Immobilized triazine bis[mercapto amine] complexes of Pd(0) anchored nickel ferrite as a nanocatalyst for C–C coupling reaction

Article abstract of DOI:10.1080/00958972.2018.1458229

Immobilized triazine bis[mercapto amine] complexes of Pd(0) (NiFe₂O₄@TABMA-Pd(0)) was easily synthesized and applied as highly efficient and versatile nanocatalyst for the synthesis of various trans stilbenes with high performance fo

Full text of DOI:10.1080/00958972.2018.1458229

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Immobilized triazine bis[mercapto amine]
complexes of Pd(0) anchored nickel ferrite as a
nanocatalyst for C-C coupling reaction
Hossein Naeimi & Fatemeh Kiani
To cite this article: Hossein Naeimi & Fatemeh Kiani (2018): Immobilized triazine bis[mercapto
amine] complexes of Pd(0) anchored nickel ferrite as a nanocatalyst for C-C coupling reaction,
Journal of Coordination Chemistry, DOI: 10.1080/00958972.2018.1458229
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Publisher: Taylor & Francis
Journal: Journal of Coordination Chemistry
DOI: http://doi.org/10.1080/00958972.2018.1458229
Immobilized triazine bis[mercapto amine] complexes of Pd(0) anchored nickel
ferrite as a nanocatalyst for C-C coupling reaction
HOSSEIN NAEIMI* and FATEMEH KIANI
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 87317-51167, I.R. Iran
Immobilized triazine bis[mercapto amine] complexes of Pd(0) (NiFe O @TABMA-Pd(0)) was
2
4
easily synthesized and applied as highly efficient and versatile nanocatalyst for the synthesis of
various trans stilbenes with high performance for the Heck coupling reaction of several types of
aryl halides under thermal conditions. In short reaction time, excellent yields of trans stilbene
derivatives have been achieved using NiFe O @TABMA-Pd(0) catalyst.
2
4
Keywords: NiFe O @TABMA-Pd(0), Styrene, Aryl halide, Heterogeneous catalyst, Trans
2
4
stilbene derivatives
1
. Introduction
One method for carbon–carbon bond forming is Heck coupling [1-3], which involves reaction
between aryl halides and olefins in the presence of a base. Initially, aryl, benzyl, and vinyl
halides are used as electrophiles, but many alkyl compounds are employed as the electrophiles
[4]. Carbon–carbon bond formation by transition-metal catalyzed coupling reactions is a
significant procedure in organic synthesis [5]. This method first reported in 1971 has become a
powerful tool for various organic syntheses, preparation of advanced enantioselective natural
products and pharmaceutically active ingredients, polymerization processes, production of
pharmaceuticals, agrochemicals, advanced materials and fragrances [6-8]. Previously, phosphine
ligands have been applied to stabilize active palladium intermediates, and great effects have been
*
Corresponding author. Email: naeimi@kashanu.ac.ir
1

