2492 Langmuir 2007, 23, 2492-2496

Anchoring of Copper Complex in MCM-41 Matrix: A Highly Efficient

Catalyst for Epoxidation of Olefins by tert-BuOOH
Sreyashi Jana, Buddhadeb Dutta, Rajesh Bera, and Subratanath Koner*
Department of Chemistry, JadaVpur UniVersity, Kolkata 700 032, India

ReceiVed August 15, 2006. In Final Form: NoVember 15, 2006

A complex moiety containing copper (II) has been anchored covalently into the organic-modified Si-MCM-41
to prepare a new catalyst. The amine group containing organic moiety 3-aminopropyl-triethoxysilane has been first
anchored on the surface of Si-MCM-41 via silicon alkoxide route. The amine group upon condensation with salicyldehyde
affords a bidentate ligand in the mesoporous matrix for anchoring copper(II) ions. The prepared catalyst has been
characterized by UV-vis, electron paramagnetic resonance (EPR), and infrared (IR) spectroscopic analysis, small-
angle X-ray diffraction, and N2 sorption study. A remarkable difference in the pore structure has been observed after
the immobilization of copper(II) complex in Si-MCM-41. The catalyst showed excellent catalytic efficiency in
epoxidation reactions with various olefinic compounds including styrene and allyl alcohol, using tert-BuOOH as
oxidant. Notably, styrene shows unprecedented high conversion (97%) as well as epoxide selectivity (89%) with
tert-BuOOH over the Cu-MCM-41 catalyst.

Introduction Scheme 1. (a) Modification of Si-MCM-41 Channel Wall:

