ScientificJournalofFrontierChemicalDevelopment

December2012,Volume2,Issue4,PP.6980

Novel Immobilized Tridentate Schiff Base

Mo(VI) Catalyzed the Epoxidation of Olefins
Xuemei Huang1,

Xiangkai Fu * 1,2,

Yuedong Li 1,

Ziyong Jia 1

1.College of Chemistry and Chemical Engineering, Research Institute of Applied Chemistry Southwest China University, The Key
Laboratory of Applied Chemistry of Chongqing Municipality, Chongqing 400715, China
2 .The Key Laboratory of Eco-environments in Three Gorges Region, Ministry of Education, Chongqing 400715, China

Abstract
New types of supported Shiff base Mo() catalysts were obtained by anchoring tridentate Schiff base Mo(VI) on a series of
immobilized Shiff base ligand which were obtained by chloromethyl, diamine modified zirconium poly(styrene-phenylvinyl
phosphonate)-phosphate (ZPS-PVPA) reacted with aldehyde or ketone. All the prepared catalysts were characterized by FT-IR,
UV-vis, XPS, SEM, TG and elemental analysis. The catalytic capabilities were investigated for the epoxidation of cyclooctene,
styrene, -methylstyrene with tert-Butyl hydroperoxide (TBHP) as oxidant. The results showed that the heterogeneous catalysts
exhibited excellent catalytic efficiency. Surprisingly, up to 99% ee values were obtained when -methylstyrene was chosen as
substrate in this oxidant system. Furthermore, these catalysts were easily separated and reused ten times without significant loss of
activities.
Keywords:

Zirconium

Poly

(Styrene-Phenylvinylphosphonate)-Phosphate;

Chloromethyl;

Immobilized

Schiff

Base

Dioxomolybdenum(VI); Olefin Epoxidation; Tert-Butyl Hydroperoxide

Mo()

1*1,211
1. 400715
2. 400715
-(-)- (ZPS-PVPA)

Mo()
FT-IRUV-visXPSSEMTEMTG TBHP
- Mo()
- 99%
10
(-)-Mo()

[1]
- 69 Copyright 2012 Ivy Publisher

-O[2]

[3-6]
[7,8]
[9,10]-

[11]
salen Mn(III) ZPS-IPPA[12]--ZPS-PVPA[13-15]
salen Mn(III) salen Mn(III)

10

1
1.1
-(99%)Alfa Aesar
MoO2(acac)2[16]
FT-IR( Bruker RFS100/S)DR UV-2550 -(
Shinadu)ESCALAB250XTAS-986G (
)KYKY-EM 3200TECNA I10 ( Philips)3H-2000 I
()SBTQ600 (USA)GC-2014
( Shimadu)FID(HP19091 G-B21330 m0.32 mm0.25 m)

1.2
1.2.1 -(ZAMPS- PVPA)
-ZPS-PVPAZCMPS-PVPA[17] (1)
50 mLZCMPS-PVPA (2.63 g)K2CO3 (4.5 g0.03 mol)(5 mL)5min
(1,2-1,2-)n(Cl)n()=11070 24 h
ZAMPS-PVPA 1a, 1b
1.2.2 (2a ~ 2h)( 2)
[18-23](1.2 g)
3,5--2--2 mmol24
h80 (2a ~ 2h)
- 70 Copyright 2012 Ivy Publisher

PO3H2

PO3H2

reflux

EtOAC

PVPA

H2
H
ZrOCl2
C C C C n * NaH PO
2
4
H2 m
Ph
Ph
St-PVPA
CH3OCH2Cl

Zr(HPO4)1.35[O3PC(Ph)CH2(CHCH2)m]0.65.nH2O

=ZPS-PVPA )

