Synthesis and study of binuclear calix[4]arene Schiff base Mn(II) complexes as catalyst in the presence of PhIO for the catalytic oxidation of olefin

Article abstract of DOI:10.1007/s10847-012-0116-x

The binuclear Mn(II) complexes of calix[4]arene substituted 2-vanillin and 2-hydroxy naphthaldimine, Schiff bases (Mn₂L¹ and Mn ₂L²) have been synthesized, characterized and employed as models to mimic monooxyge

Full text of DOI:10.1007/s10847-012-0116-x

J Incl Phenom Macrocycl Chem (2012) 74:473–480
DOI 10.1007/s10847-012-0116-x
SHORT COMMUNICATION
Synthesis and study of binuclear calix[4]arene Schiff base Mn(II)
complexes as catalyst in the presence of PhIO for the catalytic
oxidation of olefin
•
Ravindra V. Patel Jayesh G. Panchal
•
•
Bhoomika R. Mistry Shobhana K. Menon
Received: 19 February 2011 / Accepted: 20 January 2012 / Published online: 29 February 2012
Ó Springer Science+Business Media B.V. 2012
Abstract The binuclear Mn(II) complexes of calix[4]ar-
ene substituted 2-vanillin and 2-hydroxy naphthaldimine,
Schiff bases (Mn2L1 and Mn2L2) have been synthesized,
characterized and employed as models to mimic monoox-
ygenase in the catalytical oxidation of olefins. The kinetic
mathematical model (oxygen rebound mechanism) for
olefin cleavage catalyzed by the complexes has been pro-
posed. The results show that, compared to the calix[4]ar-
ene-free analogous, the mono and multinuclear complexes
of calix[4]arene Schiff bases as catalyst exhibit high
activity in the olefin catalytic oxidation.
oxygen [3–5]. The method is mild and is an environment
friendly process. However, the cost of porphyrin is high. It
was also found that Schiff base complexes are effective
catalysts for aerobic oxidation of olefins [6]. Parallel to the
porphyrin chemistry, the same catalytic reactions are
mimicked by various transition metal complexes, in par-
ticular Schiff base complexes, because of their cheap and
easy synthesis and chemical and thermal stability [7–10].
A number of previous works on phase transfer catalysis
showed that cyclodextrins and cyclodextrin based
calix[4]arene catalysts, [11–14] which combine the prop-
erties of phase transfer agent and metal complex with the
function of molecular recognition, can change the reaction
selectivity and can increase the activity of catalysts. There
are very limited studies on the oxidation of an olefin cat-
alyzed by calix[4]arene metal complexes [15]. Recently, a
few papers have been reported where in calix[4]arene
complexes have been used as oxidation catalyst and in
alkene epoxidation [16–18]. In earlier report [19] on the
calix[4]arene Schiff base complexes and their catalytic
oxidation study. In the present work, solid complexes of
calix[4]arene Schiff bases (2-vanillin and 2-hydroxy
naphthaldehyde) with the metal Mn(II), were prepared and
were used as catalyst for the oxidation of the olefins e.g.
styrene and cyclohexene.
Keywords Calix[4]arene Schiff base ꢀ Binuclear
Mn(II)complexes ꢀ Catalytic oxidation ꢀ Olefin
Introduction
Multifunctional systems are the most interesting in metal
complex catalysis, which is a widespread and rapidly
developing area of science and technology, but yet little
studied subject of investigation. A great deal of attention
has been paid to supramolecular catalysis, which suggests
the use of compounds capable of molecular recognition as
components of catalyst systems. Manganese Schiff base
complexes are often described as good epoxidation cata-
lysts, due to their high activity and selectivity [1] which
mimic the function of cytochrome P-450 [2].Such metal
complexes showed high activity and stability in catalytic
oxidation of hydrocarbon compounds with molecular
Experimental
Materials
All the chemicals used were of A.R. Grade of Aldrich and
E. Merck unless otherwise specified. Iodosylbenzene was
prepared by the method reported by Lucas et al. [20].The
substrates, styrene, cyclohexene and oxidation products
R. V. Patel ꢀ J. G. Panchal ꢀ B. R. Mistry ꢀ S. K. Menon (&)
Department of Chemistry, School of Sciences,
Gujarat University, Ahmedabad 380009, India
e-mail: shobhanamenon07@gmail.com
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benzaldehyde, styrene oxide, cyclohexene oxide, cyclo-
hexene-1-one were obtained from Aldrich.
