conditions are as follows:
:250:100:140:490, Cat.:co-catalyst:olefin:UHP:acetic anhydride and reactions were run at room temperature
for 3hours. CH Cl :MeOH(0.5:0.5) as solvent.
1
2
2
Fig. 7. Oxidation of various olefins by [SBA-15-long-chain-NH
NH @Mn(TCPP)OAc]. The reaction conditions are as follows: 1:250:100:140:490, Cat.:co-
catalyst:olefin:UHP:acetic anhydride and reactions were run at room temperature for 3 hours. CH Cl :MeOH
0.5:0.5) as solvent.
2
@Mn(TCPP)OAc] and SBA-15-short-chain-
2
2
2
(

Fig. 8. The recovery and reuse of [SBA-15-long-chain-NH
NH @Mn(TCPP)OAc]. The reaction conditions are as follows: 1:250:100:140:490, Cat.:co-catalyst:4-methyl
styrene:UHP:acetic anhydride and reactions were run at room temperature for 3hours. CH Cl : MeOH (0.5:0.5)
as solvent.
2
@Mn(TCPP)OAc] and [SBA-15-short-chain-
2
2
2

Scheme 1 Schematic representation of the preparation of [SBA-15-short-chain-NH
and [SBA-15-long-chain-NH @Mn(TCPP)OAc].
2
@Mn(TCPP)OAc]
2

Scheme 2 Proposed catalytic cycle.

Table 1
Influence of solvent in the oxidation of cyclooctene. The reaction conditions are as follows:1:250:100:140:600,
Cat.:co-catalyst:olefin:UHP:acetic anhydride and reactions were run at room temperature for 3hours.
Entry
Catalyst
Solvent
CH Cl
Conversion %
1
2
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
2
2
33
38
MeOH
3
4
Long-chain@Mn(TCPP)OAc
Short-chain@Mn(TCPP)OAc
CH
2
2
Cl
Cl
2
2
:MeOH (0.5:0.5)
:MeOH (0.5:0.5)
70
49
CH
Table 2
Influence of activator in the oxidation of cyclooctene. The reaction conditions are as follows: 1:250:100:140:X,
Cat.: co-catalyst: olefin:UHP:activator and reactions were run at room temperature for 3hours,
2 2
CH Cl :MeOH(0.5:0.5) as solvent.
Entry
Catalyst
Acetic anhydride/UHP
Conversion %
1
2
3
4
5
6
7
8
9
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Short-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Short-chain@Mn(TCPP)OAc
-
0
11
21
37
60
70
70
49
6
0.5
1
1.5
2.5
3.5
4.2
3.5
3.5a
3.5a
10
3
a
acetic acid as activator

Table 3
Influence of imidazole in the oxidation of cyclooctene. The reaction conditions are as follows:1:X:100:140:490
Cat.:olefin:co-catalyst:UHP:anhydride and reactions were run at room temperature for 3hours,
2 2
CH Cl :MeOH(0.5:0.5) as solvent.
Entry
Catalyst
Co-catalyst (mmol)
Conversion %
1
2
3
4
5
6
7
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Long-chain@Mn(TCPP)OAc
Short-chain@Mn(TCPP)OAc
Short-chain@Mn(TCPP)OAc
-
43
59
67
70
70
34
49
0.079
0.12
0.16
0.23
-
0.16