APTES/CHCl3; (b) Condensation with Salicylaldehyde in
Epoxides are very useful and versatile intermediates for the Methanol; (c) Metal Complex Formation: Cu(NO3)2‚3H2O/
synthesis of many commodity and fine chemicals, and studies MeOH
on epoxidation of CdC bond have received a lot of attention.1
The traditional procedure for epoxidation of alkene is oxidation
by stoichiometric amount of peracids.2 However, peracids are
very expensive, are hazardous to handle, and are nonselective
for the epoxide formation and also lead to formation of undesirable
products, creating a lot of waste.3 Many catalytic epoxidation
methods, including asymmetric epoxidation, have been devel-
oped,4 but selective epoxidation of alkenes using heterogeneous
catalysts and clean oxidants under mild conditions is still a
challenge.5 Catalysts derived by immobilization of transition-
metal complex in microporous or mesoporous matrixes6-8 by
various means have been employed in epoxidation reactions.6c,7,8
These materials are, particularly, gaining importance in catalysis
research owing to their potential applications in industry.
processes.9 The recycling of coproduct, that is, tert-BuOH, has
Alkyl hydroperoxides are used on a large scale in industrial
been realized in the Sumitomo process. Oxidation of cyclohexene
epoxidation, for example, in Halcon-Arco and Sumitomo
using Mn-exchanged NaY zeolite gives allylic product, di-(2-
* To whom correspondence should be addressed. Tel: +91 33 2414 6666 cyclohexenyl)-ether in 98% yield, but epoxidation is impossible
ext. 2505; fax: +91 33 2414 6584; e-mail: snkoner@chemistry.jdvu.ac.in. in case of aromatic olefin-like styrene.10 Krijnen and co-workers
(1) Gerhartz, W.; Yamamoto, Y. S.; Kandy, L.; Rounsaville, J. F.; Schulz, G. used Ti-silsesquioxanes impregnated on MCM-41 in heteroge-
Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed.; Verlag Chemie:
Weinheim, Germany, 1987; Vol. A9, p 531. neous epoxidation catalysis; a catalyst concentration of 1 mol
(2) Organic Peroxide; Swern, D., Ed.; Wiley-Interscience: New York, 1971; % of Ti is sufficient to convert an otherwise unreactive olefin
Vol. 2. 1-octene for 80%, with 80% epoxide selectivity,11 but leaching
(3) (a) Barf, G. A.; Sheldon, R. A. J. Mol. Catal. A 1995, 102, 23. (b) Mukaiyama,
T.; Yamada, T. Bull. Chem. Soc. Jpn. 1995, 68, 17. of Ti compound sometimes creates problem with such catalysts.
(4) (a) Pietikäinen, P. Tetrahedron Lett. 1999, 40, 1001. (b) Jacobsen, E. N.; TS-1 or Ti-containing molecular sieves are also able to perform
Zhang, W.; Muci, L. C.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. the selective oxidations of olefins by H2O2.12 Covalently grafted
(c) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974.
(5) (a) Fraile, J. M.; Garcia, J.; Mayoral, J. I.; Vispe, E. J. Catal. 2000, 189, [RuII(TCPP)(CO)(EtOH)] (TCPP ) meso-tetrakis-(4-chlorophen-
40. (b) De, D. E. Vos; Jacobs, P. A. Catal. Today 2000, 157, 05. yl)-porphyrin) complex onto MCM-41 showed impressive
(6) (a) Thomas, J. M. Angew. Chem., Int. Ed. 1999, 38, 3588. (b) Koner, S.;
Chaudhari, K.; Das, T. K.; Sivasanker, S. J. Mol. Catal. A 1999, 150, 295. (c) turnovers (max 300 h-1) in alkene epoxidation reactions with
Koner, S. Chem. Commun. 1998, 593. (d) Ganesan, R.; Viswanathan, B. J. Phys.
Chem. B 2004, 108, 7102. (e) De, Vos, D. E.; Thibault-Starzyk, F.; Jacobs, (9) Brégeault, J.-M. Dalton Trans. 2003, 3289.
P. A. Angew. Chem., Int. Ed. Engl. 1994, 33, 431. (f) Balkus, K., Jr.; Eisa, M.; (10) Farzaneh, F.; Sadeghi, S.; Turkian, L.; Ghandi, M. J. Mol. Catal. A 1998,
Levedo, R. J. Am. Chem. Soc. 1995, 117, 10753. (g) Seelan, S.; Sinha, A. K.; 179, 255.
Srinivas, D.; Sivasanker, S. J. Mol. Catal. A 2000, 157, 163. (h) Lee, C.-H.; (11) (a) Krijnen, S.; Abbenhuis, H. C. L.; Hanssen, R. W. J. M.; Van, Hooff,
Wong, S.-T.; Lin, T.-S.; Mou, C.-Y. J. Phys. Chem. B 2005, 109, 775. (i) Murphy, J. H. C.; Van, Santen, R. A. Angew. Chem. 1998, 110, 374. (b) Krijnen, S.; Mojet,
E. F.; Ferri, D.; Baiker, A.; Doorslaer, S. V.; Schweiger, A. Inorg. Chem. 2003, B. L.; Abbenhuis, H. C. L.; Van, Hooff, J. H. C.; Van, Santen, R. A. Phys. Chem.
42, 2559. Chem. Phys. 1999, 1, 361. (c) Abbenhuis, H. C. L.; Krijnen, S.; Van Santen,
(7) Bedioui, F. Coord. Chem. ReV. 1995, 144, 39, and references therein. R. A. Chem. Commun. 1997, 331.
(8) (a) Pillinger, M.; Gonçalves, I. S.; Lopes, A. D.; Madureira, J.; Ferreira, (12) (a) Corma, A.; Navarro, M. T.; Pérez Pariente, J. Chem. Commun. 1994,
P.; Valente, A. A.; Santos, T. M.; Rocha, J.; Menezes, J. F. S.; Carlos, L. D. 147. (b) Schmidt, I.; Krogh, A.; Wienberg, K.; Carlsson, A.; Brorson, M.; Jacobsen,
Dalton Trans. 2001, 1628. (b) Kim, G.-J.; Kim, S.-H. Catal. Lett. 1999, 57, 139. C. J. H. Chem. Commun. 2000, 2157 and references therein.