Physical measurement
The spectra were scanned on Hitachi Model UV-3210 spec-
trophotometer. Discover BenchMate system-240 V (CEM
Corporation) microwave synthesizer was used for synthesis.
The FT-IR spectra were recorded as KBr pellet on Bruker
Tensor-27. The MALDI-TOF MS was run on a Micromass
TofSpece 2E instrument, using a nitrogen 337 nm laser (4 ns
pulse).1H NMR spectra was scanned on 400 MHz FT-NMR
Bruker Avance-400 and 13C NMR spectra was recorded on a
Bruker DPX-300 spectrometer with tetramethylsilane (TMS)
as internal standard in dueterated DMSO. Gas chromato-
graphic/mass spectrometric (GC/MS) analyses were carried
out using a Schimadzu GC-17A series gas chromatograph
equipped with a SG BP 1 column (0.32 mn 9 30 mt) and
helium as carrier gas and mass spectrometric detection was
performed on QP5050 series A mass spectrometer. The
electron spin resonance spectra were recorded using tetracyno
ethylene (TCNE) as a reference standard which has
g = 2.00277 on E112 ESR Spectrometer.
Synthesis of ligand
p-tert-butylcalix[4]arene (1)was synthesized by microwave
technique developed in our laboratory [19]. The synthesis
of the intermediates, debutylated calix[4]arene [21], azoc-
alix[4]arene [22] and tetraaminocalix[4]arene [23] were
according to the literature methods.
Scheme 2 Synthesis of calix[4]arene Schiff bases
mixture was heated at 300 watt output power for 15 min to
obtain corresponding calix[4]arene. The purity was
checked by TLC and the results of mp, FT-IR, 1H NMR,
13C NMR and MS were compared with standard sample.
Microwave-assisted synthesis of 5,11,17,23-tetra-butyl-
25,26,27,28 tetrahydroxyl calix[4] arene 1
Synthesis of calix[4]arene Schiff bases Tetraaminoca-
lix[4]arene (10 mmol) and aldehydes (40 mmol) (Scheme
2) in anhydrous ethanol (100 ml) were stirred for 2 h under
N2 atmosphere. The yellow precipitate was filtered and
recrystallized from ethanol and chloroform.
For the microwave synthesis of 1 (Scheme 1), 10 g of
p-tert-butylphenol was mixed with NaOH (0.05 g, 1.2
mmol) dissolved 0.5 ml of water and 6.2 ml 37% formal-
dehyde solution and was heated in a Discover BenchMate
system-240 V(CEM Corporation) microwave at 300 watt
output power for 5 min to give a yellow solid. To this was
added 7 ml of diphenyl ether and 1 ml toluene and the
Calix[4]arene Schiff base, H4L1 Yield 2.5 g (83%). m.p.
120 °C. FT-IR (KBr) t: 3221 cm-1(–OH), 2958 cm-1
,
1603 cm-1 (CH=N). H NMR (CDCl3) d 9.5(s, 4H, Ar
OH) 13.9 (s, 4H, Ar OH) 8.52 (s, 4H, Ar CH=N) 2.52(s,
8H, CH2)7.15(m, 12H, ArH)7(m, 8H, ArH) 3.83(s, 12H,
CH3). 13CNMR(CDCl3) d160 (CH=N), 159, 151, 149,
144.7, 128.9, 127.8, 124.1, 119.6, 118.1 and 113(ArC),
1
56.2(–OCH3),
13.0(–CH2–).
MALDI-TOF
MS(m/
z) 1022(M ? 1). Anal. calc. for C60H52N4O12: C, 70.58; H,
5.13; N, 5.49% Found: C, 70.61; H, 5.12; N, 5.47%.
Calix[4]arene Schiff base, H4L2 Yield 2.5 g (83%). m.p.
Scheme 1 Microwave-Assisted synthesis of 5,11,17,23-tetra-butyl-
25,26,27,28 tetrahydroxyl calix[4] arene 1
205 °C. FT-IR (KBr)t: 3166 cm-1(–OH), 1904 cm-1
,
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J Incl Phenom Macrocycl Chem (2012) 74:473–480
475
1671 (CH=N) cm-1. 1H NMR (CDCl3) 9.85(s, 4H, Ar OH)
12.65 (s, 4H, Ar OH) 9.33 (s, 4H, Ar CH=N) 2.58(s, 8H,
CH2) 7.83 (m, 24H, ArH) d7.02(m, 8H, ArH). 13CNMR
(CDCl3)d 153.8(CH=N), 172, 157, 145.1, 135.8, 129.1,
128.0, 127.8, 125.2, 124.9, 122, 118.6 and 116.4(Ar C), 13
(–CH2–). MALDI-TOF MS(m/z) 1103(M?). Anal. calc.
for C72H52N4O8: C, 78.53; H, 4.76; N 5.09% Found: C,
78.40; H, 4.79; N, 5.19%.