ZCMPS-PVPA

Ph

ZPS-PVPA

1a R =

PhCH3

CH2Cl
H2N

CH2Cl (

ZnCl2

NH2

80 12 h

CH2HN

NH2

1b R =

PhCH3

CH2Cl
H2N

NH2

80 12 h

CH2HN

NH2

1a

PhCH3

CH2Cl
H2N

NH2

80 12 h

CH2HN

NH2
1b

1.2.3 (-)-3a ~ 3h
0.6 g ()0.30 g 20 mL60

24 h
80 3a ~ 3h
[20-23]

R
CHO

R
CH2HN

reflux

NH2

OH

20 h

CH2HN

N
HO

2b R =
2f R =

MoO2(acac)2 EtOH

R
3a R =

CH2HN
N
O Mo O
OEtOH

3e R =

CH2HN
N
O Mo
O
O
EtOH

3b R =
3f

R=

R
CH2HN
N
O Mo
O
O
EtOH

3c R =
3g R =

CH2HN
N
O Mo
O
O
EtOH

3d R =
3h R =

1.3
[20,23]15mL0.03 g0.02 mmol
12-3 mL90 L1.0 mmol135 L1.0 mmol75
75 %0.30 mL (2.0 mmol, m/m)3 mL
2 min3 mL

3 mL2 min

- 71 Copyright 2012 Ivy Publisher

2
2.1
2.1.1
3 3b 3c
ZAMPS-PVPA(1a)(2b2c)1628 cm-1C=N1600-1500 cm-1
(C=C)(C=N)(Car-O)1550 cm-1(Car-O)
1500 cm-1930-940 cm-1(
s)910-895

cm-1(as)MoO2

[24]3400-3200 cm-11030 cm-1O-HC-O

3 (a) 1a(b) 2b(c) 3b(d) 2c(e) 3c

4
ZAPS-PVPA1a(a)2b(b)C=N200~400 nm
253366500 nm3b253328400 nmMoO2(acac)2
[15,17,25]

4 (a) 1a; (b) 2b(c) 3b; (d) MoO2(acac)2

2.1.2 X-
X-5
3bX-3b
- 72 Copyright 2012 Ivy Publisher

232.1 eV235.3 eVMo 3d5/2Mo 3d3/23bMo+6

[26]

5 3bX-

2.1.3

AAS1
3b3c3f3g0.36-0.48 mmol/gBET
ZPS-PVPA186 m2/g
(3a-3h)79105 m2/g
[15,17]
1

BET (m2/g)

(mmol/g)

ZPS-PVPA

186

1a

92

1b

105

3b

79

0.36

3c

83

0.43

3f

98

0.40

3g

91

0.48

2.1.4
63b3b

[15, 14,17,25]

- 73 Copyright 2012 Ivy Publisher

(a)

(b)

6 (a)3bSEM (b)3bTEM

2.1.5

3b718012.94 %
180~65041.25 %
Zr(HPO4)2650~1000 Zr(HPO4)2ZrP2O7
150 C
[23,24,27]

7 3b

2.2

TBHP

2
[28-31]2
-

-MCM-41[28]

ZAPS-PVPA1
2
[15,14,17,32]3
-
- 74 Copyright 2012 Ivy Publisher


[14,15, 33]
1,2-3a~3d1,2-
3e~3h13e~3h3a~3d
2-
-3e~3h[34]
tert-BuOH( TBHP)
[28]
-TBHP
99%
[35-37]-
12-

2 TBHP 3a3h - a
Substrateb

Eed (%)

TOFe 104 (s-1)

Catalyst

Time (h)

Conversion(%)

Selectivity(%)

3a

100

97

3b

100

99

17.2

3c

100

99

17.4

3d

100

99

17.4

3e

95

97

16.0

3f

98

96

16.3

3g

98

97

16.5

3h

98

97

16.5

3a

12

46

38

2.02

10

3b

12

57

50

3.30

11

3c

12

60

50

3.47

3d

12

62

33

2.37

3e

12

21

63

1.53

14

3f

12

47

54

2.94

15

3g

12

47

47

2.56

16

3h

12

50

55

3.18

17

3a

12

78

56

99

5.06

18

3b

12

90

60

99

6.25

19

3c

12

90

62

99

6.46

3d

12

92

67

99

7.13

21

3e

12

43

64

99

3.19

22

3f

12

45

69

99

3.59

Entry

4
5

12
13

20

Bc

Cc

16.8

2 TBHP 3a3h - a
Entry

Substrateb

Catalyst

Time (h)

