Catalytic performance of Keplerate polyoxomolybdates in green epoxidation of alkenes with hydrogen peroxide

Article abstract of DOI:10.1039/c5ra12488c

In this work, the catalytic perspective of three Keplerate polyoxometalates, Mo₇₂M₃₀ (M = V, Cr, Fe) in the epoxidation of various alkenes is considered. The catalytic reactions were performed in water under mild conditions and high to excellent conversions and selectivities were obtained using H₂O₂ as oxidant and Mo₇₂Cr₃₀ as the best catalyst. Keplerate POM catalysts have shown a very good recyclability, up to five times, without any appreciable decreases in catalytic activity and selectivity.

Full text of DOI:10.1039/c5ra12488c

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Catalytic performance of Keplerate polyoxomolybdates in green epoxidation of alkenes
with hydrogen peroxide
a
* a
b
a
Fariba Jalilian, Bahram Yadollahi , Mostafa Riahi Farsani, Shahram Tangestaninejad, Hadi
a
c
Amiri Rudbari, Rouhollah Habibi
a
Department of Chemistry, University of Isfahan, Isfahan 81746ꢀ73441, Iran
b
Department of Chemistry, Shahrekord Branch, Islamic Azad University, Shahrekord, Iran
c
Kimiatrava Tech. Co., Science & Technology Town (STT), Isfahan University of Technology,
Iran
Abstract
In this work, the catalytic perspective of three Keplerate polyoxometalates, Mo M (M = V, Cr,
7
2
30
Fe) in the epoxidation of various alkenes are considered. The catalytic reactions were performed
in water at mild conditions and high to excellent conversions and selectivity was obtained using
H O as oxidant and Mo Cr as the best catalyst. Keplerate POM catalysts have been shown a
2
2
72 30
very good recyclability, up to five times, without any appreciable decreases in catalytic activity
and selectivity.
Keywords: Keplerate polyoxometalates, catalysis, epoxidation, hydrogen peroxide, alkenes,
water
1. Introduction
*
Corresponding Author. Tel: +98ꢀ31ꢀ37934934; fax: +98ꢀ31ꢀ36689732; eꢀmail: yadollahi@chem.ui.ac.ir,
yadollahi.b@gmail.com
1

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Selective oxidation of olefins to epoxides is among the important reactions in chemical industry
1
–2
and organic chemistry. To develop environmentally benign synthetic methodologies, there is a
great interest in new and more efficient catalytic oxidations based on lowꢀcast, accessible and
3
–5
environmentally benign catalysts and oxidants.
The oxidation of olefins with aqueous
hydrogen peroxide has received much attentions, since H O is clean, inexpensive, safe, readily
2
2
6
available, high content of active oxygen species and gives water as the sole byꢀproduct.
Furthermore, using from nontoxic solvents such as water, which is safer, cheaper, and more
environmentally friendly compared to other solvents in use today, is a major problem in these
7
reactions.
Polyoxometalates (POMs), as a class of metalꢀoxygen clusters, because of the different structures
and the diversity in shapes, charges, compositions, solubility and reactivity showed a lots of
8
–9
applications. Increasing in POMs usage are evidently revealed in various literatures in the
1
0–12
fields of catalysis, material science, medicine, analytical chemistry and so on.
In the last
decades various types of POMs have drawn wide attention as effective and important catalysts
1
3–24
for epoxidation of alkenes.
VI
VI
5
Metal oxide based nanocapsules of the type {(Mo )Mo } (linker) which called Keplerates
12
30
2
5
was firstly reported by Müller and coworkers. Keplerate POMs have attracted considerable
interest and indicated a lot of applicability in various fields such as chemical science, molecular
2
6
physics, magnetochemistry, biological sciences, materials science, and even mathematics.
However, despite extremely promising potential in different fields of science the catalytic
properties of Keplerate POMs in the oxidation of organic compounds really needs to be further
2
7
investigations. For the first time, the catalytic activity of Keplerate POMs in the oxidation of
2
8
sulfides was reported. Selective epoxidation of an aqueous suspension of olefins under mild
2

