Imidazolium-based ionic liquid functionalized reduced graphene oxide supported palladium as a reusable catalyst for Suzuki-Miyaura reactions

Article abstract of DOI:10.1039/c7nj04312k

A novel palladium immobilized on reduced graphene oxide heterogeneous catalyst was prepared. The reduced graphene oxide was functionalized by imidazolium-based ionic liquids containing polyethylene glycol monomethyl ether moieties. The prepared catalyst can achieve Suzuki-Miyaura reactions efficiently in green solvents under mild conditions and could be recycled for five catalytic runs without the loss of activity.

Full text of DOI:10.1039/c7nj04312k

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PAPER
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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Pl Ne ae swe Jd oo u nr no at l ao df j Cu sh te mm ai sr tgr iyn s
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DOI: 10.1039/C7NJ04312K
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Imidazolium-based ionic liquids functionalized reduced graphene
oxide supported palladium as a reusable catalyst for Suzuki-
Miyaura reactions
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
DOI: 10.1039/x0xx00000x
Xin Shi and Chun Cai*
www.rsc.org/
1
3
A novel palladium immobilized on reduced graphene oxide and magnetic nanoparticles. They have been used as green
heterogeneous catalyst was prepared. The reduced graphene media and functional materials for supports of catalysts,
oxide was functionalized by an imidazolium-based ionic liquids surface modifying agents, stationary phases in separation
1
4
containing polyethylene glycol monomethyl ether moieties. The technologies and electrodes in electrochemistry. SILs are
prepared catalyst can achieve Suzuki-Miyaura reactions efficiently able to stabilize the nanoparticles and create an ionic liquid
in green solvent under mild conditions and could be recycled based nano-environment on the surface of material to
1
5
through five catalytic runs without loss of activity.
enhance their interaction with substrates. Thus, SILs can
improve the reaction efficiency when applied as a support in
catalysis. Design and preparation of novel and efficient
heterogeneous metal catalyst containing ILs may afford an
Palladium-catalyzed transformations have seen a fascinating
1
development in the past decades. It plays a crucial role in
1
6
organic synthesis by catalyzing various common
transformations especially carbon-carbon and carbon-
2
heteroatom bond formation. Homogeneous palladium
opportunity to practical engineering applications.
Over the last decade, remarkable progress has been
accomplished in the development of new graphene derivatives
as benign, abundant and readily available catalysts and
catalysts feature high levels of activity since they are uniform
on a molecular level and readily dissolved in the reaction
medium. Homogeneous catalysts present several drawbacks
such as a loss of expensive metal, difficult separation from the
reaction mixture, deactivation of catalyst through the
1
7
supports for organic transformations. Among them, highly
oxidized graphene oxide (GO) is easily functionalized as
supports to covalent immobilization of homogeneous
1
8
catalyst. Alone this line, we report here a novel Pd on GO-
based catalyst, consisting of imidazolium-based ILs containing
polyethylene glycol monomethyl ether (mPEG), which have the
ability to stabilize Pd nanoparticles and improve water
agglomeration and difficult recycling, which limits the large-
3
scale application in industry. Therefore, designing
a
heterogeneous palladium catalyst with high efficiency is of
great interest for both academic and industry fields. In this
context, various inorganic and organic supports have been
1
9
dispersivity for use in aqueous phase catalysis. The activity of
the catalyst was demonstrated by employing the Suzuki-
Miyaura coupling as model reactions. The catalysts promoted
formation of C-C bonds in water at room temperature and
could be reused for five subsequent runs without loss of
activity and there was no need for washing and purification of
the catalyst after each run.
4
explored, such as mesoporous and amorphous silica,
5
6
7
polymers, metal oxides , magnetic nanoparticles and MOF.
8
However, most of them have serious drawbacks like a
complicated synthesis process, hampered diffusion kinetics, or
9
tedious separation.
II
The concept of supported ionic liquids (SILs) becomes very
attractive recently because they refer to ionic liquids (ILs) that
are immobilized on supports by either covalent or noncovalent
The immobilization Pd and Pd onto the IL-functionalized GO
was illustrated in Scheme 1. GO was reduced by ascorbic acid
2
to obtain reduced graphene oxide (RGO). Then, the azide-
0
1
0
2
1
bonds and retain the advantages of ILs and supports. ILs have
12
functionalized RGO was achieved by a reported procedure
1
been linked to a variety of supports, such as silica, resins,
1
and the ILs were attached to the RGO by Cu-catalyzed azide-
alkyne click reaction. Ultimately, the IL-functionalized RGO
(RGO-IL) was reacted with Pd(OAc)2 generating the
heterogeneous Pd catalyst (RGO-IL-Pd). Two catalysts with
imidazolium moiety modified by mPEG200 (RGO-IL-Pd 1a) and
mPEG500 (RGO-IL-Pd 1b) were prepared.
