Science in China Series B: Chemistry

2009

www.scichina.com
chem.scichina.com
www.springerlink.com

SCIENCE IN CHINA PRESS

Springer

Chiral Mn() salen complex immobilized on

imidazole-modified mesoporous material via
co-condensation method as an effective catalyst
for olefin epoxidation
LOU LanLan1, YU Yi1, YU Kai2, JIANG Shu1, DONG YanLing1 & LIU ShuangXi1
1
2

Institute of New Catalytic Materials Science, College of Chemistry, Nankai University, Tianjin 300071, China;
College of Environmental Science and Engineering, Nankai University, Tianjin 300071, China

An imidazole modified mesoporous material has been prepared through a co-condensation procedure
and adopted to covalently anchor chiral Mn() salen complex. The active centers in the as-synthesized
catalyst were presented in the form of ionic species. The results of XRD, FTIR, DRUV-Vis, and N2 sorption confirmed the successful immobilization of chiral Mn() salen complex inside the channels of the
modified support and the maintenance of the mesoporous structure of parent support in the immobilized catalyst. This heterogeneous catalyst exhibited comparable catalytic activity and enantioselectivity to those of the homogeneous counterpart in the asymmetric epoxidation of unfunctionalized olefins.
Furthermore, notably high turnover frequencies have been obtained over this heterogeneous catalyst
for the relatively short reaction time and low catalyst amount, due in part to the ionic property as well as
the uniform distribution of the active centers.
imidazole-functionalized mesoporous material, chiral Mn() salen complex, co-condensation, asymmetric epoxidation, unfunctionalized olefins

1 Introduction
The asymmetric epoxidation of unfunctionalized olefins
is highly significant in the synthesis of a variety of
valuable chiral building blocks that can be easily converted into other useful chiral compounds through
stereoselective ring-opening or functional group transformations[1], and thus is widely used in the synthesis of
fine chemicals, pharmaceuticals and agrochemicals.
Chiral Mn( ) salen complexes have proven to be
highly efficient homogeneous catalysts for the asymmet
ric epoxidation of unfunctionalized olefins[2 4]. However,
the catalysts generally present problems in separation
and recycling under homogeneous catalytic system.
Consequently, the heterogenization of chiral Mn()
salen complexes has received great attention in the last

decade[5 17] due to efficient product purification and

easy catalyst recovery. However, in most cases, the heterogeneous chiral Mn() salen catalysts would show
lower activity and/or enantioselectivity than their homogeneous counterparts.
Recently, room temperature ionic liquids have attracted attention as important solvents in synthesis and
catalysis owing to their strong solvent power for many
organic and inorganic substances[18,19]. Some efforts
have been made to allow chiral Mn() salen complexes
to be recovered by using ionic liquid biphasic system[20],
supported ionic liquid system[21], as well as anchoring
ionic liquid moiety onto chiral Mn() salen complex[22,23],
Received May 31, 2009; accepted July 16, 2009
doi: 10.1007/s11426-009-0209-6

Corresponding author (email: sxliu@nankai.edu.cn)

Supported by the National Natural Science Foundation of China (Grant No.
20773069), and the Specialized Research Fund for the Doctoral Program of Higher
Education (Grant No. 200800551017)

Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422

and satisfactory catalytic activities have been obtained.

Lately, we have described a kind of ionic liquid containing chiral Mn() salen unit covalently anchored on
mesoporous materials via a post-grafting process. The
heterogeneous catalysts exhibited quite good catalytic
activity and enantioselectivity in the asymmetric epoxidation of unfunctionalized olefins within a short reaction
time, owing to the ionic properties of the active centers
as well as the large pore sizes of the mesoporous supports[24].
In this work, we described another kind of supported
chiral Mn() salen catalyst, in which the active center
is also presented in the form of ionic liquid. A template
directed co-condensation procedure was adopted to synthesize imidazole-functionalized mesoporous MCM-41
material, which was then acting as the support to covalently immobilize chiral Mn() salen complex, leading
to the formation of ionic active centers. Co-condensation
(one-pot synthesis) is an alternative method to synthesize organically functionalized mesoporous materials.
The organic units in materials synthesized by co-condensation are generally more homogeneously distributed
than in materials obtained through a post-grafting
process[25]. Thus, using the imidazole-functionalized
mesoporous material prepared via co-condensation as
matrix to immobilize chiral Mn() salen catalyst would
lead to more uniform distribution of the active centers.
Along with the consideration of ionic property of the
active centers, higher catalytic activities could be expected over as-synthesized heterogeneous chiral Mn()
salen catalyst.

