Layered crystalline chiral salen Mn(III) complexes immobilized on organic polymer-inorganic hybrid zinc phosphonate-phosphate as efficient and reusable catalysts for the unfunctionalized olefin epoxidation

Article abstract of DOI:10.1016/j.inoche.2016.01.001

Chiral Mn(III) salen complexes grafted on ZnPS-PVPA (zinc poly(styrene-phenylvinyl-phosphonate)-phosphate) upon alkyldiamines through a facile method are evaluated by the asymmetric epoxidation of unfunctionalized olefins. Superior catalytic performances

Full text of DOI:10.1016/j.inoche.2016.01.001

Layered crystalline chiral salen Mn(III) complexes immobilized on organic
polymer–inorganic hybrid zinc phosphonate-phosphate as efficient and
reusable catalysts for the unfunctionalized olefin epoxidation
Jing Huang, Li Yuan, Jiali Cai, Xiaohong Chen, Dengwei Qi
PII:
DOI:
Reference:
S1387-7003(16)30001-6
doi: 10.1016/j.inoche.2016.01.001
INOCHE 6205
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
25 October 2015
1 January 2016
3 January 2016
Please cite this article as: Jing Huang, Li Yuan, Jiali Cai, Xiaohong Chen, Dengwei
Qi, Layered crystalline chiral salen Mn(III) complexes immobilized on organic poly-
mer–inorganic hybrid zinc phosphonate-phosphate as efficient and reusable catalysts for
the unfunctionalized olefin epoxidation, Inorganic Chemistry Communications (2016), doi:
1
0.1016/j.inoche.2016.01.001
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ACCEPTED MANUSCRIPT
Layered crystalline chiral salen Mn(III) complexes immobilized on organic polymer–inorganic
hybrid zinc phosphonate-phosphate as efficient and reusable catalysts for the unfunctionalized
olefin epoxidation
*a,b
a
c
a
d
Jing Huang, LiYuan, Jiali Cai, Xiaohong Chen, Dengwei Qi
a
Research Center for Advanced Computation, Xihua University; College of Science, Xihua
University, Chengdu, 610039, PR China. E-mail:hj41012@163.com;
Institute for Clean Energy & Advanced Materials, Southwest University, Chongqing 400715, PR
China.
b
c
College of Rongchang, Southwest University, Chongqing, PR China.
Ba Shu Middle School, Chongqing 400023, PR China.
d
Abstract
Chiral Mn(III) salen complexes grafted on ZnPS-PVPA (zinc poly(styrene-phenylvinyl-
phosphonate)-phosphate) upon alkyldiamines through a facile method are evaluated by the
asymmetric epoxidation of unfunctionalized olefins. Superior catalytic performances are obtained
(
conv%, up to >99; ee%, up to >99) whenever with m-CPBA or NaClO or NaIO as the oxidant.
4
The additives such as NMO, PPNO as well as imidazole play different roles in the corresponding
oxidation system. In addition, the supported catalysts could be reused nine times with the retention
of their efficiency. These results highlight the potentiality of ZnPS-PVPA as the support for
immobilizing chiral salen Mn (III) to be employed in oxidation reactions.
Keywords: Asymmetric epoxidation; unfunctionalized olefins; Jacobsen’s catalyst; heterogeneous
catalyst; alkyldiamines
1

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
Introduction
Asymmetric epoxidation of unfunctionalized prochiral olefins, catalyzed by chiral (salen)
Mn (III) complexes, has proven to be one of the most useful reactions in organic syntheses since
the obtained chiral epoxides contain two new stereocentres and can be easily transformed into a
large variety of compounds active in the industrial, biological, pharmaceutical and agricultural
fields [1-8]. Although great success has been achieved, the recovery and reuse of such
Jacobsen’s chiral salen Mn(III) complex is often troublesome [9-12]. Therefore, efforts have
been put on heterogenizing the Jacobsen catalyst by anchoring chiral (salen)Mn(III) complexes on
solid surfaces in order to enhance their stability, activity, selectivity, recovery and recycling
[13-18].
We have devoted ourselves to immobilizing homogeneous chiral salen Mn(III) on a series of
hybrid materials, such as zirconium oligostyrenylphosphonate-phosphate (ZSPP) and zirconium
poly (styrene-phenylvinylphosphonate)-phosphate (ZPS-PVPA) and zinc poly(styrene-phenylvinyl
phosphonate)-phosphate (ZnPS-PVPA) as well as calcium poly(styrene-phenylvinyl-
phosphonate)-phosphate (CaPS-PVPA). Moreover, the heterogeneous chiral salen Mn(III)
catalysts indicate superior disposition in asymmetric epoxidation of unfunctionalized
olefins[19-26].
With the purpose of having clearer insight into surface anchoring that assures no catalyst
leaching and high efficiency, we have now developed salen Mn(III) complex immobilized on
ZnPS-PVPA through alkyldiamines, especially designed to maintain the Mn(III) environment
unaltered after surface grafting. The aim of this work is to evaluate the influence of the synergy
of ZnPS-PVPA and the linkers as well as the chiral ligand on the performance and stability of
the heterogeneous catalysts.
Scheme 1


