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Synthesis of PEG Supported Palladium Nanoparticles: Simple and

recyclable palladium catalytic system for Heck reaction



P. Ahmadian Namini, A. A. Babaluo
*
, M. Tahmasebpour
Nanostructure Materials Research Center (NMRC), Sahand University of Technology,
P.O. Box 51335/1996, Tabriz, I.R.Iran
Research Center of Polymeric Materials, Sahand University of Technology,
P.O. Box 51335/1996, Tabriz, I.R. Iran.

Abstract
Palladium nanoparticles with narrow size distribution as a catalytic system for Heck
reaction were synthesized by applying poly(ethyleneglycol) (PEG) and Pd(OAc)
2
. PEG
acts as a reducing agent for reduction of Pd
2+
to Pd and also as a stabilizer for synthesized
palladium nanoparticles. Both XRD and TEM results exhibit production of nanoparticles
with about 7nm in diameter. This polymeric palladium catalyst is relatively inexpensive,
environmentally benign, and simply functionalizable and can be easily recovered from
the products.

Keywords: Palladium; nanoparticle; PEG; Heck reaction; catalyst

Introduction
Heck reaction is one of the most versatile and useful tools in organic synthesis.
From the corresponding alkene and aryl compounds, the Heck reaction provides a direct
route to synthesize the important olefins [1]. The Heck coupling, one of the most
important palladium catalyzed CC bond formation reactions, is a process described as
olefin arylation (Scheme 1) [15].
+
R
R R
X
R

Scheme 1.

*
E-mail: a.babaluo@sut.ac.ir
[Pd]

-HX
Arylated olefins, the final products of Heck reaction, have very broad application
in synthesis of pharmaceuticals, agrochemicals, and natural products [4,5]. Therefore,
very intensive research is addressed to elaboration of new, simple and efficient catalytic
systems for Heck coupling reaction [5].
In recent years, there are growing interests on the catalytic properties of transition
metal nanoparticles because of their large surface area and a great ratio of atoms
remaining at the surface. Although many researches have been done, there is still the
paramount challenge for the wide application of transition metal nanoparticle as catalysts
in the industry, i.e. how to separate and recycle them completely from the products. One
approach to separate and recycle metal nanoparticles is to immobilize them onto a
polymeric or inorganic support, making it really easy and simple to separate the catalyst
from the reaction products mixture [6].
In this context, using polymers that are soluble in some solvents but insoluble in
others is gaining increasing importance as scaffolds on which to attach reagents and
catalysts. This methodology allows the reaction to be conducted in a homogeneous phase
using a solvent that dissolves the polymer as a medium, and after completion of the
reaction, the catalytic system can be recovered by precipitation, adding a second solvent
in which the polymer becomes insoluble [7].
Polyethylene glycol (PEG) has been emerging as a very convenient support for
the synthesis of a variety of catalysts, ligands and organic compounds. It is relatively
inexpensive, environmentally benign and can readily be functionalized. It is soluble in
many organic solvents but insoluble in some others such as diethyl ether. These
properties render it very attractive as a mobile support wherein a reaction catalyzed by
the PEG supported catalyst. This reaction can be carried out under homogeneous
condition while the PEG-catalyst system can be easily recovered after extracting the
reaction mixture with diethyl ether [8]. Herein, we report a new and facile route for
preparation of nano-Pd by exploiting PEG, which was found to act as both reducing agent
and stabilizer [1].



2. Experimental
2.1. Materials
The characteristics of the materials used in this work are given in Table 1.

Table 1. Characteristics of materials
Materials Function Molecular formula Characteristics Supplier
Palladium acetate Palladium Precursor C
4
H
6
O
4
Pd
Solid Brown Powder
Mw: 224.49 Merck
1
Poly(ethyleneglycole) Reducing agent HO(C
2
H
4
O)
n
H
Ave. Molecular Weight:
2000, 6000 and 35000 Merck
1
Methane Dichloride Solvent CH
2
Cl
2
Transparent Liquid Merck
1
1
E.Merck, D 6100 Darmstadt, Germany.

2.2. Preparation of nano-Pd
0.05 gr palladium acetate was added into 4 gr PEG 6000 [9] at 80
o
C by magnetic
stirring. The resulting light yellow homogeneous solution was further stirred for 2 h at the
same temperature. During this process the color of the solution changed from light yellow
to brown and finally turned black, indicating the formation of nano-Pd. The process then
followed by ultrasonic irradiation of solution for 1 h at the same temperature. Then the
mixture of PEG and palladium nanoparticles was cooled immediately to ambient
temperature to form a solidified mixture.

2.3. Characterization
The X-ray Diffraction (XRD) patterns of Pd nanoparticles were determined on a
TW3710 Philips XPert diffractometer using CuK as radiation and CuK as a filter
(=1.54 ). Data were collected in the range 5 2 80 with a 0.02 2-step and 2 sec
per step (40 kV and 30 mA). The average size of crystallites was calculated from the
peak broad (111) by using the DebyeScherrer equation [10]. The transmission electron
micrographs (TEM) were obtained by employing CM-200 FEG Philips microscope. TEM
samples were prepared by solving Pd/PEG in CH
2
Cl
2
and then drops of prepared
colloidal solution were placed onto a carbon-coated copper grid.
40 38 44 36 42
2

3. Results and discussion
3.2. Crystal structure
The crystalline properties of the prepared samples were investigated by XRD. The
result of XRD pattern was shown in Fig. 3(a). The two prominent peaks of PEG (at 2 =
19.2 and 23.4) were presented in this pattern, indicating the presence of pure polymer,
also the characteristic peak of Pd (about 2 =40) was presented [11]. In addition, the
standard XRD pattern of the palladium nanoparticles was shown in Fig. 3(b). The
obtained cluster size of palladium nanoparticles using the Scherrer formula showed that
the synthesized nanoparticles size is less than 10 nm.



















a
0 10 20 30 40 50 60 70 80 90
2
PEG
38 39 40 41 42 43 44 45 46
2
I
n
t
e
n
s
i
t
y
b
Fig. 3. (a) XRD pattern of the synthesized Pd nanoparticles by 0.05 gr Pd(OAc)
2
into 4 gr
PEG 6000, (b) standard XRD pattern for palladium [12].
3.3. Particle size and morphology
Fig. 4 presents the TEM image of palladium nanoparticles prepared by adding
0.05 gr Pd(OAc)
2
into 4 gr PEG 6000. TEM image of this sample exhibits palladium
nanoparticles with narrow size distribution and average dimensions about 7nm.


Fig. 4. TEM images of Pd nanoparticles prepared at 0.05 gr of Pd(OAc)
2


Conclusion
The obtained results are presented as follow:
Polymer supported nano-Pd catalyst was synthesized by applying
poly(ethyleneglycol) (PEG) and Pd(OAc)
2
as a catalyst system for Heck reaction.
The obtained results of XRD confirmed the formation of palladium nanoparticles
with cluster size less than 10nm.
TEM image showed palladium nanoparticles with narrow particle size distribution
and average dimension 7nm.


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