Scheme 1

1418

2 Experimental
2.1 Synthesis of the heterogeneous catalyst
The heterogeneous Mn() salen catalyst im-41/C1 was
prepared as shown in Scheme 1.
N-(3-triethoxysilylpropyl)imidazole (denoted as TESI)
was prepared by the reaction of imidazole with
(3-chloropropyl)triethoxysilane[26]. An imidazole-containing ordered silica hybrid MCM-41 material im-41 was
then synthesized via co-condensation between tetraethyl
orthosilicate (TEOS) and TESI with cetyltrimethylammonium bromide (CTAB) as the template. In a typical
synthesis, CTAB was dissolved in warm deionized water,
and to this solution ammonia was added under vigorous
stirring. The required quantity of TEOS and TESI was
then added dropwise into the solution. After stirring for
an additional 0.5 h at room temperature, a gel with a
molar composition of 0.95 TEOS/0.05 TESI/0.12
CTAB/8 NH4OH/114 H2O was obtained. The gel was
transferred into a Teflon-lined autoclave for crystallization at 383 K for 60 h. The solid product was recovered
by filtration, washed, dried and then Soxhlet-extracted
with acidic ethanol for 72 h to remove the template.
The chiral Mn() salen complex C1 was prepared as
described previously[24]. Then the imidazole-functionalized mesoporous material of im-41 (1.0 g) and C1
(0.04 g) were refluxed under vigorous stirring in 60 mL
of toluene for 24 h (Scheme 1). The solid product
im-41/C1 was collected by filtration, washed with dichloromethane, and Soxhlet-extracted with acetone for
20 h. The loading of complex C1 in the heterogenized

The synthesis of immobilized Mn() salen catalyst im-41/C1.

LOU LanLan et al. Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422

catalyst was 0.034 mmolg1, based on Mn content determined by ICP-AES.

2.2 Catalyst characterization
The content of Mn in the heterogeneous catalyst was
determined by ICP-AES on an ICP-9000(N+M) spectrometer (TJA Co.,). Powder X-ray diffraction (XRD)
patterns were recorded using an R/max-2500 diffractometer with CuK radiation (40 kV and 100 mA). FTIR
spectra in the 4004000 cm1 region were measured
using KBr pellets on a Bruker Vector 22 spectrometer.
Diffuse reflectance UV-Vis (DRUV-Vis) spectra were
acquired with a Shimadzu UV-2550 UV-Vis spectrophotometer from 220 to 800 nm. N2 adsorption-desorption isotherms at 77 K were conducted on a Micromeritics TriStar 3000 apparatus. Surface areas were calculated
using the BET equation, and the pore size distributions
were estimated using the BJH model.
2.3 Catalytic test
Asymmetric epoxidation reactions were carried out using
0.68 mol% of catalyst with styrene and -methylstyrene
as substrates (1 mmol) in the presence of m-CPBA/NMO
as oxidant in 10 mL of dichloromethane at 273 K. Conversions (with toluene as an internal standard) and enantiomeric excess (ee) values were determined by gas
chromatography with a chiral -cyclodextrin capillary
column (RESTEK RT-BetaDEXse, 30 m 0.25 mm
0.25 m).

ous catalyst im-41/C1. The pattern of im-41 exhibited

three XRD peaks assigned to (100), (110), and (200)
reflections, which is typical for 2D hexagonal lattice. On
immobilization of chiral Mn(III) salen complex C1, a
marginal decrease in the relative intensities of the XRD
reflections was observed, indicating that the mesoporous
structure of im-41 retained intact after the immobilization.
The FTIR spectra in the scan range 12003300 cm1
of im-41 and im-41/C1 are given in Figure 2. The intensities of the IR bands near 3000 and 1400 cm1, which
were due to CH stretching vibrations and CH
deformation vibrations of alkyl groups, respectively,
increased with the immobilization of chiral Mn()
salen complex C1. In the spectrum of im-41, the IR
band attributed to C=N stretching vibrations appeared at
around 1637 cm1, which was overlapped by the OH
bending vibrations of adsorbed water. On immobilization of chiral Mn() salen complex C1, the band at
1637 cm1 shifted to 1619 cm1, which was attributed to
the presence of C=N in salen ligand, which participated
in coordination with manganese ions. Furthermore, a
new characteristic band of Mn() salen appeared at
1544 cm1. The IR spectra confirmed the successful
immobilization of chiral Mn() salen complex C1 on
imidazole-functionalized mesoporous material.