Conversion(%)

Selectivity(%)

- 75 Copyright 2012 Ivy Publisher

Eed (%)

TOFe 104 (s-1)

23

3g

12

59

72

99

4.92

24

3h

12

71

75

99

6.16

25

10

36

26

12

26

27

12

43

97

Reactions were performed in 1,2-dichloroethane (3 mL) with catalyst (2 mmol%), substrate (1 mmol), n-nonane (internal standard,

1 mmol), and TBHP (2 mmol) at 75C.

b

A =cyclooctene, B = styrene, C=-methylstyrene

Selectivity toward the formation of epoxide [38].

(S)-form [38].

Turn over frequency (TOF) = [mol of product]/[mol of catalyst] time (s-1).

Reaction was carried out without catalyst.

2.3

3d

4 mL5 min
80 6 h

36
6
99%95%99%94%

[14,15,17,25]
3

3d a
Conversion (%)

Selectivity(%)b

TOFc103(s-1)

Run

Time

99

>99

1.74

99

>99

1.72

99

>99

1.72

98

>98

1.68

97

>98

1.70

95

94

1.65

95

94

1.65

94

92

1.58

92

91

1.57

10

92

92

1.52

11

91

90

1.45

12

89

89

1.42

The reaction conditions are the same as in Table 2 entry 1-8.

Selectivity toward the formation of epoxide.

Same as in Table 2.
- 76 Copyright 2012 Ivy Publisher

2.4
4
3b1,2-1,2-
Mo
[28,39]-oxo[2]1,2-

3b a

4
Solvent

Time

Conversion (%)

Selectivity(%)b

TOFc103(s-1)

Toluene

80

99

1.38

n-Hexane

96

99

1.65

100

99

1.72

Ethyl acetate

40

96

0.67

Ethanol

62

96

1.03

Acetonitrile

68

97

1.15

1,2-dichloroe
thane

The reaction conditions are the same as in Table 2 entry 1-8, and n-hexane at 68 C.

Same as in Table 3.

Same as in Table 3.

2.5
3e5
50 C11%50C80 C
11%98%TBHP[28]75 C

5
Entry

Substrate

50
60
70

cyclooctene

80
a

Catal.

Time (h)

Conv.(%)

Select.b(%)

3e

11

100

3e

76

100

3e

92

99

3e

98

97

Reactions were performed in 1,2-dichloroethane (3 mL) with catalyst (2 mmol%), substrate (1 mmol), n-nonane (internal standard, 1
mmol), and TBHP (2 mmol) at 75 C.

Selectivity toward the formation of epoxide.