reported for Pd-catalyzed carbon-carbon coupling reactions. However, the oxygen and water
sensitivity, expense, toxicity and lack of recoverability of these ligands prevents their use in a
diversity of synthetic applications.
Mizoroki–Heck coupling reactions are usually catalyzed by soluble palladium complexes
containing diverse ligands in water or organic solvents [9-13]. These homogeneous systems are
the first option of chemists because of their high activity and selectivity; however, these are
difficult to separate and reuse, often due to pollution with final products limiting their use in
synthetic and industrial applications [14, 15]. To overcome these drawbacks, research on
developing effective procedures for Pd complexes on several different solid supports, such as
clays, [16] activated carbon, [17] microporous polymers, [18] and magnetic nanoparticles, have
been performed.
Herein, we study a highly active catalytic system based on a Pd complex for Heck
coupling reactions of styrene with various aryl halides using DMF as solvent.
2
2
. Experimental
.1. General procedure for the synthesis of NiFe O @TABMA-Pd(0)
2
4
Nickel ferrite nanoparticles (NiFe O ) were synthesized by using co-precipitation according to
2
4
the procedure reported [19]. The core-shell NiFe O @SiO nanoparticles were obtained by a
2
4
2
Stober method with minor modifications [20, 21]. The surface of silica nanoparticles can be
easily functionalized through aminopropyltriethoxysilane according to the procedure reported
[22]. For synthesis of ligand 3, to a mixture of 1 (0.50 g) in dry toluene (30 mL) at 0 C,
1
,3,5-trichlorotriazine (TCT) (2 mmol, 0.37 g) and diisopropylethyl amine (2 mmol, 0.34 mL)
were added and the mixture was stirred at 0 C for 3 h. After consumption of TCT and
production of 2, cysteaminium chloride (4 mmol, 0.45 g) and diisopropylethyl amine (4 mmol,
0
.68 mL) were slowly added to this mixture and refluxed in dry toluene for 24 h. The residue
was separated from the mixture by an external magnet, washed with CH Cl several times and
2
2
dried at 80 C to obtain 3. The final catalyst nanoparticles were prepared as brown solids by
addition of Pd(OAc) (10 mg, 0.45 mmol) to a dispersed mixture of 3 in acetonitrile (5 mL)
2
under nitrogen at room temperature. Then, the mixture was stirred for 6 h at 60 C and an
additional 45 min at 70 C. The final complex was collected by an external magnet and washed
repeatedly with ethanol to remove the unreacted Pd(OAc) , and then dried under air to obtain 4
2
2

(
scheme 1). The 10 ml NaBH solution (1 mmol) was added to the above solution with
4
mechanical stirring at room temperature for 24 h. Then, the catalyst was separated from the
mixture by centrifugation, washed several times with methanol to remove unreacted Pd(OAc)2
and dried under vacuum to obtain a black solid powder.
Cl
N
Cl
N
Cl
O
O
Si
NH2
N
O
O
Si
N
Dry toluene
H
NiFe2O4
OEt
+
N
N
NiFe O
2
4
N
OEt
Cl
Cl
(1)
(2)
2
Cysteamonium Chloride
Dry toluene
AcO OAc
Pd
S
N
S
NH2
NH2
S
N
S
NH
N
N
N
Pd(OAc)2
O
Si
OEt
N
H
O
Si
N
H
NiFe2O4
O
NiFe2O4
N
Acetonitrile
O
OEt
NH
Pd
AcO OAc
(4)
(3)
Scheme 1. Synthesis of the catalyst NiFe O @TABMA-Pd(0).
2
4
For synthesis of trans-stilbene derivatives, a mixture of selected aryl halide (1 mmol),
styrene (1.2 mmol) and NEt (2 mmol) in the presence of 0.015 g catalyst at 130 C was reacted
3
in DMF as solvent for 2.5-12 h according to table 1. The progress of the reaction was monitored
by thin layer chromatography (n-hexane/ethyl acetate, 4:1). After completion of the reaction, the
catalyst was separated by an external magnet, washed with absolute ethanol, dried, and used for
the next reactions without further purification. After separation of the catalyst, ethyl acetate
(15 mL) was added and the organic phase was washed with water (3 × 10 mL), and dried over
anhydrous MgSO . The resulting solution was evaporated under vacuum to give the crude
4
product. Column chromatography of the crude product on silica gel using n-hexane or different
mixtures of n-hexane, ethyl acetate as the eluents afforded the highly pure product.
3
. Results and discussion
The method for preparation of the catalyst is shown in scheme 1. In order to characterize the
catalyst structure, the synthesized nano catalyst was analyzed using Fourier transform infrared
3