Procedure for kinetic studies
Styrene and cyclohexene were used as the substrate for
kinetic studies with complexes Mn2L1 and Mn2L2 as cat-
alyst. All the kinetic studies were carried out at
25 °C 1 °C using a thermostat. In one set of experiments
various amounts of olefin (0.5, 1.0, 1.5, 2.0, 2.5, 3.0,
3.5 mmol) were taken keeping all the other factors con-
stant. In another set, catalyst amount was similarly varied.
Addition of PhIO was considered as zero time. Stirring was
stopped for 1–2 min and aliquots (1 lL) were withdrawn
every 15 min for GC analysis.
Synthesis of calix[4]arene Schiff base metal complexes
A solution of H4L1 or H4L2(1.0 mmol) and Mn (OAc)2.
4H2O (2 mmol) in anhydrous ethanol (30 mL) was stirred
for 2 h under N2 at 80 °C, then the mixture was cooled and
filtered, washed with methanol to give metal complexes,
and the pure product was obtained after recrystallization
from ethanol (95%).
Mn2L1: dark brown, yield 77%. m.p. [223 °C. FT-
IR(KBr)t: 3442(–OH) cm-11637 (–CH=N) cm-1.MALDI-
TOF MS(m/z) 1127(M ? 2). Anal. calc. for C60H48N4O12
Mn2: C, 70.58; H, 5.13; N, 5.49; M, 7.24% Found: C,
70.12; H, 5.43; N, 5.59; M, 9.20.
Initial rate for the reaction in all the kinetic studies was
calculated by graphical method. log [initial rate] was then
plotted against log[catalyst] or log [olefin] using linear
regression. The slope of the straight line thus obtained
yielded the order of the reaction with respect to catalyst or
alkene.
Result and discussion
Mn2L2: dark brown, yield 77%. m.p. [245 °C. FT-
IR(KBr)t: 3255 (–OH)cm-1, 1678 (–CH=N)cm-1 MALDI-
TOF MS(m/z) 1213(M ? 1). Anal. calc. for C72H48N4O8
Mn2: C, 78.53; H, 4.76; N, 5.09; M, 7.80% C, 78.10; H, 4.89;
N, 5.29; M, 7.28%.
Physical characterization of calix[4]arene Schiff base
and Mn complexes
The synthesis scheme of calix[4]arene Schiff base is given
in Scheme 2. The spectroscopic methods (FTIR, 1H NMR,
13C NMR and MALDI-TOF–MS) have been employed to
elucidate the structures of the compounds (H4L1 and H4L2).
FTIR data show that the investigated bonds, which can be
assigned to the stretching of imine (C=N) of both com-
pounds were observed at the frequencies of 1599 to
1640 cm-1. The bands appearing at 3166 to 3421 cm-1 in
the spectra of compounds can be ascribed to the presence
of hydroxy (–OH) group.
1H NMR data of the compounds showed a peak due to
the presence of azomethine proton (CH=N) at the chemical
shift d = 8.54 to 9.33 ppm. While the multiplet owing to
the presence of aromatic protons was observed within the
range of d = 7.0 to 7.83 ppm, the phenolic protons was
observable within the range of d = 9.5 to 13.9 ppm.
13C NMR data of the compounds showed a peak due to
the presence of azomethane carbon (CH=N) observable at
the chemical shift d = 160 and 153.8 ppm. The aromatic
carbon showed peaks observable at d = 172 to 113.3 ppm;
aliphatic carbon at d = 56.4 ppm and methylene bridge
carbon showed peak at d = 13.0 ppm. The percentage of
C, H and N are from the analysis and are in agreement with
the calculated values. The metal content was studied by
AAS.
Oxidation of olefins
All the reactions were carried out in a Schlenk tube under
dinitrogen atmosphere. Styrene (2.5 mmol), catalyst
(0.01 mmol) dissolved in a water-dioxane mixture (2:6 v/v)
and chlorobenzene (internal standard) were mixed and the
reaction mixture was de-aerated by flushing N2 for 10 min.