2.6
Sobczak[30][40-42]
8
- 77 Copyright 2012 Ivy Publisher

t-BuOOHMoO2
t-BuOO-TBHP
t-BuOH

O
Mo

(CH3)3C OH

EtO
H

(CH3)3C O
O H

EtOH

Mo O H
O O C(CH )
3 3
O

EtOH

N
O
H O
CH2

Mo O H
O O C(CH )
3 3
O

N
H
CH2

N
H
CH2

8 TBHP3a-3h

3
ZPS-PVPA

10

REFERENCES
[1] K. A. Jorgensen. Transition-metal-catalyzed Epoxidations[J]. Chem. Rev., 1989, 89: 431-458.
[2] X. L. Wang, G. D. Wu, J. P. Li, et al. Selective Oxidation of Benzyl Alcohol Catalyzed by Cr(salen) Complexes Immobilized on
MCM-41[J]. J. Mol. Catal. A: Chem., 2007, 276: 86-94.
[3] D. A. Annis, E. N. Jacobsen. Polymer-Supported Chiral Co(Salen) Complexes: Synthetic Applications and Mechanistic
Investigations in the Hydrolytic Kinetic Resolution of Terminal Epoxides[J]. J.Am.Chem.Soc., 1999, 121: 4147-4154.
[4] N. T. S. Phan, D. H. Brown, P. Styring. A Polymer-supported Salen-type Palladium Complex as a Catalyst for the SuzukiMiyaura
Cross-coupling Reaction[J]. Tetrahedron Lett., 2004, 45: 7915-7919.
[5] Y. S. Kim, G. In, C. W. Han, et al. Studies on Synthesis and Application of XAD-4-salen Chelate Resin for Separation and
Determination of Trace Elements by Solid Phase Extraction[J]. Microchem. J., 2005, 80: 151-157.
[6] B. Bahramian, V. Mirkhani, M. Moghadam, et al. Selective Alkene Epoxidation and Alkane Hydroxylation with Sodium Periodate
Catalyzed by Cationic Mn(III)-Salen Supported on Dowex MSC1[J]. Appl. Catal. A: Gen., 2006, 301: 169-175.
[7] T. Shichi, K. Takagi. Clay Minerals as Photochemical Reaction Fields[J]. J. Photochem. Photobiol. C: Photochem. Rev., 2000, 1:
113-130.
[8] czka, K. Cholewa. Kowalska, M. Kogut. Organic-Inorganic Hybrid Glasses of Selective Optical Transmission[J]. J. Non. Cryst.
- 78 Copyright 2012 Ivy Publisher

Solids, 2001, 287: 10-14.