*Corresponding author: Fax: +86 288772 0200; Tel: +86 288772 0037; E-mail: hj41012@163.com;
2

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Scheme 2
All the supported catalysts 4a-d and chiral salen Mn(III)Cl have indicated the same band at
−
1
1
638 cm (Fig. S1) owing to the vibration of imine group. According to the azomethene (C=N)
-
1
stretching band, chiral salen Mn(III)Cl appear at 1613 cm and the supported catalysts emerge at
-1
−1
the vicinity of 1617 cm . The band around 3408 cm is observed for the catalysts, which is
-
1
ascribed to the stretching vibration of N-H groups. The stretching vibration at 1030 cm which is
assigned to characteristic vibrations of the phosphonate and phosphate in the support, is obviously
weakened by virtue of the electronic structure changes for the host-guest interaction.
The spectra of 4a-d have displayed features similar to those of chiral salen Mn(III)Cl on the
basis of UV-vis observation (Fig. S2). The band at 335 nm could be attributed to the charge
transfer transition of salen ligand. The band at 433 nm is due to the ligand-to-metal charge transfer
transition. The bands at 510 nm is assigned to the d-d transition of salen Mn(III) complex. There
manifest some deviations owing to an interaction between the salen Mn(III) complex and the
alkyldiamine modified ZnPS-PVPA.
According to the catalyst 4d (shown in Fig. 1), the initial weight loss is 3.5% below 180℃,
which is due to surface-bound or intercalated water in this stage. In the temperature range of
180-700℃, the organic moieties decompose, accompanied with 56.8% weight loss in this stage.
Obviously, the catalyst 4d still keep high stability lower than 180℃. In general, organic reactions
of heterogeneous catalysis are carried out below 180℃. Therefore, the catalyst 4d has adequate
thermal stabilities to be applied in heterogeneous catalytic reactions.
Fig. 1
Based on the desorption isotherm (Fig. 2), BJH analysis indicates a broad and non-uniform
distribution of pore size (in the range 2-18 nm), which demonstrates that the mesoporous structure
exist in the catalyst. The nitrogen adsorption-desorption isotherms are characteristic type V,
accompanied with a sharp increase in N adsorption at higher P/P values (~0.9) and a distinct
2
0
hysteresis loop (type H ). The pore diameters of the particles are mainly varied from 1nm to 18
1
nm, and a small quantity of the particles are below 2 nm as well as the less is distributed over 50
3

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nm in diameter.
Fig. 2
The corresponding textural parameters calculated by N adsorption-desorption isotherms and
2
Mn content of the immobilized catalysts are shown in Table 1.
Table 1
By means of chloromethylation, obvious increases are observed in BET surface area (1 vs 2,
2
-2
3
from 4.9 to 36.9 m /g), and in the pore volume (1 vs 2, from 1.3 to 18.8210 cm /g) as well as in
the average pore diameter (1 vs 2, from 3.5 to 10.21 nm). Although the chloromethylation of the
support contributes to the interlayer distance enlarged, the chloromethyl is relatively small so that
the corresponding textural parameters still increase. In contrast with this phenomenon, decreases
2
are observed in BET surface area (2 vs 4d, from 36.9 to 28.02 m /g) and in the pore volume (2 vs
-2
3
4
d, from 18.82 to 4.442 10 cm /g) as well as in the average pore diameter (2 vs 4d, from 10.21
to 0.61 nm) upon the immobilization of salen Mn (III) on ZnPS-PVPA. Owing to the steric bulkyl
salen Mn (III) introduced in ZnPS-PVPA, some caves, holes and channels would be occupied,
which contribute to the corresponding structure parameters ultimately decreasing. On account of
these facts, it could be deduced that some chiral salen Mn (III) complexes are immobilized on the
external surface of ZnPS-PVPA and others are inserted into the mesopores.
Fig. 3
According to SEM of 4d (Fig. 3B), the surface morphology varies from the smooth
anomalous structure for ZnPS-PVPA (Fig. 3A) to the loose amorphous configuration after the
immobilization of salen Mn (III). And many small caves and channels with irregular shapes also
2
exist, which would increase the surface area of the catalyst (from 4.9 to 28.02 m /g) and provide
enough chance for the substrates to access to the catalytic active sites.
Fig. 4
Shown in Fig. 4, great changes of TEM image of the catalyst 4d have taken place according
to ZnPS-PVPA. TEM photography of ZnPS-PVPA (Fig. 4A) manifests the spheroid structure and
the sizes of the particle in the range of 70-80 nm. While for the catalyst 4d (Fig. 4B), the
configuration is loose. The channels, holes and cavums could be also discerned clearly. Therefore,
4