Iodosyl benzene (90.5 mmol) was then added and the
reaction mixture was stirred for about 4 h. 2 lL aliquots
were withdrawn from the reaction mixture and analysed by
gas chromatography using FID detector. The reaction
mixture was extracted with 3 9 20 mL dichloromethane,
followed by the separation of the organic phase. The
organic phase was washed with saturated FeSO4 solution,
dried over magnesium sulfate, evaporated and analysed by
GC using the internal standard method. After 4 h there is
no further increase in the yield of epoxide which indicates
that the reaction is complete. Authenticated standard
samples were used for the identity of the products; the total
conversion and product distribution were evaluated with
calibration curves, which were obtained by injecting
known amount of authenticated standard. Products were
identified by comparison with standard samples and by
GC/MS.
The synthesis scheme of Mn complexes with the ligand
is as given in the following equation:
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spectra of the complexes (Table 1) were recorded at room
temperature.
Oxidation of olefins
(i) Oxidation of styrene and cyclohexene with manganese
complexes of calix[4]arene Schiff bases are shown in
Figs. 3 and 4.
(ii) Effect of the binuclear complexes on catalytic
oxidation of styrene and cyclohexene
Fig. 1 Structure of Mn2L1
In order to investigate the effect of calix[4]arene ring on
the catalytic oxidation performance of Mn(II) Schiff base
complexes, the oxidation of styrene and cyclohexene using
PhIO as oxidant was chosen as a model reaction. The
dioxygen affinities of Mn(II) complexes were influenced
greatly by the structure of the Schiff base. Calix[4]arene
ring will probably favours oxygen molecule to approach
the coordination center of Mn(II) complexes and stabilize
the bond of Mn=O for its hydrophobicity of outer ethylene
group and orderly arrangement of inner oxa atom. (Mn)2L1
and (Mn)2L2 show more excellent catalytic oxidation per-
formance in selectivities for styrene oxide compared to the
other complexes reported [24] in the literature because of
the presence of two metal centers.
Fig. 2 Structure of Mn2L2
(iii) Selection of single oxygen donor
Table 1 ESR Spectral data of the complexes
The chemical catalytical oxidation with dioxygen
requires the presence of a reducing agent in large excess
(e.g. hydride [25], H2/Pt [26], Zinc [27]) as well as a proton
donor (CH3COOH).
Compound
Polycrystalline state (298 K compound)
g
k
g\
gav
G
A\
A
k
Mn2L1
Mn2L1
2.27
2.20
2.02
2.09
2.070
2.077
2.93
2.87
150
155
27
29
So far the most efficient catalytic method for olefin
oxidation had been with ‘single-oxygen donors’ such as
H2O2 or alkyl hydro peroxides, but with these reagents, the
most selective reaction was observed when run in anhy-
drous conditions [28]. Concentrated solutions of these
oxidants were sensitive to radical-chain decomposition
[29]. NaOCl is also known as a strong oxidant but it could
not provide a good chemical model of P-450 enzyme,
whereas Iodosylbenzene had given similar result as given
by NaOCl and also it gave easy way to understand the
Cytochrome P-450 enzyme model [30–32].
H4L1=H4L2 þ MnðCH3COOÞ2 ꢀ 4H2O
! Mn2L1=Mn2L2 þ 4CH3COOH
The probable structures of Mn(II) complexes are given
in Figs. 1 and 2.
Thermal stability of calix[4]arene Schiff base
complexes
The oxidation of olefin is due to the macrocyclic effect
of calix[4]arene rings that probably facilitates the oxygen
molecules to approach the coordination center of Mn(II)
complexes and form the Mn=O bond through the hydro-
phobicity of the outer ethylene group and the orderly
arrangement of the inner oxygen atoms. Moreover, the
calix[4]arene ring’s special conformation in (Mn)2L1 and
(Mn)2L2 can offer large steric hindrance, and possibly
favor the formation of the active Mn=O and stabilize the
species.
Thermal stability of the calix[4]arene Schiff bases was
studied using TG–DTA analysis, which showed that the
complexes are stable and decomposed above 300 °C.