3 Results and discussion

3.1 Characterization of the materials
Shown in Figure 1 are XRD patterns for the imidazole-functionalized material im-41 and the heterogene-

Figure 2

Figure 1

Powder XRD patterns of (a) im-41 and (b) im-41/C1.

FTIR spectra of (a) im-41 and (b) im-41/C1.

Figure 3 depicts the DR UV-Vis spectra for chiral

Mn() salen complex C1, imidazole-functionalized material im-41, and heterogeneous catalyst im-41/C1. The
spectrum of im-41/C1 reveals features similar to those of
complex C1, while there is no obvious absorption in the
spectrum of im-41. The bands at 286 and 325 nm could
be due to the charge transfer transition of salen ligand,

LOU LanLan et al. Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422

1419

3.2 Studies of catalytic activity

Figure 3 DR UV-Vis spectra of (a) Mn() salen complex C1, (b)

im-41/C1 and (c) im-41.

and the bands at 438 and 510 nm were attributed to

ligand-to-metal charge transfer transition and d-d transition of Mn() salen complex, respectively. After immobilization of Mn() salen complex on im-41, a blue
shift from 286, 438, and 510 nm to 259, 419, and 496
nm, respectively, was observed, indicating the presence
of interaction between complex C1 and the mesoporous
material. The results of DR UV-Vis analysis further confirmed the immobilization of C1 on the material im-41.
The mesoporous material im-41 and the heterogeneous catalyst im-41/C1 were characterized by N2 sorption.
Both of them exhibited type IV isotherms and uniform
pore sizes, suggesting that the mesoporous structure was
maintained in the immobilized catalyst. The corresponding textural parameters are presented in Table 1. A
large decrease in BET surface area, pore volume, and
pore size was observed on immobilization of C1, indicating that the chiral Mn() salen complex is present
inside the channels of imidazole-modified mesoporous
material.
Table 1

Structure parameters of im-41 and im-41/C1

Sample
im-41
im-41/C1

SBET (m2g1) Pore volume (cm3g1) Pore diameter (nm)

706
0.79
2.46
578
0.56
1.90

The heterogeneous catalyst im-41/C1 was evaluated in

the epoxidation of styrene and -methylstyrene. The
results are listed in Table 2. For comparison, the chiral
Mn() salen pre-catalyst C1 was also investigated under the same reaction conditions.
As shown in Table 2, catalyst im-41/C1 exhibited
comparable catalytic activity and enantioselectivity to
homogeneous catalyst C1. The imidazole-functionalized
material im-41 was catalytically inactive for the epoxidation of -methylstyrene (entry 5), indicating that the
chiral Mn(III) salen unit was the unique active center in
the immobilized catalyst. It is noteworthy that the olefin
epoxidation over heterogeneous catalyst im-41/C1 can
reach completion after only 1 h, providing an extraordinarily high turnover frequency (TOF) of ca. 135 h1 at this
point (entries 2 and 6). These TOF values were comparable to those for homogeneous catalyst C1 and remarkably higher than those of mesoporous materialimmobilized catalysts reported in refs. [14,15,27,28]. In
most cases, relatively long reaction time was required
over heterogeneous catalyst, owing to diffusional con
straints[13 17,27,28]. As mentioned previously[24], the ionic
property of active centers may facilitate entry of reactants and oxidants into the channels of the catalysts and
contact with the active sites, thus leading to shortened
reaction time and increased catalytic activity.
For comparison, the heterogeneous catalyst MCM41im/C1 was also synthesized, which was a supported
chiral Mn() salen-containing ionic species on mesoporous MCM-41 via a post-grafting process (Scheme 2). It
can be observed that the present catalyst im-41/C1 exhibited rather higher catalytic performance compared
with catalyst MCM41-im/C1 (entries 3 and 7). Higher
conversions were obtained over im-41/C1 for the epoxidation of styrene and -methylstyrene with a relatively