10.1021/la062409t CCC: $37.00 © 2007 American Chemical Society

Published on Web 01/17/2007
Anchoring of Copper Complex in MCM-41 Matrix
Figure 1. IR spectra of (a) Si-MCM-41; (b) MCM-41-(SiCH2-
CH2CH2NH2)x. IR spectrum of the Cu-MCM-41 catalyst has been
shown in the inset.
Figure 2. X-band Continuous Wave EPR spectrum of Cu-
MCM-41.
tert-BuOOH, however, epoxide selectivities were only moder-
ate: with cyclohexene, the allylic alcohol (33%) and ketone
(57%) were the main products, while in the case of styrene, 70%
benzaldehyde was produced.13
Herein we report the preparation, characterization, and catalytic
study of a catalyst derived by organic modification of MCM-41
and anchoring of copper(II) through complex formation into
MCM-41; the prepared catalyst exhibits an excellent catalytic
activity in epoxidation reactions with a variety of olefinic
compounds using tert-BuOOH as oxidant.
Experimental
Materials. The solvents were purchased from Merck (India) and
were distilled and dried before use. Styrene, norbornene, allyl alcohol,
cyclooctene, cyclohexene, and tert-BuOOH (70% aq) were purchased
form Aldrich and were used as received.
Catalyst Preparation. Mesoporous Si-MCM-41 was prepared
according to the literature method14 with slight modification, using
C16H33N(CH3)3Br (CTMABr) as the template and tetra-butylam-
monium bromide (TBABr) with a molar composition of the
reactants: 1.0 SiO2:0.48 CTMA+:0.96TBA+:0.39 Na2O:0.29
H2SO4:50-110 H2O. The gel mixture was stirred for 24 h at room
temperature and then was transferred into a Teflon lined autoclave
(13) Liu, C.-J.; Li, S.-G.; Pang, W.-Q.; Che, C.-M. Chem. Commun. 1997, 65.
(14) Das, D.; Tsai, C.-M.; Cheng, S. Chem. Commun. 1999, 473.
Langmuir, Vol. 23, No. 5, 2007 2493
Figure 3. Small-angle XRD pattern of (a) Si-MCM-41; (b) Cu-
MCM-41.
Figure 4. N2 adsorption/desorption isotherms of Si-MCM-41 (a)
and Cu-MCM-41 (b). Adsorption points are marked by filled squares,
and that for desorption ones are by open circles.
and was statically heated at 100 °C for 4 days. The product was
washed with copious amount of deionized water and was collected
by filtration and was dried in open air. The collected product was
calcined at 560 °C for 6 h in air and then for 6 h in nitrogen before
using for organic modification. This mesoporous material is
designated as Si-MCM-41.
Organic modification of Si-MCM-41 with 3-aminopropyltri-
ethoxysilane (3-APTES) has been performed by stirring 0.1 g of
Si-MCM-41 with 0.18 g (0.81 mmol) of 3-APTES in chloroform
at room temperature for 12 h under N2 atmosphere. The white solid
MCM-41-(SiCH2CH2CH2NH2)x thus produced was filtered and
washed with chloroform and dichloromethane. This solid was then
refluxed with salicylaldehyde (50mmol, 6.46 g) in methanol (10
cm3) for 3 h at 60 °C. The resulting yellowish solid was then collected
by filtration and was dried in a desiccator. Finally, the Cu-MCM-
41 was prepared by dissolving Cu(NO3)2‚6H2O (0.17 mmol, 0.04
g) in methanol and by stirring the above said yellowish solid (0.122
g) in suspension at room temperature for 12 h. The green solid thus
formed during stirring was filtered, washed with methanol using
Soxhlet, and dried under vacuum (Scheme 1). The catalyst thus
obtained is designated as Cu-MCM-41. Atomic absorption spec-
trometric result showed copper content of the catalyst is ca. 0.41%
(wt). The elemental analysis shows the molar ratio for N:Cu ≈ 2.2
2494 Langmuir, Vol. 23, No. 5, 2007 Jana et al.

Table 1. Heterogeneous Alkenes Epoxidation Catalyzed by Cu-MCM-41f

a
Benzaldehyde. b 2-Cyclohexen-1-ol was formed. c exo-Epoxynorbornane. d R-(+)-glycidol. e Turn over frequency ) moles converted/mol of
active site/time. The products of the epoxidation reactions were collected at different time intervals and were identified and quantified by Varian
CP-3800 gas chromatograph equipped with an FID detector and a CP-Sil 8 CB capillary column. f Reaction conditions: alkenes (1 g); catalyst (50
mg); tert-BuOOH (2 mL); acetonitrile (8 mL).