[9] Y. Song, X. Yao, H. Chen, et al. Highly Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by A Novel Recyclable
Chiral Poly-salenMn(III) Complex[J]. J. Chem. Soc., 2002, 1: 870-873.
[10] B.M. Choudary, T. Ramani, H. Maheswaran, et al. Catalytic Asymmetric Epoxidation of Unfunctionalised Olefins Using Silica,
LDH and Resin-Supported Sulfonato-Mn(salen) Complex[J]. Adv. Synth. Catal., 2006, 348: 493-498.
[11] J. Gong, X. D. Li, B. Ding, et al. Preparation and Characterization of H4SiMo12O40/poly(vinyl alcohol) Fiber Mats Produced by
an Electrospinning Method[J]. J. Appl. Polym. Sci., 2003, 89: 1573-1578.
[12] Tu X B, Fu X K, Hu X Y, et al. Chiral Salen Mn(III) Immobilized on Sulfoalkyl Modified ZSP-IPPA as an Effective Catalyst for
Asymmetric Epoxidation of Unfunctionalized Olefins [J]. Inorg. Chem. Commun., 2010, 13: 404-407.
[13] Gong B W, Fu X K, Chen J X. Synthesis of a New Type of Immobilized Chiral Salen Mn(III) Complex as Effective Catalysts for
Asymmetric Epoxidation of Unfunctionalized Olefins [J]. J. Catal., 2009, 262: 9-17.
[14] X. C. Zou, X. K. Fu, Y. D. Li, et al. Highly Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Chiral
Jacobsens Catalyst Immobilized on Phenoxy-Modified Zirconium Poly(syrene-phenylvinylphos- phonate)phosphate[J]. Adv.
Synth. Catal., 2010, 352: 163-170.
[15] W. S. Ren, X. K. Fu, H. B. Bao, et al. Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Chiral Salen Mn(III)
Catalyst Immobilized on Zirconium Oligostyrenylphosphonate-phosphate[J]. Catal. Commun., 2009, 10: 788-793.
[16] G. J. Chen, J. W. M. Donald, W. E. Newton. Synthesis of Molybdenum(IV) and Molybdenum(V) Complexes Using Oxo
Abstraction by Phosphines. Mechanistic Implications[J]. Inorg. Chem., 1976, 15: 2612-2615.
[17] B. W. Gong, X. K. Fu, J. X. Chen, et al. Synthesis of A New Type of Immobilized Chiral Salen Mn(III) Complex as Effective
Catalysts for Asymmetric Epoxidation Of Unfunctionalized Olefins[J]. J. Catal., 2009, 262: 9-17.
[18] J. H. Clark, D. J. Macquarrie, E. B. Mubofu. Preparation of A Novel Silica-supported Palladium Catalyst and Its Use in the Heck
Reaction[J]. Green. Chem., 2000, 2: 53-56.
[19] C. D. Nunes, M. Pillinger, A. A. Valente, et al. Dioxomolybdenum(VI)-Modified Mesoporous MCM-41 and MCM-48 Materials for
the Catalytic Epoxidation of Olefins[J]. Eur. J. Inorg. Chem., 2003, 2003: 3870-3877.
[20] M. Masteri-Farahani, F. Farzaneh, M. Ghandi. Synthesis and Characterization of Molybdenum Complexes with Bidentate Schiff
Base Ligands within Nanoreactors of MCM-41 as Epoxidation Catalysts[J]. J. Mol. Catal. A: Chem., 2006, 248: 53-60.
[21] T. Luts, W. Suprun, D. Hofmannb, et al. Epoxidation of Olefins Catalyzed by Novel Mn(III) and Mo(IV) Salen Complexes
Immobilized on Mesoporous Silica Gel: Part I. Synthesis and Characterization of Homogeneous and Immobilized Mn(III) and
Mo(IV) Salen Complexes[J]. J. Mol. Catal. A: Chem., 2007, 261: 16-23.
[22] T. Luts, R. Frank, W. Suprun, et al. Epoxidation of Olefins Catalyzed by Novel Mn(III) and Mo(IV)-Salen Complexes Immobilized
on Mesoporous Silica Gel (2) Study of the Catalytic Epoxidation of Olefins[J]. J. Mol. Catal. A: Chem., 2007, 273: 250-258.
[23] M. Masteri-Farahani, F. Farzaneh, M. Ghandi. Synthesis of Tetradentate N4 Schiff Base Dioxomolybdenum (VI) Complex within
MCM-41 as Selective Catalyst for Epoxidation of Olefins[J]. Catal. Commun., 2007, 8: 6-10.
[24] Z.D. Tomi, A. Kapor, A. miri, et al. Comparison of Structural Features of Three New Cis-dioxomolybdenum(VI) Complexes with
2-hydroxy-1-naphthaldehyde-S-methylisothiosemicarbazone: Possible Role of Intermolecular Interactions on the Geometry of the
cis-MoO2 unit[J]. Inorg. Chim. Acta., 2007, 360: 2197-2206.
[25] W. S. Ren, X. K. Fu. Chiral Mn (III) Salen Complexes Covalently Bonded on Zirconium oligostyrenylphosphonate-phosphates as
Catalysts for Enantioselective Epoxidation of Nonfunctionalized Alkenes[J]. J. Mol. Catal. A: Chem., 2009, 312: 40-47.
[26] J. F. Moulder, W. F. Stickle, P. E. Sobol, et al. Handbook of XPS Perkin Elmer Corporation[J]. Eden Prairie, MN, 1992.
[27] H. S. Shen, X. K. Fu, H. B. Bao, et al. Synthesis and Characterization of A New Kind of Immobilized Mn(salen) and Catalytic
Epoxidation of Styrene on the Catalyst[J]. Polym. Adv. Technol., 2009, 20: 77-83.