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the catalysts could provide enough space for the epoxidation of unfunctionalized olefins and the
substrates would approach the internal catalytic active sites easily in the solution.
Table 2
On behalf of exploring the control of chirality of products, ZnPS-PVPA and 3d as well as
homogeneous catalyst 6 are employed to epoxidize indene with m-CPBA/NMO. Low olefin
enantio excesses are obtained (ee, 0% in entry 7 and 16.83% in entry 8, repectively), which
confirms that both ZnPS-PVPA and 3d are stereochemically inactive for the epoxidation of olefins.
Then, ee values increase from 54% to 86.7% (Jacobsen’s vs 6, entry 1 vs entry 9) through the
modification of alkyldiamine and further increase to 98% (6 vs 4d, entry 9 vs entry 5) upon
immobilizing on ZnPS-PVPA. In view of these results, it could be deduced that the whole
supported chiral salen Mn ( Ⅲ ) catalysts include the support ZnPS-PVPA, the linkage
alkyldiamine as well as chiral salen Mn center together contribute to the chirality of products.
Apart from this, ee values increase from 81% to 98%, conversions from 80% to >99% (entry 2-5)
with the increase of carbon number of alkylamine in the asymmetric epoxidation of indene, which
have been reported by C. Li [30] and our group [21]. Moreover, the catalytic activities of the
catalyst 4d (conv%, >99 vs 51; ee, 98 vs 8; entry 5 vs 10) and the homogeneous catalyst 6 (conv%,
89 vs 76; ee, 86.7 vs 82.5; entry 9 vs 10) obviously increase with the addition of NMO in the
epoxidation of indene, which is in accordance with the most articles reported [19-21].
According to NaClO/PPNO, the catalysts 4a-d manifest higher catalytic abilities than
Jacobsen’s catalyst (conv%, 85 - >99 vs >99; ee%, 88 - >99 vs 65; entry 12-15 vs entry 11) and
homogeneous catalyst 6 (conv%, 85 - >99 vs 86.2; ee%, 78 - >99 vs 92.6; entry 12-15 vs entry 17).
Notably, homogeneous catalyst 6 indicates 92.6% ee upon the modification of Jacobsen’s catalyst
(ee, 65%) and the catalytic ability keeps on increasing (ee, up to >99%) after the catalyst 6 is
immobilized on ZnPS-PVPA. Meanwhile, the catalytic activity indicates similar varying tendency
to m-CPBA/NMO, accompanying with the increase of the chain length in the epoxidations of
α-methylstyrene (conv%, from 85 to >99; ee, from 88 to >99; entry 12-15). In addition, ee values
still increase in the presence of PPNO (ee%: 81 vs >99, entry 16 vs 15; 67.5 vs 92.6, entry 18 vs
17), which agrees with the most literatures reported [19-21].
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As for NaIO /imidazole, the heterogeneous catalysts 4a-d display superior catalytic
4
properties to Jacobsen’s catalyst (ee%, >99 vs 69; entry 20-23 vs entry 19) and comparable
catalytic abilities to the catalyst 6 (conv%, >99 vs 86; ee%, >99 vs 82; entry 20-23 vs 25).
Simultaneously, ee values vary from 69% (Jacobsen’s catalyst, entry 19) to 82% (the catalyst 6,
entry 25) through the modification of alkyldiamine, followed by going on increasing to >99% (the
catalyst 4d, entry 23) upon the immobilization of the catalyst 6 onto ZnPS-PVPA. Moreover, both
the conversions and enantioselectivities of the catalysts 4a-d all exceed 99%, which is not
involved in the length of the linkage. Interestingly, the superior catalytic activities could still be
maintained whether the axial ligand imidazole is added or not (conv%, >99 vs >99; ee%, >99
vs >99; entry 23 vs entry 24). While for the homogeneous catalyst 6, the catalytic disposition
increase a little in the presence of imidazole (conv%, 86 vs 83; ee%, 82 vs 79, entry 25 vs 26). In
view of the results reported, the catalytic tests indicate excellent catalytic abilities (conv%, 97;
ee%, >99) in the absence of axial ligand imidazole and lower abilities (conv%, 70; ee%, 88) [31]
with the addition of imidazole.
Table 3
After recycling for twelve consecutive times, the results are listed in Table 3. Notably, the
catalytic ability decreases slightly and still indicates favourable disposition in the ninth recycling
(conv.%, 89; ee%, 91). The effective separating the chiral salen Mn(III) complexes by the solid
support ZnPS-PVPA could avoid the generation of the inactive μ-oxo-Mn(IV) species and
ultimately could contribute to the superior stability of the catalyst. The decrease of the yield could
be attributed to the decomposition of the chiral Mn (III) salen complex under epoxidative
conditions[32] and the loss of the hyperfine granules of the heterogeneous chiral Mn (III) salen
catalysts. The Mn content of the catalyst 4d reduces from 0.73 mmol/g (the fresh) to 0.45 mmol/g
after recycling for 9 times.
In summary, chiral salen Mn(III) anchored onto ZnPS-PVPA upon alkyldiamines have been
synthesized and indicate comparable or even higher enantioselectivities than homogeneous
catalyst. Moreover, the supported chiral Mn (III) salen catalysts are relatively stable and could be
recycled nine times in the asymmetric epoxidation of -methylstyrene. Our present investigation
6