Table 2. Epoxidation of Styrene with tert-BuOOH Catalyzed by a Variety of Catalysts

% yield of products
catalyst conversion (wt %) epoxide others TONa reference
Cu-MCM-41 97 86 11 2963 (124)b this study
CuCl16Pc-MCM-41 47 25 22 1472 24
Co2+-NaX 74 12 62 24 26
Co2+-MCM-41 79 7 72 287 26
Au/Al2O3 7 <1 6 1 25
Au/Tl2O3 64 60 4 54 25
CuY 21 6 15 106 23
CuPcY 95 23 72 1264 23
a TON ) moles converted/mol of active site. b TOF ) Turn Over Frequency.

Table 3. Epoxidation of Styrene with Various Oxidants Over Catalytic Reactions. The catalytic reactions were carried out in
the Cu-MCM-41 a glass batch reactor according to following procedure. Substrate,
oxidant styrene conversion (wt %) % yield of epoxide solvent, and catalysts were first mixed. The mixture was then
equilibrated to 80 °C in an oil bath. After addition of oxidant, the
none 0 reaction was stirred continuously. The products of the epoxidation
H2O2 34 6 reactions were collected at different time intervals and were identified
tert-BuOOH 97 86
and quantified by gas chromatography.
PhIO 15 10

and for C:Cu ≈ 18.5, which indicates that the copper(II) ions have
N2O2 ligand environment as shown in Scheme 1.
Catalyst Characterization. Infrared and electronic spectra were
measured on Shimadzu S-8400 Fourier transform infrared (FTIR)
spectrometer and Shimadzu CP-3101 UV-vis spectrophotometer,
respectively. The copper content of the sample was estimated on
a Varian Techtron AA-ABQ atomic absorption spectrometer.
Elemental analysis, for carbon, hydrogen, and nitrogen (CHN), was
undertaken on a Perkin-Elmer 240C elemental analyzer. Electron
paramagnetic resonance (EPR) spectra were measured on a Varian
E-112 spectrometer at room temperature. The powder X-ray
diffraction (XRD) patterns of the samples were recorded with a
Scintag XDS-2000 diffractometer using Cu KR radiation. N2 sorption
studies were undertaken using Quantachrome Autosorb Automated
Gas Sorption system. Prior to sorption experiments, samples were
outgassed at desired temperature (250 °C for Si-MCM-41 and 90
°C for Cu-MCM-41) for ca. 8-9 h under vacuum (10-3 Torr).
Other instruments used in this study were the same as reported
earlier.6b,6c
Results and Discussion
Spectroscopic Measurements. Comparison of IR spectra of
Si-MCM-41 and MCM-41-(SiCH2CH2CH2NH2)x shows the
presence of various N-H and C-H vibration bands in the 3100-
2800 cm-1 and 1550-1250 cm-1 region in the IR spectra of
MCM-41-(SiCH2CH2CH2NH2)x that are absent in the case of
Si-MCM-41 (Figure 1). This clearly indicates that 3-APTES
has been anchored into the Si-MCM-41 matrix. The characteristic
band for azomethine group of copper(II) complex moiety appears
at ca. 1626 cm-1 in the IR spectra of Cu-MCM-41. The IR band
of free azomethine group appears at 1643 cm-1 while in Cu-
MCM-41 this band is shifted to a lower frequency indicating
coordination of azomethine nitrogen with copper.15
The solid-state electronic spectra of the species Cu-MCM-
41 showed two absorption maxima at ca. 650 and 400 nm. A
(15) Bhadbhade, M. M.; Srinivas, D. Inorg. Chem. 1993, 32, 5458 and 6122.
Anchoring of Copper Complex in MCM-41 Matrix Langmuir, Vol. 23, No. 5, 2007 2495