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O
O
N3
Cl
HN
HN
NCO
Cl
NaN
3
O
RGO
O
N
3
Cl
HN
HN
O
O
n
N
N
Br
Br
N
N
O
N
HN
N
N
mPEG
x
O
N
N
O
N
N
Br
HN
N
n
O
RGO-IL
O
O
N
N
N
O
n
N
N
HN
Pd0 and PdII
Pd(OAc)
KO Bu
2
O
N
N
t
O
N
N
HN
N
O
n
1
1
a: x=200
b: x=500
RGO-IL-Pd
3
Figure 2. TGA analysis of RGO, RGO-Cl, RGO-N and RGO-IL
containing mPEG200 moiety.
Scheme 1. The preparation of RGO-IL-Pd catalysts.
X-ray photoelectron spectroscopy (XPS) was performed for
RGO-IL-Pd 1a to illustrate the surface chemical composition of
the catalyst. As shown in Figure 1, the XPS spectrum confirms
that ILs were anchored on RGO. Fresh sample exhibited a
II
higher percentage of Pd with respect to metallic Pd indicating
II
that the process was able to reduce part of Pd . The
imidazolium-based ILs were potential to act as both to s for
II
Pd and stabilizers for PdNPs. Specifically, this raised possibility
that the nanoparticles acted as both catalyst and reservoirs for
II
22
Pd species such as NHC-Pd. The measure indicated the
successful functionalization of RGO with ILs and Pd.
Thermogravimetric analysis (TGA) was further used to study
the composition of RGO-IL containing mPEG200 moiety and the
o
hybrid material showed good thermal stability up to 200 C
(Figure 2). According to BET, immobilization of Pd caused a
small decrease in surface area of support. Due to the
amorphous carbon peak is too strong, palladium peak is not
obvious in the X-ray powder diffraction (XRD) patterns (Figure
S1).
Figure 3. TEM images of (a) (b) RGO-IL-Pd 1a and (c) (d) RGO-
IL-Pd 1b. The inlet image shows the size distribution of PdNPs.
The morphology of the catalyst was directly observed by
transmission electron microscopy (TEM). As shown in Figure 3,
the PdNPs of RGO-IL-Pd 1a and 1b have a good distribution
throughout the RGO sheets with an average diameter of 3.2
nm and 5.6 nm, respectively. The functional groups on the
modified RGO are responsible for stabilizing the palladium
nanoparticles against aggregation. As shown in Figure 3b, the
crystalline fringe patterns and the lattice fringes align parallel
of PdNPs are obvious clearly. The PdNPs aggregated when
mPEG moiety was changed to methyl group (RGO-IL-Pd 1c, see
Figure S2).
C-C cross-coupling reactions, such as Suzuki-Miyaura
reaction, are powerful tools for the preparation of natural
products,
advanced materials and biologically active
compounds. Therefore, the prepared RGO-IL-Pd was explored
as the catalysts in the Suzuki-Miyaura reaction. For this
purpose, coupling of 4-bromoanisole (2a) with phenylboronic
acid (3a) was selected as the model reaction. Among the
solvents tested, H
2
O-EtOH (1:1 v/v) was the optimal choice
(Table 1, entries 1-5). The reaction provided a 96% yield of the
desired product 4a with RGO-IL-Pd 1a (0.5 mol%) at room
temperature (Table 1, entries 6-8). The commercial Pd/C
couldn’t catalyze the reaction and 4a was only obtained in a
moderate yield with RGO-IL-Pd 1c (Table 1, entries 9-11). It
was confirmed that RGO-IL-Pd 1a exhibited the superior
catalytic activity and the imidazolium-based IL modified by
mPEG played the crucial role. After extensive experiments
2 3
using different bases, we found that K CO facilitate the
reaction most (Table 1, entries 12-14). Finally, the normative
reaction conditions were defined. A mixture of 2a and 3a (1.3
equiv.) was reacted in the presence of RGO-IL-Pd 1a (0.5
Figure 1. Survey XPS data for (a) RGO-IL-Pd 1a, (b) N 1s region
and (c) Pd 3d region.
2 3 2
mol%), K CO (2 equiv.) in H O-EtOH (1:1 v/v) at room
temperature for 3 h.
2
| J. Name., 2012, 00, 1-3
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a,b
Table 1. Optimization for the Suzuki—Miyaura coupling
reaction
Table 2. RGO-IL-Pd 1a catalyzed Suzuki reaction
a
Br
B(OH)
2
R
2
R
1
+
R2
Br
B(OH)2
R
1
catalyst
4
+
3
2
base, solvent
MeO
MeO
4a
2a
3a
o
T ( C) Yield (%)
b
Entry
Catalyst
Solvent
c
1
2
RGO-IL-Pd 1a H2O/EtOH (1:1)
80
80
80
80
80
25
25
25
25
25
25
25
25
25
95
46
92
61
90
97
96
81
89
74
n.d.