Table 2 Asymmetric epoxidation of unfunctionalized olefins catalyzed by homogeneous and heterogeneous catalysts a)
Entry
Catalyst b)
Substrate
Time (h)
Conv. (%) c)
ee (%) d)
TOF (h1) e)
1
styrene
1
>99
49(R)
147
C1
2
im-41/C1
1
92
42(R)
135
3
1
90
42(R)
60
MCM41-im/C1
4
1
>99
42(R)
147
C1
-methylstyrene
5
1

im-41
6
im-41/C1
1
96
36(R)
141
1
88
38(R)
59
7
MCM41-im/C1
a) Reaction conditions: reaction temperature 273 K, solvent: CH2Cl2, oxidant system: m-CPBA/NMO, substrate 1.00 mmol, substrate/m-CPBA/NMO =
1:2:5; b) the catalyst was 0.68 mol% of olefins for C1 and im-41/C1 while 1.5 mol% for MCM41-im/C1; c) conversion% determined by GC with chiral
column using toluene as the internal standard; d) ee% determined by GC with RESTEK RT-BetaDEXse chiral column; e) turnover frequency (TOF) is
calculated by the expression [product]/[catalyst] time (h1).
1420

LOU LanLan et al. Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422

Scheme 2

The synthesis of immobilized Mn(III) salen catalyst MCM41-im/C1.

small amount of catalysts under identical reaction time,

thus giving notably higher TOF values than those for
MCM41-im/C1 (e.g., 141 vs. 59 h1 for -methylstyrene).
This can be attributed mainly to the more uniform distribution of active sites in catalyst im-41/C1, which was
synthesized through a co-condensation procedure. The
active sites could be accessed more readily and effectively, which would be responsible for the enhanced
catalytic activity.
The heterogeneous catalyst was separated by filtration
after the reaction. The filtrate was detected by ICP-AES,
and only a slight Mn leaching (0.7%) was found, indicating that the Mn() salen complex is strongly anchored on the mesoporous material. Moreover, no further increase in the conversion occurred while fresh re-

Zhang H, Li C. Asymmetric epoxidation of 6-cyano-2,2-dimethyl-

actant was added to the filtrate.

4 Conclusions
The chiral Mn() salen complex was covalently supported in the form of ionic liquid on the mesoporous
material functionalized by imidazole through a co-condensation procedure. The catalyst exhibited comparable
catalytic activity and enantioselectivity to those of the
homogeneous counterpart in the asymmetric epoxidation
of styrene and -methylstyrene. In particular, this catalyst can complete epoxidation rapidly with a relatively
low amount of catalysts, thus providing notably high
TOF values (ca. 135 h1), which is attributed in part to
the ionic properties as well as the uniform distribution of
the active centers.

Strategies for the immobilisation of homogeneous catalysts. Chem

als. Tetrahedron, 2006, 62: 66406649

Soc Rev, 2004, 33: 108122

Zhang W, Loebach J L, Wilson S R, Jacobsen E N. Enantioselective

Li C. Chiral synthesis on catalysts immobilized in microporous and

Fan Q H, Li Y M, Chan A S C. Recoverable catalysts for asymmetric

epoxidation of unfunctionalized olefins catalyzed by salen manganese

complexes. J Am Chem Soc, 1990, 112: 28012803
3

mesoporous materials. Catal Rev -Sci Eng, 2004, 46: 419492

Srinivasan K, Michaud P, Kochi J K. Epoxidation of olefins with

cationic (salen)manganese() complexes. The modulation of cata-

organic synthesis. Chem Rev, 2002, 102: 33853466

10

lytic activity by substituents. J Am Chem Soc, 1986, 108: 23092320

4

Rev, 2005, 105: 16031662

11

the first irreversible step. J Am Chem Soc, 1994, 116: 425426

Chem Rev, 2006, 106: 39874043

12

32173274
6

Baleizo C, Garcia H. Chiral salen complexes: An overview to recoverable and reusable homogeneous and heterogeneous catalysts.

Leadbeater N E, Marco M. Preparation of polymer-supported ligands

and metal complexes for use in catalysis. Chem Rev, 2002, 102:

Xia Q H, Ge H Q, Ye C P, Liu Z M, Su K X. Advances in homogeneous and heterogeneous catalytic asymmetric epoxidation. Chem

Zhang W, Lee N H, Jacobsen E N. Nonstereospecific mechanisms in

asymmetric addition to alkenes result in enantiodifferentiation after

McMorn P, Hutchings G J. Heterogeneous enantioselective catalysts:

chromene on Mn(salen) catalyst immobilized in mesoporous materi-

Li C, Zhang H, Jiang D, Yang Q. Chiral catalysis in nanopores of

mesoporous materials. Chem Commun, 2007, 547558

Song C E, Lee S G. Supported chiral catalysts on inorganic materials.