relatively weak band appearing in the visible region is assigned

to d-d transitions whereas a broad and strong band appearing
in the range 450-350 nm can be attributable to ligand charge-
transfer bands.15 In the case of immobilization of Cu(salen) into
NaY zeolite, a similar type of spectrum has been observed in an
earlier study.6c The principle g values calculated by the usual
methods from EPR spectra (Figure 2) are in agreement with
those reported for other copper(II) Schiff base complexes.6c,6i,16
The g|| and g⊥ values of Cu-MCM-41 are calculated to be 2.28
and 2.07, respectively. The hyperfine coupling due to metal ion
ACu (63Cu, I ) 3/2) was well-resolved in the present case and A||
value is calculated to be 160G. Continuous Wave EPR have
been studied extensively for copper(II) complexes. Copper(II)
systems with g|| > g⊥ > 2.0023 suggest that the unpaired electron
occupies the orbital, which is the characteristic of a tetragonally
elongated coordination environment of copper(II). These are
mainly square planar complexes sometimes with a weak
coordination at the fifth position. Talzi et al. reported copper(II)
complexes with N2O2 ligand geometry to show g|| values of
2.27-2.28 and A|| value of around 160G.17 Spectroscopic studies
of Cu-MCM-41, therefore, clearly indicate that copper(II)
complex formed in MCM-41 matrix is a square planar one as
shown in Scheme 1.
XRD Studies. The X-ray diffraction pattern of Si-MCM-41
shows a typical three-peak pattern18 with a very strong d100 )
40.44 Å reflection at 2θ ≈ 2.18° and two other weaker reflections
at 2θ ≈ 3.75° and 2θ ≈ 4.32° for d110 and d200, respectively, from
the quasi-regular arrangement of mesopores with hexagonal
symmetry (Figure 3). Si-MCM-41 shows an additional peak at
2θ ≈ 5.71° which can be assigned to d210 reflection. All the
peaks are well-resolved indicative of good quality material. Cu-
MCM-41 exhibits a strong d100 reflection with the spacing of ca.
39.28 Å and two other weaker reflections at 2θ ≈ 3.96° and 2θ
≈ 4.62° for d110 and d200, respectively, while the weakest reflection
for d210 has been buried in the background noise. Comparison
of X-ray powder diffraction patterns of Cu-MCM-41 and Si-
MCM-41 shows that the typical three-peak pattern of MCM-41 Figure 5. Reaction profile for the epoxidation of (A) norbornene
has been retained after the anchoring of copper(II) complex in (-), cyclooctene (0), and allylalcohol (b) and (B) cyclohexene (9)
and styrene (4) with tert-BuOOH in the presence of Cu-MCM-41
Si-MCM-41. However, all the diffraction lines shifted to the catalyst.
higher angles. A similar type of behavior was observed by Brukett
et al. in phenyl-modified mesoporous sieves19 and by Lim and 41 and subsequent complex formation with copper(II) are not
Stein for directly synthesized thiol-MCM-41.20Upon postsynthetic inconsistent.
grafting, an overall decrease in the intensity of the diffraction N2 Sorption Studies. The nitrogen sorption experiments
lines was noticed. This result could be attributed to the lowering showed that the Si-MCM-41 has the BET surface area of 950
of local order, such as variations in the wall thickness, or might m2 g-1 and the mesopore volume (Vp) of 0.66 (cm3 g-1). The
be due to the reduction of scattering contrast between the channel average pore diameter is calculated to be 26.4 Å using the BJH
wall of silicate framework and Schiff base ligand present in method for Si-MCM-41. All the calculated values are in
Cu-MCM-41, as it was previously mentioned by Lim and Stein.20 agreement with those reported for good quality mesoporous
Marler et al. have reported that the intensity of the diffraction MCM-41.22 The N2 adsorption isotherm as well as pore size
lines decreases systematically on increase in concentration of distribution of the Cu-MCM-41 was different from that of Si-
organic sorbates in boron-containing MCM-41.21 Therefore, shift MCM-41. Cu-MCM-41 displays a considerably lower N2 uptake
of the diffraction lines to the higher angle and decrease in the (BET surface area 90 m2 g-1) in comparison to the Si-MCM-41
intensity of the peaks upon organic modification of Si-MCM- (Figure 4).
Epoxidation Reactions. Aromatic and aliphatic alkenes react