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VI
V
reaction conditions catalyzed by (NH ) [Mo 72Mo 60O372 (CH COO) (H O) ] was the other
4
42
3
30
2
72
2
9–30
work.
It was also reported that Mo M is thermodynamically stable to oxidation and
72 30
28
contains transition metals (molybdenum and iron) capable of activating various oxidants.
3
1
Furthermore, Mo M have been shown very well stability in various solvents. In continuation
7
2
30
3
2
of our current research, a novel method for oxidation of organic compounds with hydrogen
peroxide as a green oxidant in the presence of Keplerate POMs and especially in sustainable
media was developed. In this regard, for the first time, the catalytic epoxidation of different
alkenes
using
30%
H O
catalyzed
by
three
Keplerate
POMs,
2
2
VI
VI
5
VI
VI
5
IV
IV
Na K (VO) [{(Mo )Mo O (H O) } {(Mo )Mo O (H O) (SO )} {V O(H O)} {V O}
8
14
2
21
2
3 10
21
2
3
4
2
2
20
10(
{KSO } ) ].150H O
{Mo V },
4 5 2
2
72 30
VI
III
30
Mo 72Fe O (CH COO) {Mo O (H O)} {H Mo O (H O)}(H O) ].150H O
{Mo Fe }
252
3
12
2
7
2
2
2
2
8
2
2
91
2
72 30
VI
III
and [{Na(H O) }[Mo 72Cr O (CH COO) (H O) }].120H O {Mo Cr }, in aqueous
2
12
30 252
3
19
2
94
2
72 30
media are described (Scheme 1).
Scheme 1. Catalytic epoxidation of alkenes with H O catalyzed by Mo V , Mo Cr and
2
2
72 30
72
30
Mo Fe
30
7
2
2. Results and discussion
In our previous work, the catalytic activity of Keplerate POMs, Mo M (M = V, Cr, Fe), in
7
2
30
successfully conversion of different sulfides into the corresponding sulfones under mild reaction
conditions with high to excellent yields were showed. Also, the reusability of these catalysts was
3

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very good and spectral results showed that the structure of recycled catalyst is preserved and it is
3
3
stable since catalytic recycling.
In this work, at first, the catalytic efficiency of three Keplerate POMs (Mo Fe Mo Cr , and
7
2
30,
72
30
Mo V ) in the epoxidation of olefins was tested using cyclooctene as a model compound. In
7
2
30
order to obtain the optimum amounts of Keplerate POM catalysts, the epoxidation of cyclooctene
was studied by various amounts of Mo Cr . From the results in Figure 1, by increasing in the
7
2
30
catalyst amounts up to 10 ꢁmol of Mo Cr the yields of epoxide was improved. In the presence
72
30
of higher amounts of Keplerate catalyst the selectivity for epoxide was decreased. In this system,
it was also showed that the presence of catalyst is crucial for the oxidation reaction. So, 10 ꢁmol
of Mo Cr which provides the highest yields for epoxidation of cyclooctene was chosen as the
7
2
30
best amount of catalyst.
Figure 1. The effect of Mo Cr amounts in the epoxidation of cyclooctene by 30% hydrogen
7
2
30
peroxide in water after 2.5 h reaction. Reaction conditions: cyclooctene (1 mmol), H O (1
2
2
mmol) and catalyst at 50 °C. Yields refer to GC yield.
In the oxidation reaction of cyclooctene by different amounts of H O , the optimum amount of
2
2
hydrogen peroxide was obtained in the presence of 10 ꢁmol catalyst after 2.5 h reaction. The
results in Figure 2 show that 1 mmol of 30% H O is sufficient for completion of the reaction at
2
2
4

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request time. Thus, 1 mmol of hydrogen peroxide was chosen as the best amount of oxidant in
this catalytic epoxidation system.
Figure 2. The effect of hydrogen peroxide amounts in the epoxidation of cyclooctene (1 mmol)
catalyzed by Mo Cr (10 ꢁmol) at 50 °C after 2.5 h reaction. Yields refer to GC yield.
7
2
30
By the optimal reaction conditions – 10 ꢁmol of catalyst, 1 mmol of 30% H O , 50 °C
2
2
temperature, and water as solvent – selective epoxidation of various alkenes with Mo V ,
7
2
30
Mo Cr , and Mo Fe as catalyst were investigated (Table 1). As it could be seen in Table 1,
7
2
30
72 30
epoxidation of styrene was gave styrene oxide as the main product by 98% selectivity (Table 1,
entry 4). The catalytic epoxidation of cyclic alkenes such as cyclohexene, cyclooctene, and
indene were efficiently proceeded to afford the corresponding epoxides in high to excellent
yields (Table 1, entries 1ꢀ3, 5). Also, nonactivated aliphatic alkenes such as 1ꢀoctene has been
converted into the corresponding epoxide selectively (Table 1, entry 6). In 2ꢀcylohexeneꢀ1ꢀol
(Table 1, entry 7) C=C double bond was selectively oxidized into corresponding epoxide and
hydroxyl functional groups remained intact.
Among three Keplerate POM catalysts in epoxidation of various alkenes under the same reaction
conditions, Mo Cr was shown higher catalytic activity than two others. Albeit, Mo V was
72
30
72 30
also demonstrated a better catalytic activity respect to Mo Fe .
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30
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Table 1. Epoxidation of different alkenes with 30% H O catalyzed by Mo M (M = V, Fe, Cr)
2
2
72 30
a
in water
b
Epoxide (%)
Mo V
Entry Alkene
Time (h)
Mo Fe
Mo Cr
72 30
7
2
30
72 30
1
2
5
5
10
7
83
63
92
75
3
4
2.5
3
7
8
86
85
97
96
c
5
6
6
6
7
6
80
79
91
87
OH
7
6.5
6
83
92
a
Reaction conditions: the reactions were run at 50 °C in 3 mL of aqueous suspension of olefin (1
mmol), 10 ꢁmol of Mo M (M = V, Fe, Cr) as catalyst and 1 mmol of 30% H O .
7
2
30
2
2
b
c
Yields refer to isolated yields.
The selectivity of epoxides was 98% and 2% benzaldehyde was also produced.
It was reported that the catalytic activity of POMs could be inversely correlated to the rate of
34
hydrogen peroxide dismutation. So, in this work hydrogen peroxide dismutation by Mo Cr ,
7
2
30
Mo V , and Mo Fe was also studied. Our results showed that in the presence of Mo Cr
30
7
2
30
72 30
72
decomposing of hydrogen peroxide was performed with lower rate compared to Mo V and
7
2
30
also Mo Fe . Thus, this is rationale for Mo Cr which shows a better catalytic activity than
7
2
30
72
30
the two other Keplerate catalysts. From Figure 3 the inversely correlations between catalytic
activity of Mo M (V, Cr, and Fe) catalysts and the rate of hydrogen peroxide decomposition in
7
2
30
the absence of substrate could be deduced. It was also demonstrated that Keplerate structure of
30
Mo Fe could be preserved in the presence of a large excess of H O .
7
2
30
2
2
6