(
FT-IR) spectra, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy
EDX), vibrating sample magnetometer (VSM), and also, thermo-gravimetric analysis (TGA)
(
techniques.
Figure 1 shows the FT-IR spectrum of NiFe O NPs, NiFe O @SiO , NiFe O @SiO –
2
4
2
4
2
2
4
2
-1
NH NPs and NiFe O @TABMA from 400–4000 cm . The spectrum presents characteristic
2
2
4
-1
-1
bands at 3415, 2920, 1620, 597 and 421 cm . Bands at 3415 and 1620 cm can be assigned to
-1
the stretching modes of absorbed water. The band at 597 cm is attributed to Fe―O vibration.
-1
The band at 421 cm can be assigned to Ni―O vibrations. In all three spectra, the peaks of
−
1
NiFe O were observed at 421–601 cm , which could be attributed to the absorption of Fe―O
2
4
and Ni―O bonds. In NiFe O @SiO , NiFe O @SiO –NH , and final catalyst spectra the intense
2
4
2
2
4
2
2
−
1
peaks at 1091, 1095 and 1096 cm were derived from the Si–O–Si stretching vibrations. These
peaks proved that SiO has coated the surface of NiFe O . In the NiFe O @SiO –NH spectrum,
2
2
4
2
4
2
2
−
1
the peaks at 1635 and 1540 cm could be attributed to the C–N stretch and NH bending
2
−
1
−1
vibration. The peak at 2945 cm is related to the CH stretch, the peak at 1466 cm is related to
2
−
1
bending vibration of CH and the peak at 3439 cm is assigned to the N–H stretch. These peaks
2
confirmed that NiFe O @SiO –NH NPs are prepared. The FT-IR spectrum of
2
4
2
2
−
1
−1
−1
NiFe O @TABMA showed absorption bands at 1625 cm (C=N), 2983 cm (C–H), 3421 cm
2
4
−
1
(
N–H stretching vibration) and 778 cm (C–S stretching vibration).
Figure 2 shows the SEM image of NiFe O and NiFe O @TABMA-Pd(0); spherical
2
4
2
4
morphology with an average diameter of 25-35 nm for NiFe O and 40 nm for
2
4
NiFe O @TABMA-Pd(0) was observed. Also, the elemental analysis for catalyst was
2
4
performed. Figure 3 shows the EDX spectra of NiFe O @TABMA-Pd(0). The results showed
2
4
the presence of C (26.7), N (15.98), O (33.43), Si (3.68), S (4.80), Fe (6.17) and Pd (7.59) in the
composites which confirm that the catalyst has been synthesized.
The loading of Pd in NiFe O @TABMA-Pd(0) was determined using inductively
2
4
-1
coupled plasma atomic emission spectroscopy (ICP-AES) and was 4.93 wt% (0.27 mmol g ).
Thermal stability of the catalyst was investigated by TGA and the related curves are
demonstrated in figure S1 (Supporting Information). Herein TGA analysis curves of
NiFe O @SiO and NiFe O @TABMA-Pd(0) are compared. Both curves have similar
2
4
2
2
4
characteristics. As demonstrated in figure 4a, 6% decrease in weight before 150 °C is attributed
to removal of surface hydroxyl groups and physically adsorbed solvent and water molecules
4