86
81
69
c
RGO-IL-Pd 1a
RGO-IL-Pd 1a
RGO-IL-Pd 1a
RGO-IL-Pd 1a
RGO-IL-Pd 1a
H
H
2
O
O
c,d
3
2
c
4
H2O/THF (1:1)
c
c
5
H
H
2
O/EtOH (2:1)
O/EtOH (1:1)
6
2
7
RGO-IL-Pd 1a H2O/EtOH (1:1)
e
8
RGO-IL-Pd 1a
RGO-IL-Pd 1b
RGO-IL-Pd 1c
Pd/C
H
H
2
O/EtOH (1:1)
O/EtOH (1:1)
9
2
1
0
1
H2O/EtOH (1:1)
F
CF3
1
H
H
2
O/EtOH (1:1)
O/EtOH (1:1)
f
1
2
RGO-IL-Pd 1a
2
OMe
g
13
RGO-IL-Pd 1a H2O/EtOH (1:1)
RGO-IL-Pd 1a O/EtOH (1:1)
F
MeO
4j,
90%
MeO
MeO
MeO
MeO
4l, 88%
h
4k, 82%
1
4
H
2
O
a
OMe
Reaction conditions: 2a (0.5 mmol), 3a (1.3 equiv.), 0.5 mol%
b
Pd, K
2 3
CO (2 equiv.), solvent (2 mL), 3 h, under air. Yield was
determined by GC, using n-dodecane as the internal standard.
c
4n, 95%
MeO
4o, 97%
4m, 90%
MeO
MeO
d
e
mol% Pd. 8 h. 0.25 mol% Pd. Cs
f
1
2
CO
3
was used as the
tBu
g
h
base. KOH was used as the base. Et
CN
3
N was used as the base.
After optimization of the reaction conditions, we turned to
explore the substrate scope of the established system. A
variety of aryl bromides and arylboronic acids with electron-
4
p, 98%
4q, 88%
a
Reaction conditions: aryl bromide (0.5 mmol), arylboronic
CO (2 equiv.), RGO-IL-Pd 1a (0.5 mol% Pd),
donating or electron-withdrawing functional groups could acid (1.3 equiv.), K
b
reacted smoothly, giving the corresponding products in good r.t. 3 h and H O/EtOH (1:1 v/v, 2 mL). Isolated yield.
2
3
2
to excellent yields (Table 2). The substrates carrying
substituents at the ortho/meta/para position were well
Br
B(OH)2
tolerated in this transformation. This catalytic system was also
found to be applicable for the gram-scale synthesis of Suzuki-
Miyaura coupling reaction (Scheme 2). When 1.1 g of 4-
bromoanisole was treated with phenylboronic acid in the
presence of RGO-IL-Pd 1a (0.5 mol%). The product 4a was
isolated in 81% yield (0.89 g) with 3 h. Comparing with other
reported heterogeneous Pd catalysts, our method with RGO-
IL-Pd 1b is simpler, lower temperature, more efficient and less
2 3
RGO-IL-Pd 1a, K CO
+
MeO
,
2
H O/EtOH, r.t.,air
MeO
2a (1.1 g)
3a
4a (81 %, 0.89 g)
Scheme 2. Gram-scale synthesis of 4-methoxybiphenyl using
RGO-IL-Pd 1a
.
2
3
time consuming for the Suzuki reaction (Table S1).
The recyclability of RGO-IL-Pd 1a Suzuki-Miyaura coupling
reaction was examined. After the reaction, the product was
extracted with n-hexane and the aqueous phased was loaded
with the reactants and base for the next run. Then, the catalyst
reused in five consecutive runs without losing of efficiency
(Figure 4). TEM analysis of the catalyst after the five run
confirmed that the palladium nanoparticles remained
monodisperse mostly with a mean diameter of 6.9 nm. (Figure Figure 4. Recycling of the RGO-IL-Pd 1a in the Suzuki-Miyaura
S3). XPS spectrum of catalyst after recovery was similar with reaction.
II
the spectrum of fresh catalyst, even most of Pd was reduced
to metallic Pd (Figure S4). ICP-MS analysis of palladium
content in the filtrate after the first cycle was below 0.3 ppm.
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These observations confirmed the high efficacy and robust
nature of this catalyst.
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5
In summary, we successfully developed novel, efficient and
recyclable Pd catalysts, consisting of mPEGylated imidazolium-
based ionic liquids on RGO. These catalysts were proved to be
efficient in Suzuki-Miyaura coupling reaction with green
solvent at room temperature. The ILs containing mPEG played
an important role in stabilizing the NPs and improving the
activity of the catalyst. The catalyst exhibited good reusability
,
Gruttadauria and C. Aprile, Catal. Sci. Technol., 2016, 6,
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New Journal of Chemistry
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DOI: 10.1039/C7NJ04312K
Pd supported on ionic liquids functionalized RGO was fabricated and the catalyst shown excellent
performance for Suzuki- Miyaura coupling reaction.