Chem Rev, 2002, 102: 34953524

13

Zhou X G, Yu X Q, Huang J S, Li S G, Li L S, Che C M. Asymmetric

epoxidation of alkenes catalyzed by chromium binaphthyl Schiff base

LOU LanLan et al. Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422

1421

complex supported on MCM-41. Chem Commun, 1999, 17891790

14

Kim G J, Shin J H. The catalytic activity of new chiral salen com-

supported ionic liquid phase. Tetrahedron Lett, 2006, 47: 65136516

22

plexes immobilized on MCM-41 by multi-step grafting in the asym-

salen Mn() complexes as tunable separation catalysts for enanti-

metric epoxidation. Tetrahedron Lett, 1999, 40: 68276830

15

Kureshy R I, Ahmad I, Khan N H, Abdi S H R, Singh S, Pandia P H,

oselective epoxidation of styrene. J Catal, 2008, 255: 287295

23

Jasra R V. New immobilized chiral Mn() salen complexes on pyri-

16

tive epoxidation of styrene. J Catal, 2009, 263: 284291

24

anchored chiral Mn() salen-containing ionic species on mesoporous

tionalized olefins catalyzed by the Mn(salen) catalysts immobilized in

materials as effective catalysts for asymmetric epoxidation of un-

Bigi F, Moroni L, Maggi R, Sartori G. Heterogeneous enantioselective

functionalized olefins. J Catal, 2007, 249: 102110

25

mesoporous organic-inorganic hybrid materials. Angew Chem Int Ed,

complexes supported on amorphous or MCM-41 silica through a new

2006, 45: 32163251

26

Welton T. Room-temperature ionic liquids. Solvents for synthesis and

Wasserscheid P, Keim W. Ionic liquids-new solutions for transition

20

Song C E, Roh E J. Practical method to recycle a chiral (salen)Mn

J Mater Chem, 2000, 10: 25262531

27

metal catalysis. Angew Chem Int Ed, 2000, 39: 37723789

epoxidation catalyst by using an ionic liquid. Chem Commun, 2000,

Lazarin A M, Gushikem Y, deCastro S C. Cellulose aluminium oxide

coated with organofunctional groups containing nitrogen donor atoms.

catalysis. Chem Rev, 1999, 99: 20712084

19

21

Hoffmann F, Cornelius M, Morell J, Frba M. Silica-based

epoxidation of olefins catalysed by unsymmetrical (salen)Mn()

triazine-based linker. Chem Commun, 2002, 716717
18

Lou L L, Yu K, Ding F, Peng X, Dong M, Zhang C, Liu S. Covalently

Zhang H, Zhang Y, Li C. Enantioselective epoxidation of unfuncthe nanopores of mesoporous materials. J Catal, 2006, 238: 369381

17

Tan R, Yin D, Yu N, Zhao H, Yin D. Easily recyclable polymeric ionic

liquid-functionalized chiral salen Mn() complex for enantioselec-

dine N-oxide-modified MCM-41 as effective catalysts for epoxidation

of nonfunctionalized alkenes. J Catal, 2005, 235: 2834

Tan R, Yin D, Yu N, Jin Y, Zhao H, Yin D. Ionic liquid-functionalized

Kim G J, Kim S H. Immobilization of new salen Mn complex over

MCM-41 and its activity in asymmetric epoxidation of styrene. Catal
Lett, 1999, 57: 139143

28

Silva A R, Wilson K, Clark J H, Freire C. Covalent attachment of

837838

chiral manganese() salen complexes onto functionalised hexagonal

Lou L L, Yu K, Ding F, Zhou W, Peng X, Liu S. An effective approach

mesoporous silica and application to the asymmetric epoxidation of

for the immobilization of chiral Mn() salen complexes through a

alkenes. Microporous Mesoporous Mater, 2006, 91: 128138

1422

LOU LanLan et al. Sci China Ser B-Chem | Sep. 2009 | vol. 52 | no. 9 | 1417-1422