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Figure 3. H O decomposition in the presence of Mo M (V, Cr and Fe) catalysts. Reaction
2
2
72 30
conditions: H O (10 mmol), catalysts (100 ꢁmol), water (3 mL) at 50 °C.
2
2
The epoxidation reaction of cyclooctene was used for studying the recyclability of these
Keplerate POM catalysts. In this regard, the catalysts was simply recovered after each run of the
oxidation reaction and using ethyl acetate, as a safe solvent, the organic products were isolated.
Aqueous solution of the Keplerate catalyst was recycled for the next round of the reaction
without further purification. The reusability of as mentioned POM catalysts, for at least five
times, without any significant loss of catalytic activity is one of the advantages in this catalytic
system (Table 2).
Table 2. Recycling of Mo M (Cr and V) catalysts in the epoxidation of cyclooctene by H O
2
7
2
30
2
a
according to the procedure mentioned in Table 1
Epoxide (%)
Run
Mo Cr
Mo V
7
2
30
72 30
1
2
3
4
5
97
97
97
95
95
86
86
85
85
83
a
Yields refer to GC yields.
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As it could be seen in Figure 4, similar XRD patterns for fresh and recycled Mo Cr catalysts in
7
2
30
the epoxidation of alkenes were obtained. This stated that the structure of catalyst is preserved
and it is stable since catalytic recycling.
Figure 4. The XRD pattern of Mo Cr fresh (red) and recovered in run 3 (black) and run 5
7
2
30
(pink)
Sustainable oxidation of olefins by H O in water as solvent shows lot of potential advantages
2
2
for this catalytic system in both environmental and economic aspects. The applicability and
efficiency of this green system was shown by comparing the catalytic results with some of the
reported methods on the epoxidation of cyclohexene. From Table 3, it could be seen that the
proposed catalytic system has superior results in comparison to most of the other methods.
Additionally, our catalytic system has a very well reusability along with using a nontoxic
solvent.
Table 3. Catalytic results for the oxidation of cyclohexene in the presence of different POM
a
catalysts
Entry Catalyst
Solvent
Conv. (Yields) (%) Ref.
4
–
1
2
3
4
[γꢀSiW O ]
[γꢀ1,2ꢀH SiV W O ]
(diperoxotungsto)phosphates
CH CN
84 (>99)
90 (99)
17
17
14
20
10
34
3
4
–
CH CN/tꢀBuOH
2
2
10 40
3
C H
88 (100)
36 (100)
6
6
[NMe ] [(MePO ){MePO (OH)}W
C H
4
3
3
2
6
6
6
8