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points to the generation of a general platform that will pave the way for heterogeneous
epoxidation reactions of alkenes generating no Mn catalyst waste and allowing continuous
recycling.
Supplementary data
FT-IR spectra, UV-vis spectrum, Experimental section.
Acknowledgement
This work is financially supported by the Fundamental Research Funds for the Central
Universities (XDJK2013C120), the Xihua University Key Projects (Z1223321), Sichuan Province
Applied Basic Research Projects (2013JY0090), the Department of Education of Sichuan Province
Projects (13ZB0030), Chongqing Special Funding for Postdoctoral (Xm2014028) and Chongqing
Postdoctoral Daily Fund (Rc201419).
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Figures captions:
Scheme 1 Synthesis of the heterogeneous catalysts
Scheme 2 Synthesis of homogeneous catalysts
Fig 1 TG curves of heterogenerous catalyst 4d
Fig 2 The nitrogen adsorption-desorption isotherm and pore distribution of the catalyst 4d
Fig 3 SEM photograph of (A) ZnPS-PVPA and (B) the catalyst 4d
Fig 4 TEM photograph of (A) ZnPS-PVPA and (B) the catalyst 4d
Fig. S1 FT-IR spectra of (1) 4d; (2) the neat chiral salen Mn (III)
Fig. S2 Solid reflectance UV-vis spectra (A) the neat chiral salen Mn (III);(B)the catalyst 4d
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9

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Tables
Table 1 The physical properties of ZnPS-PVPA, 2 and 4d
Surface
Pore volum
Average pore Mn content
Sample
2
-2
3
area (m /g) (10 cm /g) diameter (nm) (mmol/g)
1
2
4.9
1.3
3.5
10.21
0.61
-
-
36.9
28.02
18.82
4.442
4
d
0.73
10