ESR studies
The electron spin resonance spectra for the paramagnetic
complexes were recorded using tetracyno ethylene (TCNE)
as a reference standard which has g = 2.077. The ESR
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J Incl Phenom Macrocycl Chem (2012) 74:473–480
477
Fig. 3 Catalytical oxidation of
Styrene
Fig. 4 Catalytical oxidation of
Cyclohexene
Table 2 The catalytical oxidation of styrene by Mn(II) Schiff base complexes
Catalyst
Substrate
Product
Conversiona
TOFb
Epoxide yield
Selectivityc
Time (h)
Mn2L1
Mn2L2
Styrene
Styrene
Styrene Oxide
Styrene Oxide
78
72
0.70
0.73
77
71
99
96
4
4
Reaction was carried out at room temperature with Mn(II) complex catalyst (0.01 mmol), the PhIO (0.1 mmol), Styrene (2.5 mmol)
a
Conversion determined by GC using an internal standard
Turnover frequency is calculated by the expression [product]/[catalyst] 9 time s-1
b
c
Selectivity [epoxide yield (%)/conversion (%)] 9 100
Table 3 The catalytical oxidation of cyclohexene by Mn(II) Schiff base complexes
Catalyst
Substrate
Product
Conversiona
TOFb
Epoxide yield
Selectivityc
Time (h)
Mn2L1
Mn2L2
Cyclohexane
Cyclohexane
Cyclohexane epoxide
Cyclohexane epoxide
94
88
1.23
0.90
85
74
90.45
84.40
4
4
Reaction was carried out at room temperature with Mn(II) complex catalyst (0.01 mmol), the PhIO (0.1 mmol), Cyclohexene (2.5 mmol)
a
Conversion determined by GC using an internal standard
Turnover frequency is calculated by the expression [product]/[catalyst] 9 time s-1
b
c
Selectivity [epoxide yield (%)/conversion (%)] 9 100
Catalytical reaction
The selectivity of this reaction was highly dependent of
the initial concentration of olefin where the ratio catalyst/
olefin is kept constant in Fig. 6. For a ratio of 0.4%, the
selectivity increases from 40 to 100% by changing the
olefin concentration from 0.5 to 3.5 mmol. At 2.5 mmol
the conversion was completed within 4 h and the selec-
tivity of styrene oxide reaches 99%. So the increase in
olefin concentration up to 2.5 mmol leads to an efficient
catalytical oxidation of styrene.
(i) Oxidation of olefin with different manganese com-
plexes of calix[4]arene Schiff bases.
Oxidation of olefin with different Mn complexes of
calix[4]arene Schiff bases are shown in Tables 2 and 3
and the oxygen rebound mechanism are shown in
Fig. 5.
(ii) Influence of olefin concentration on the selectivity of
the reaction.
(iii) Influence of the concentration of PhIO
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Fig. 5 Oxygen rebound mechanism of Mn(II) calix[4]arene Schiff
base
Fig. 8 Influence of concentration of PhIO on styrene oxidation
a 0.2 mmol, b 0.4 mmol, c 0.6 mmol
for three different catalyst/olefin ratios: 0.25, 0.4 and 2.5%
(0.0006–0.06 mmol of catalyst). The oxidation selectivity
was nearly the same in all cases (75–80%).The main effect
observed with an increase in catalyst/olefin ratio was the
increase of the reaction rate. For small amount of complex
(less than 0.01 mmol), the conversion was not completed,
most likely the formation of Mn=O of the catalyst after
6–8 h influence the concentration of PhIO
The influence of the concentration of PhIO had been
studied in the oxidation of 2.5 mmol of styrene in the
presence of Mn2L1. Figure 8 shows the Styrene oxide
formation for three different concentration of PhIO. The
main effect observed with an increase in the concentration
of PhIO was the increase of the reaction rate.
Fig. 6 Styrene oxidation at different initial concentration
a 0.5 mmol, b 1.5 mmol, c 2.0 mmol, d 2.5 mmol (% styrene oxide)
Kinetic study
The kinetic studies using different concentrations of sty-
rene and cyclohexene using Mn2L1 and Mn2L2 as catalysts
(25 °C 1 °C) showed that the reaction was zero order
with respect to alkene (slope = 0.1). This is expected,
since a large excess of the alkene was being used, the
reaction becomes virtually independent of the alkene
concentration. Studies using various concentration was of
fractional order with respect to the catalyst concentration
(slope = 0.5).This supports the suggested reaction mech-
anism. Apparently, rate of the reaction does not depend
directly on the concentration of the catalyst but is depen-
dent on the intermediate Mn=O formed by the reaction of
metal centre with the oxidant. Hence, order of the reaction
is fraction with respect to catalyst concentration.
Fig. 7 Influence of the catalyst concentration of styrene oxidation
a 2.5%, b 0.4%, c 0.25% PhIO
Catalyst reuse and stability
The influence of catalyst concentration has been studied
in the oxidation of 2.5 mmol of styrene in the presence of
Mn2L1. Figure 7 shows the cyclohexene epoxide formation
The stability of catalyst was studied in repeated epoxida-
tion reactions. The epoxidation of styrene and cyclohexene
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479
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