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O (O ) (OH) (OH )]
1
3
2 4
2
2
5
6
7
[πꢀC H N(CH ) CH ] [PW O ]
CHCl3
CH Cl /CH CN
2 2 3
95 (97)
48 (16)
80 (97)
92 (>99)
24
18
23
ꢀ
5
5
2 15
3 3
4
16
8
–
[P W MnO ]
2
17
61
(CPB) [PW O ]
CH CN
3
12 40
3
8
Mo Cr
H O
2
7
2
30
a
The oxidant for entries 1–5 and 8 was H O , F PhI(TFAc) for entry 6 and UHP for entry 7.
2
2
5
2
The mechanism of alkenes epoxidation in the presence of POM catalysts using H O as oxidant
2
2
has been extensively investigated by several groups. In this regard, different active species such
3
−
3−
as Q [HPO {WO(O ) } ], [(PO ){WO(O ) } ] , [(PO ){WO(O ) } {WO(O ) (H O)}] ,
2
4
2 2 2
4
2 2 4
4
2 2 2
2 2
2
2
−
[
(PO (OH)){WO(O ) } ] , and some of the other hydroperoxo intermediates have been
3 2 2 2
3
5
proposed. In this work, the favor reaction path for the oxidation reaction by Mo M
30
7
2
Keplerates could also be as above.
3
. Experimental
.1. General Methods and Materials: Mo , Mo V , Mo Fe and Mo Cr prepared
3
1
32
72 30
72 30
72 30
3
6
according to the literature methods. All common laboratory chemicals were reagent grade,
commercially prepared and used without further purification. Elemental analyses for C, S, Cr,
Fe, V, Mo and K were carried out on a PerkinꢀElmer 7300 DV and Leco CHNSꢀ932 elemental
1
analyzer. Infrared spectra (KBr pellets) were recorded on a JASCO FT/IRꢀ6300 instrument. H
NMR spectra were recorded on a Bruker 400 (296 K) using CDCl as solvent and TMS as an
3
internal reference. The oxidation products were quantitatively analyzed by gas chromatography
(
GC) on a Chrompack CP 9001 instrument using a SILꢀ5CB column (50m, 32mm, 5ꢁm) and
FID detector. UVꢀvis spectra were recorded on a JASCO Vꢀ670 UVꢀvis spectrophotometer (190ꢀ
700 nm). Powder Xꢀray diffraction (XRD) data were obtained on a D8 Advanced Bruker using
Cu Kα radiation (2θ = 5ꢀ80°).
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3
.2. Synthesis of Mo Cr : CrCl ·6H O (8.6 g, 32.27 mmol) was added to a solution of
72 30 3 2
Na MoO ·2H O (9.0 g, 37.2 mmol) in a H O (80 mL)/CH COOH (100%; 35 mL) mixture. After
2
4
2
2
3
stirring for 5 min it was acidified with 1M HCl (17 mL; resulting pH ~2), and the solution was
heated under reflux for 45 min. The cooling of resulting green solution to room temperature gave
the pale green precipitate. Elemental analysis: Found: C, 2.53; Cr, 8.86; Mo, 38.80. Calc. for
–
1
Mo Cr : C, 2.58; Cr, 8.81; Mo, 38.99%. IR (KBr pellet, cm ): 1622 (m, H O), 1547 (m, COO),
7
2
30
2
1423 (w, COO), 953 (m, (Mo=O)), 796 (s), 635 (w), 580 (s), 455 (w).
The synthesis method for Mo Fe and Mo V are presented in Supplementary Material. The
7
2
30
72 30
XRD patterns of these three Keplerate POM are also shown in Figure S1.
.3. General procedure for epoxidation of alkenes: The Keplerate catalyst (10 ꢁmol), an
3
alkenes (1 mmol) and water (3 mL) were added to a glass tube under air. Then, hydrogen
peroxide (1 mmol, 30%) was added and the reaction mixture was stirred for appropriate time in a
preheated oil bath at 50 °C. The reaction progress was monitored by TLC and GC, and the yield
of products was determined by GC analysis using toluene as the internal standard. After
completion of the reaction ethyl acetate, 3 × 2 mL was added, and the extraction of organic phase
was followed by evaporation of solvent. Higher purification of products was achieved by
chromatography over silica gel (eluent: nꢀhexane/ethyl acetate 80:20). For the recyclability
reactions, an aqueous solution of catalyst was used for the next runs.
4. Conclusion
In summary, the Keplerate catalysts Mo M (M = V, Cr and Fe) were used as efficient catalysts
7
2
30
for epoxidation of various olefins to epoxides at 50 °C in water using 30% H O . Among three
2
2
Keplerate POM catalyst, Mo Cr showed the highest conversions and selectivity for
72
30
epoxidation of alkenes. In this system, Mo M (M = V and Cr) catalysts efficiently reused
7
2
30
1
0

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many times without any loss of activity. Furthermore to the aboveꢀmentioned advantageous, the
use of nontoxic and ecoꢀfriendly reagents, green solvents, and safe workup procedures makes
this catalytic methodology appropriate for industrial goals.
Acknowledgement
We are grateful to Prof. Achim Müller and Prof. Hartmut Bögge (the University of Bielefeld) for
their helps. Support for this research by the University of Isfahan is acknowledged.
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