- 79 Copyright 2012 Ivy Publisher

[28] M. Masteri-Farahani, F. Farzaneh, M. Ghandi. Synthesis and Characterization of Molybdenum Complexes with Bidentate Schiff
Base Ligands Within Nanoreactors of MCM-41 as Epoxidation Catalysts[J]. J. Mol. Catal. A: Chem., 2006, 248: 53-60.
[29] T. Luts, R. Frank, W. Suprun, et al. Epoxidation of Olefins Catalyzed by Novel Mn(III) and Mo(IV)-Salen Complexes Immobilized
on Mesoporous Silica gel (2) Study of the Catalytic Epoxidation of Olefins[J]. J. Mol. Catal. A: Chem., 2007, 273: 250-258.
[30] J. Sobczak, J. J. Ziolkowski. The Catalytic Epoxidation of Olefins with Organic Hydroperoxides[J]. J. Mol. Catal. A: Chem., 1981,
13: 11-42.
[31] Y. Sui, X. R. Zeng, X. N. Fang, et al. Syntheses, Structure, Redox and Catalytic Epoxidation Properties of Dioxomolybdenum(VI)
Complexes with Schiff Base Ligands Derived From Tris(Hydroxymethyl)Amino Methane[J]. J. Mol. Catal. A: Chem., 2007, 270:
61-67.
[32] S. H. Cho, N. D. Walther, S. T. Nguyen, et al. Anodic Aluminium Oxide Catalytic Membranes for Asymmetric Epoxidation[J].
Chem. Commun., 2005, 53315333.
[33] N. A. Caplan, F. E. Hancock, P. P. C. Bulman, et al. Heterogeneous Enantioselective Catalysed Carbonyl- and Imino-ene Reactions
using Copper bis(oxazoline) Zeolite Y[J]. Angew. Chem. Int. Ed., 2004, 43: 1685-1688.
[34] M. Masteri-Farahani, F. Farzaneh, M. Ghandi. Synthesis of Tetradentate N4 Schiff Base Dioxomolybdenum (VI) Complex within
MCM-41 as Selective Catalyst for Epoxidation of Olefins[J]. Catal. Commun., 2007, 8: 6-10.
[35] T. Hashihayata, Y. Ito, T. Katsuki. The First Asymmetric Epoxidation Using A Combination of Achiral (salen)Manganese(III)
Complex and Chiral Amine[J]. Tetrahedron, 1997, 53: 9541-9552.
[36] B. M. Choudary, U. Pal, M. L. Kantam, et al. Asymmetric Epoxidation of Olefins by Manganese(III) Complexes Stabilised on
Nanocrystalline Magnesium Oxide[J]. Adv. Synth. Catal., 2006, 348: 1038-1042.
[37] Y. Wang, Z. Q. Wu, Z. K. Li, et al. Asymmetric Epoxidation of Styrenes Catalyzed by Molybdenum Complexes with Amino
Alcohol Ligand[J]. Tetrahedron Lett., 2009, 50: 2509-2511.
[38] W. Zhang, J.L. Loebach, S.R. Wilson, et al. Enantioselective Epoxidation of Unfunctionalized Olefins Catalyzed by Salen
Manganese Complexes[J]. J. Am. Chem. Soc., 1990, 112: 2801-2803.
[39] M. Minelli, J. H. Enemark, R. T. C. Brownlee, et al. The Nuclear Magnetic Resonance Properties of Chromium, Molybdenum and
Tungsten Compounds[J]. Chem. Rev., 1985, 68: 169-278.
[40] C. D. Nunes, A. A. Valente, M. Pillinger, et al. Molecular StructureActivity Relationships for the Oxidation of Organic
Compounds Using Mesoporous Silica Catalysts Derivatised with Bis(halogeno)dioxomolybdenum(VI) Complexes[J]. Chem. Eur.
J., 2003, 9: 4380-4390.
[41] R. A. Sheldon, J. A. V. Doorn. Metal-catalyzed Epoxidation of Olefins with Organic Hydroperoxides: I. A Comparison of Various
Metal Catalysts[J]. J. Catal., 1973, 31: 427-437.
[42] S. Mukherjee, S. Samanta, B. C. Roy, et al. Efficient Allylic Oxidation of Cyclohexene Catalyzed by Immobilized Schiff Base
Complex Using Peroxides as Oxidants[J]. Appl. Catal. A: Gen., 2006, 301: 79-88.

1987-

1945.12-

E-mail: hxm_123456@126.com

Emailfxk@swu.edu.cn

- 80 Copyright 2012 Ivy Publisher