(16) Schweiger, A.; Jeschke, G. Principles of Pulse Electron Paramagnetic with tert-BuOOH to produce epoxides with remarkable selectivity
Resonance; Oxford University Press: Oxford, U.K., 2001. in good yield using Cu-MCM-41 as catalyst in acetonitrile. The
(17) Talzi, E. P.; Nekipelov, V. M.; Zamaraev, K. I. J. Russ. Phys. Chem.
1984, 58, 165. results of the catalytic epoxidation of different substrates are
(18) (a) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, given in Table 1. The epoxidation of styrene with tert-BuOOH
J. S. Nature 1992, 359, 710. (b) Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz,
M. E.; Kresge, C. T.; Schmidt, K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard,
gives styrene oxide in 86% yield (selectivity ∼89%) (Table 1)
E. W.; McCullen, S. B.; Higgins, J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, under the heterogeneous condition; along with this, a small (11%)
114, 10834. amount of benzaldehyde is also detected. Turnover frequency of
(19) (a) Burkett, S. L.; Sims, S. D.; Mann, S. Chem. Commun. 1996, 1367.
(b) Fowler, C. E.; Burkett, S. L.; Mann, S. Chem. Commun. 1997, 1769. ∼124 has been attained for the epoxide production. Epoxidation
(20) Lim, M. H.; Stein, A. Chem. Mater. 1999, 11, 3285.
(21) Marler, B.; Oberhagemann, U.; Vortmann, S.; Gies, H. Microporous Mater. (22) Kruk, M.; Jaroniec, M.; Sakamoto, Y.; Terasaki, O.; Ryoo, R.; Ko,
1996, 6, 375. C. H. J. Phys. Chem. B 2000, 104, 292.
2496 Langmuir, Vol. 23, No. 5, 2007
of styrene with tert-BuOOH over a variety of catalysts under
heterogeneous condition has been studied in the recent past (Table
2). Seelan et al. studied epoxidation of styrene over copper-
phthalocyanine immobilized NaY catalyst which shows over
95% conversion with epoxide selectivity ∼24%.23 Selectivity of
the epoxide improves (∼53%) when copper-perchloro-phtha-
locyanine has been anchored onto MCM-41, however, conversion
remains within 47%.24 Gold particles dispersed on metal oxides
have also been used as catalysts in styrene epoxidation reaction
that gives a yield of ca. 60%, with a 94% epoxide selectivity.25
Recently, Tang et al. have studied this reaction over Co-NaX/
Co-MCM-41 using tert-BuOOH as well as molecular oxygen
as oxidant.26 Molecular oxygen is the better oxidant than tert-
BuOOH in this case, and yet conversion remained below 45%.
In fact, in the epoxidation of styrene with tert-BuOOH over
copper/copper complex immobilized zeolite or molecular-sieves
catalysts, epoxide selectivity rarely goes above 40%.27
The heterogeneous oxidation of cyclohexene (Table 1)
proceeded smoothly, showing an excellent conversion ∼94% to
form cyclohexene oxide as the major product with 83% selectivity;
along with this, 2-cyclohexen-1-ol was also generated owing to
allylic C-H oxidation. A 50-60% conversion of cyclohexene
with 77% epoxide selectivity has been obtained using Co/Mn
containing aluminophosphate (AlPO-36) catalysts.28 Molecular
oxygen with sacrificial benzaldehyde has been used as oxidant.
Using the same oxidant with sacrificial isobutyraldehyde copper-
perchlorophthalocyanine-MCM-41 yields 80% of cyclohexene-
epoxide with 95% selectivity.24 Bulkier cycloalkenes such as
norbornene and cyclooctene (Table 1) have also been effectively
converted to selectively exo-epoxynorbornane (conversion 97%,
selectivity 100%) and cyclooctene oxide (conversion 90%,
selectivity 100%), respectively, while these two cycloalkenes
are poor substrates for the ruthenium-dichlorophenylporphyrin-
MCM-4113 or TS-1 catalyzed epoxidation.29 Allyl alcohol gives
selectively R-(+)-glycidol (conversion 73%) as epoxide under
the present heterogeneous catalytic conditions.
Even though copper(II) Schiff base complexes have been well-
known for a long time, they have scarcely been used as
homogeneous catalyst in olefin epoxidation reactions. Das et al.
have obtained a moderate yield of olefinic epoxide using copper-
(II) Schiff base complex as catalyst in the presence of 2-me-
thylpropanal and molecular oxygen in homogeneous conditions.30a
A maximum yield of ca. 15% of styrene-epoxide has been
achieved with iodosylbenzene using a variety of tetradentate
Schiff base copper complexes.30b
The efficacy of the different oxidants like tert-BuOOH, H2O2,