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Table 2 Asymmetric epoxidation of α-methylstyrene and indene catalyzed by homogeneous and heterogeneous
a
b
c
catalysts (4a-h) with m-CPBA/NMO , NaClO/PPNO and NaIO /imidazole as oxidant systems
4
d
e
f
-4 -1
Entry
Substrate
Catalyst
Oxidant system
m-CPBA/NMO
m-CPBA/NMO
m-CPBA/NMO
m-CPBA/NMO
m-CPBA/NMO
m-CPBA
Time
Conv.(%)
98
ee
TOF ×10 (s )
54.42
1
2
3
4
5
6
7
8
9
A
A
A
A
A
A
A
A
A
A
Jacobsen’s
1
1
1
1
1
1
1
1
1
1
54
81
4a
80
44.44
4b
82
85
45.58
4c
92
92
51.09
4d
99
51
98
54.99
4d
8
28.35
ZnPS-PVPA
m-CPBA/NMO
m-CPBA/NMO
m-CPBA/NMO
m-CPBA
>99
>99
89
0
54.99
3d
6
16.83
86.7
82.5
54.99
49.44
1
0
6
76
42.21
1
1
B
B
B
B
B
B
B
B
Jacobsen’s
NaClO/PPNO
NaClO/PPNO
NaClO/PPNO
NaClO/PPNO
NaClO/PPNO
NaClO
24
24
24
24
24
24
24
24
>99
85
65
88
2.31
1.96
2.02
2.18
2.29
1.30
1.99
1.90
1
1
1
1
1
1
1
2
3
4
5
6
7
8
4a
4b
4c
4d
4d
6
87
90
94
91
>99
65
>99
81
NaClO/PPNO
NaClO
86.2
82
92.6
67.5
6
1
9
B
B
B
B
B
B
B
B
Jacobsen’s
NaIO /imidazole
5
5
5
5
5
5
5
5
>99
>99
>99
>99
>99
>99
86
69
>99
>99
>99
>99
>99
82
11.11
11.11
11.11
11.11
11.11
11.11
9.65
4
2
0
4a
4b
4c
4d
4d
6
NaIO /imidazole
4
2
2
2
2
2
2
1
2
3
4
5
6
NaIO /imidazole
4
NaIO /imidazole
4
NaIO /imidazole
4
NaIO4
NaIO /imidazole
4
6
NaIO4
83
79
9.31
a
2 2
Reactions were carried out at -20 °C in CH Cl (3 mL) with indene (1 mmol), n-nonane (internal standard, 1 mmol), NMO (5 mmol),
homogeneous (5 mol%) or heterogeneous salen Mn(III) catalysts (5 mol%) and m-CPBA (2 mmol). The conversion and the ee value
were determined by GC with chiral capillary columns HP19 091G-B213, 30 m × 0.32mm × 0.25 μm.
b
2 2
Reactions were carried out at 20 ℃ in CH Cl (2 mL) with α-methylstyrene (1 mmol), PPNO (0.38 mmol) and NaClO (pH 11.5, 0.55
M, 3 mL). Other conditions are the same as aforementioned.
c
d
e
f
4 3 2
Reactions conditions: alkene (1 mmol), NaIO (2 mmol), catalyst (0.03mmol), CH CN/H O (10 mL/5 mL).
A = indene, B = α-methylstyrene.
(
S)-form.
-1
Turnover frequency (TOF) is calculated by the expression of [product]/[catalyst] × time (s ).
11

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a
Table 3 The recycles of catalyst 4d in the asymmetric epoxidation of α-methylstyrene
b
c
-4 -1
Run
1
Time
24
24
24
24
24
24
24
24
24
24
24
24
24
Conversion (%)
ee (%)
TOF ×10 (s )
2.31
>99
99
98
97
95
93
91
90
89
84
82
75
67
>99
99
2
2.29
3
98.5
98.1
96.6
96
2.27
4
2.25
5
2.20
6
2.15
7
95.4
92
2.11
8
2.09
9
91
2.06
1
0
1
87.6
82.1
76
1.94
1
1.90
1
1
2
3
1.74
62
1.55
a
Reactions were carried out at -40 ℃ in CH Cl (4 mL) with α-methylstyrene (1 mmol), n-nonane (internal
2
2
standard, 1 mmol), m-CPBA (0.38 mmol), heterogeneous salen Mn (III) catalysts (5 mol%). The conversion and
the ee value were determined by GC with chiral capillary columns HP19091G-B213, 30 m×0.32 mm×0.25 μm.
b
Same as in Table 2.
Same as in Table 2.
c
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Figures
Scheme 1
Scheme 2
13

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Fig 1
Fig 2
14

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Fig 3
Fig 4
15

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Graphic Abstract-pictogram
Layered crystalline chiral salen Mn(III) complexes immobilized on organic polymer–inorganic
hybrid zinc phosphonate-phosphate as efficient and reusable catalysts for the unfunctionalized
olefin epoxidation
*a,b
c
a
Jing Huang, Jiali Cai, Chenxiao Hong
16

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Graphical abstract-synopsis
The catalysts that alkyldiamines modified ZnPS-PVPA are used for the immobilization of chiral
salen Mn (III) display superior catalytic ability either for the experimental scale reactions or for
the large-scale reactions.
17

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Highlights


The chiral salen Mn(III) is immobilized on alkyldiamines modified ZnPS-PVPA
The heterogeneous catalysts display superior activity according to the homogeneous
catalysts


The heterogeneous catalysts could be reused at least nine times without significant loss
of activity
The catalysts could be used in large-scale reactions with superior catalytic disposition
18