trapped in the SiO layer. The weight loss of 7% between 400 and 600 °C is attributed to
2
decomposition of less stable functional groups, for example hydroxyl grafted to the silica
surface. As illustrated in figure 4b, small weight loss (10%) between 150 °C and 250 °C is
attributed to the trapped water. The organic components (40%) were lost between 250 and
4
00 °C. These results show the catalyst is stable up to 250 °C and can be used in organic
synthesis.
Magnetic properties of NiFe O nanoparticles and NiFe O @TABMA-Pd(0) were
2
4
2
4
investigated with VSM at room temperature (figure S2 (Supporting Information)). Magnetization
of samples could be completely saturated at fields up to 1.0 T and the saturation magnetization of
-1
samples decreased from 35 to 7 emug because of the functionalization by extra organic layer.
Furthermore, these results illustrate that the magnetization decreases by coating and
functionalization. It is important that a catalyst possess enough magnetic properties for its
experimental application.
To examine the catalytic performance of the nanocatalyst and to characterize optimal
conditions for Mizoroki–Heck coupling reaction, iodobenzene and styrene were selected as
model reagents and were investigated under different parameters such as solvent, various
amounts of catalyst and the effect of different temperatures.
In our first set of experiments, we examined efficiency of the different solvents in the
model reaction. Several organic solvents, acetonitrile, ethanol, dimethylformamide, dimethyl
sulfoxide and toluene, were examined. According to data in table 1, entry 4, DMF was the most
efficient solvent for this transformation. Other solvents gave only moderate yields of the product.
In continuation of this research, the activity of the catalyst in different amounts on the
reaction was investigated. No reaction was observed in the absence of catalyst at 140 °C (table 1,
entry 6). The results demonstrated that on heating and 0.015 g of the NiFe O @TABMA-Pd(0)
2
4
catalyst, the reaction time is decreased to 2.5 h and the yield increased sharply to 96% (table 1,
entry 9). The reaction temperature was also optimized. The model reaction was performed in the
presence of 0.015 g of NiFe O @TABMA-Pd(0) catalyst in DMF under various temperatures to
2
4
investigate the best operating suitable temperature. The best temperature was 130 °C (table 1,
entry 11).
In the next step, to obtain a suitable base for the coupling reaction, different bases were
studied in this reaction. Among the various bases screened, NEt was found to be the best base
3
5

for this reaction (table 2, entry 4). Bases such as Na CO and K CO gave moderate yields of the
2
3
2
3
product.
Furthermore, the kinetic effects of NiFe O @TABMA-Pd(0) on Heck cross-coupling
2
4
reaction of iodobenzene and styrene were investigated. The results are shown in figure 4. As can
be seen in figure 4, the reaction efficiency is higher and the reaction proceeds at a higher rate at
the initial times than the end times.
After optimization of the reaction conditions, a broad range of structurally diverse aryl
halides were reacted with styrene in the presence of 0.015 g of NiFe O @TABMA-Pd(0)
2
4
catalyst and 2 mmol NEt with DMF as solvent at 130 °C and the results are displayed in table 3.
3
As shown in table 3, the reaction performed efficiently in high yield between 2.5-12 h at 130 °C.
Also, in the presence of Pd nanocatalyst, excellent product yields were achieved in shorter
reaction time.
In order to show the merit of this proposed research, we compared the obtained results
with recently reported results [32-36]. For this purpose, the reactions of iodobenzene and styrene
using Pd complex in DMF at 130 °C in the presence of 2 mmol of NEt were chosen as a model
3
reaction and the comparison was performed on the basis of reaction time and obtained yields
(table 4, entry 5 vs. entries 1-4). The properties which make our research better than previous
procedures are mild reaction conditions, environmentally benign, simple recycle of the nano
catalyst by an external magnet, reusability of the catalyst for six times without considerable loss
of catalytic activity, excellent yields of trans stilbene and very short reaction times.
The recyclability of the catalyst was investigated in the coupling of iodobenzene. After
completion of the reaction, the catalytic system was separated from the reaction mixture using an
external magnet and the residual catalyst was washed, dried and reused in subsequent reactions.
After six cycles (figure 5), the catalyst had approximately the same activity and corresponding
product in high yields.
4
. Conclusion
Here we have used NiFe O @TABMA-Pd(0) as a highly active heterogeneous catalyst in the
2
4
Heck coupling reactions. This reaction produced the corresponding trans-coupled products
stereoselectively in high yields and acceptable reaction times. The catalyst can be separated by
6

an external magnet and reused several times without significant loss of activity, which is an
additional sustainable characteristic of this method.
Acknowledgments
The authors are grateful to University of Kashan for supporting this work by Grant No.
1
59148/72.
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8