and PhIO in Cu-MCM-41 catalyzed epoxidation reaction of
(23) Seelan, S.; Sinha, A. K.; Srinivas, D.; Sivasanker, S. J. Mol. Catal. A
2000, 157, 163.
(24) Karandikar, P.; Agashe, M.; Vijayamohanan, K.; Chandwadkar, A.
J. Appl. Catal. A 2004, 257, 133.
(25) Patila, N. S.; Jha, R.; Uphade, B. S.; Bhargava, S. K.; Choudhary, V. R.
Appl. Catal. A 2004, 275, 87.
(26) Tang, Q.; Zhang, Q.; Wu, H.; Wang, Y. J. Catal. 2005, 230, 384.
(27) De Vos, D. E.; Dams, M.; Sels, B. F.; Jacobs, P. A. Chem. ReV. 2002,
102, 3615.
(28) Raja, R.; Sankar, G.; Thomas, J. M. Chem. Commun. 1999, 829.
(29) Murugavel, R.; Roesky, H. W. Angew. Chem., Int. Ed. Engl. 1997, 36,
477.
(30) (a) Das, G.; Shukla, R.; Mandal, S.; Singh, R.; Bharadwaj, P. K.; Hall,
J. van; Whitmire, K. H. Inorg. Chem. 1997, 36, 323. (b) Zolezzi, S.; Spodine,
E.; Decinti, A. Polyhedron 2003, 22, 1653.
Jana et al.
styrene in heterogeneous condition has been studied. The results
of this study are given in Table 3. tert-BuOOH is the best oxidant
among the three catalysts that were used in catalytic epoxidation
reaction in the present study. Oxidants like H2O2 and PhIO are
clearly less efficient than tert-BuOOH as is evident from the
percentage of conversion of styrene. To test if the copper is
leaching out from the catalyst during reaction, the reaction mixture
was filtered out hot after the reaction is over and was subjected
to atomic absorption spectroscopic analysis. The analyses show
copper was absent in the filtrate. Besides, filtered mixture also
did not show any catalytic activity toward epoxidation reactions.
Therefore, it is clear that copper is not leaching out from the
catalyst during epoxidation.
The Cu-MCM-41 catalyst has been recovered from reaction
mixture and has been reused successively three times under the
same reaction conditions. The solid catalyst has been recovered
by filtration after each reaction and has been washed thoroughly
first with acetonitrile and then with dichloromethane. The
recovered catalyst is found to exhibit almost the same catalytic
activity for styrene epoxidation reaction by tert-BuOOH in every
run: first run, styrene conversion ) 97%, turnover ) 2963;
second run, styrene conversion ) 96%, turnover ) 2969; third
run, styrene conversion ) 97%, turnover ) 2957. No induction
period was observed in all the reactions (Figure 5).
Conclusions
In summary, we have successfully anchored the copper(II)
Schiff base complex into Si-MCM-41 matrix via covalent bond.
A remarkable difference in the pore structure has been observed
after the immobilization of copper(II) complex in Si-MCM-41.
The Cu-MCM-41 is porous but the mesoporous character of
Si-MCM-41 was not retained after modification. The catalyst
Cu-MCM-41 has shown excellent catalytic activities in ep-
oxidation reaction toward various olefins including allylic alcohol.
An unprecedented high conversion (97%) as well as selectivity
of epoxide (89%) has been observed in styrene epoxidation.
Notably, epoxidation of allylic alcohol showed considerably high
turnover frequency (166 h-1) in this study. The coordination
environment around copper(II) in Cu-MCM-41 is less crowded
and is easily approachable in comparison to the bulkier metal-
porphyrins or metal-phthalocyanins, which were anchored into
MCM-41 matrix in the earlier studies. Probably because of this,
alkyl-hydroperoxide gets enough space to bind copper in the
intermediate stages of catalytic cycle and thereby facilitates the
neucleophilic attack by the oxidant to enhance the catalytic activity
of the metal complex anchored into mesoporous matrix in the
epoxidation reactions. Hence, a better catalytic efficiency has
been observed in Cu-MCM-41.
Acknowledgment. Financial support from the Department
of Science and Technology, Government of India, by a grant
(SR/S1/IC-12/2003) (to S.K.) is gratefully acknowledged. R.B.
thanks CSIR and B.D. thanks UGC for research fellowship. We
are grateful to SAIF, IIT Madras for EPR spectral measurement.
Authors wish to thank Dr. A. Bhaumik for N2 sorption analysis,
funded by the NanoScience and Technology Initiative of DST,
New Delhi (on a chargeable basis). We are indebted to the referees
for their valuable comments.
LA062409T