Figure 1. FT-IR spectrum of a) NiFe O NPs, b) NiFe O @SiO , c) NiFe O @SiO –NH NPs
2
4
2
4
2
2
4
2
2
and d) NiFe O @TABMA.
2
4
9

Figure 2. SEM images of NiFe O nanoparticles (a) NiFe O @TABMA-Pd(0) (b).
2
4
2
4
Figure 3. EDX spectrum of the NiFe O @TABMA-Pd(0).
2
4
1
0

Figure 4. Kinetic effect diagram of NiFe O @TABMA-Pd(0) on the reaction.
2
4
Figure 5. Reusability of catalyst for the synthesis of trans stilbene.
1
1

Table 1. Optimization of the various amounts of catalyst, temperature and solventa.
X
NiFe O @TASDA-Pd(0).
2
4
DMF/130ºC
R
Entry
Cat. (g)
T (C)
Solvent
EtOH
Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
0.020
0.020
0.020
0.020
0.020
0
140
140
140
140
140
140
140
140
140
140
130
120
110
3.5
4.5
4
83
75
79
96
49
0
CH CN
3
DMSO
DMF
Toluene
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
2.5
5
15
4
0.005
0.010
0.015
0.020
0.015
0.015
0.015
61
78
96
96
96
92
87
3.5
2.5
2.5
2.5
3
1
1
1
1
0
1
2
3
4.5
a
Reaction conditions: iodobenzene (1 mmol), styrene (1.2 mmol) and NEt3
2 mmol) in solvent.
(
1
2

Table 2. Optimization of the different bases in reactiona.
Base amount
mmol)
Entry
Base
Yieldb
(
1
2
3
4
5
6
7
KOH
2
55
46
78
96
57
96
90
NaHCO3
K PO
2
2
3
4
NEt3
2
NaHCO3
NEt3
2
2.5
1.5
NEt3
a
Reaction conditions: iodobenzene (1 mmol), styrene (1.2 mmol),
30 °C, in DMF as solvent (5 mL). Isolated yield.
b
1
1
3

Table 3. Mizoroki–Heck cross-coupling of coupling of aryl halides and styrene in the
a
presence of NiFe O @TABMA-Pd(0) .
2
4
X
NiFe O @TASDA-Pd(0)
2 4
DMF, NEt ,130ºC
3
R
R
3
a-n
1
a-n
H 3-Me CHO CN 3-Cl Br COMe OMe NO2 4-Me COOMe
R
I
Br
X
a
b
c
i
d
e
f
g
h
j
k
l
m
n
Cl
b
Thermal conditions
Entry
Aryl halide
Product
Ref.
c
Time (h)/Yield (%)
1
2
3
4
5
6
7
8
9
1a
1k
1e
1d
1f
3a
3k
3e
3d
3f
2.5/96
5.5/87
6/90
[23]
[24]
[25]
[26]
[25]
[27]
[28]
[29]
[30]
[24]
[31]
[30]
[27]
[25]
5/81
7/87
1c
1l
3c
3l
3/78
7/80
1h
1j
3h
3j
7/94
6/94
1
1
1
1
0
1
2
3
4
1b
1g
1n
1i
3b
3g
3n
3i
2.5/98
7/90
11/66
9/83
1
1m
3m
12/65
a
Reaction conditions: iodobenzene (1 mmol), styrene (1.2 mmol) and NEt (2 mmol) in
3
b
c
solvent. at 130 °C. Isolated yield.
1
4

Table 4. Comparison of the results in this research with various reports in the literature.
Entry
Catalyst
Time (h)
Yield (%)a
Ref.
1
Pd/MFC
2
66
75
68
71
96
[33]
2
Palladium acetate
Chloropalladated
PdCl (SEt )
2
[34]
3
48
23
[35]
4
[36]
2
2 2
5
NiFe O @TABMA-Pd(0) 2.5
This work
2
4
a
Isolated yield.
1
5