Au-Pd bimetallic nanoparticles supported on a high nitrogen-rich ordered mesoporous carbon as an efficient catalyst for room temperature Ullmann coupling of aryl chlorides in aqueous media

Article abstract of DOI:10.1039/c8cc00475g

An ionic liquid derived highly nitrogen-rich mesoporous carbon supported Au-Pd alloy was found to be an efficient and recyclable catalyst for the Ullmann coupling reaction of various aryl chlorides at room temperature in aqueous media.

Full text of DOI:10.1039/c8cc00475g

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
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Au-Pd Bimetallic nanoparticles supported on a high nitrogen-rich
ordered mesoporous carbon as an efficient catalyst for room
temperature Ullmann coupling of aryl chlorides in aqueous media
Received 00th January 20xx,
Accepted 00th January 20xx
Babak Karimi,*a,b Hossein Barzegar,a and Hojatollah Valic
DOI: 10.1039/x0xx00000x
www.rsc.org/
An Ionic liquid derived high nitrogen-rich mesoporous carbon selectivity, compared to their monometallic counterparts.6 The
supported Au-Pd alloy was found to be an efficient and recyclable improved catalytic performance in bimetallic systems is
catalyst for Ullmann coupling reaction of varied aryl chlorides at generally attributed to the synergistic effect caused by
room temperature in aqueous media.
electronic interaction between two metals. In this context, the
alloying of Pd with Au due to their high miscibility and
astonishing activity in different chemical transformation is
encouraging among all sorts of bimetallic systems that have
been created so far.7 Despite this eye-catching feature, to the
best of our knowledge, there is solely one example of using
colloidal Au-Pd nanoclusters stabilized with soluble poly-
vinylpyrolidone (PVP) in room temperature Ullmann coupling
reaction condition.8 While this report represents an impressive
advancement in the field, the low activity of the catalyst
toward coupling of aryl bromides, the use of DMF as co-
solvent and reducing agent, and the recyclability of catalyst are
the critical issues that have to be resolved. Compared with the
homogeneous catalysts, the heterogenization of catalyst on a
suitable support, which is convenient for recycling from the
reaction mixture and readily used in flow reactors are
preferable, in particular in large-scale operations. The last
decade has witnessed with fast-growing interest on the design
and application of nanoporous carbon materials in various
fields.9 Within this context, ordered mesoporous carbons have
a special place because of their unique structural as well as
The aryl-aryl bond forming reactions are arguably among the
most versatile strategy for constructing biaryl units, which
involve in a wide range of products such as pharmaceuticals,
agrochemicals, conducting polymers, and natural products.1 In
particular, Ullmann homocoupling of aryl halide, has been
attracted increasing attentions in recent years for preparing
symmetrical biaryl systems. Although, this reaction is
traditionally promoted with excess of copper catalyst at
elevated (>200 °C) temperature,2 a substantial amount of
research has been recently dedicated to the development of
more efficient catalyst systems that use single transition
metals like Pd,3 Ni,4 and Au,5 under both homogeneous and
heterogeneous conditions. However, many of these protocols
are still conducted under extensive heating (up to 140 °C).
Since thermal enhancement of catalytic activity is energy
consuming, it would be a significant advance if one could
enhance a catalytic process at ambient temperature. In
particular, the energy issue becomes more serious in the case
of coupling reactions involving aryl chlorides, due to higher
dissociation energy of C-Cl bond as compared with C-Br or C-I
bonds. However, almost in all reported cases, a single metallic
catalyst fails to promote Ullmann coupling reaction of
chloroarenes at ambient condition effectively. Recently,
bimetallic catalysts have been drawn much attention due to
their distinctive, excellent functions regarding activity and
physiochemical
aforementioned
properties.10
But
in
addition
to
features,
nitrogen-riched
ordered
mesoporous carbons with high energy electrons and enhanced
π-bonding ability have found to exhibit extraordinary
performance as catalyst support because they can strongly
alter electron density at the catalytically active metal centers
and make them more electron-rich and reactive in certain
chemical transformations.11 Recently, we reported the
preparation of Pd nanoparticles, supported on ionic liquid
derived nanofibrillated mesoporous carbon (Pd@IFMC). This
powerful catalyst has thus far successfully applied as an
effective catalyst for aerobic oxidation of alcohols and Ullmann
homocoupling reaction in aqueous media.1a,12 The suitable
nitrogen content and excellent physiochemical as well as
electronic properties of IFMC encourage us to initially
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investigate the potential of this material to also stabilize Au-Pd carbonization
Journal Name
of
1-methyl-3-phenethyl-1H-imidazolium
bimetallic nanoparticles by emphasizing the possibility to hydrogen sulfate (MPIHS) containing 10% and 15% dissolved
perform Ullmann coupling of chloroarenes in water at room guanine, respectively, in the presence of mesoporous silica
temperature. For this reason we first prepared the (SBA-15) as hard template. After removal of SBA-15 template,
corresponding Au-Pd@IFMC by
method.13 An initial assessment of catalytic activity of Au- materials were denoted as
Pd@IFMC (1 mol% with respect to Pd content) in Ullmann arbon from ran (NMCI). As expected, the nitrogen content
coupling of chlorobenzene at room temperature in water-EtOH increases from ~6wt% (in IFMC) to 9.2 wt% in NMCI-1 and 12.6
a
simple impregnation the corresponding mesoporous carbons were obtained. The
N
itrogen-rich Ordered esoporous
M
C
I
(4:1) gave 46% conversion to biphenyl (Table 1, entry 1).
Table 1. Solvent optimization of Ullmann reaction.a
wt% in NMCI-2, respectively. Notably, further increasing of
guanine results in highly disordered carbon materials, which is
most likely due to insolubility of guanine at higher
concentration than 15%. The nitrogen loaded into materials
was homogeneously distributed in the samples on the
nanometer scale as clearly evident by high resolution
elemental mapping (Fig. 1).
Yield
(%)[b]
Entry
Catalyst
Solvent
1
2
Au-Pd@IFMC
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (1:9)
H2O/EtOH (1:3)
H2O/EtOH (1:2)
H2O/EtOH (2:1)
H2O/EtOH (3:1)
H2O/EtOH (1:1)
H2O/EtOH (5:1)
H2O/EtOH (6:1)
H2O
46
38
75
>99c
51
26
44
77
94
70
80
75
3[c]
24
-
Au-Pd@CMK-3
Au-Pd@NMCI-1
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Pd@NMCI-2
3
4
5
6
7
8
Fig. 1. Nitrogen mapping (left) and Carbon-mapping of NMCI-2 (scale bar = 0.5 µm).
9
N2 adsoprtion-desorption isotherm of both NMCI-1 and NMCI-
2 show typical type IV curves, with a steep increase of
adsorption branch at P/P0 of about 0.45-0.65 due to capillary
condensation of nitrogen in the mesopores, suggesting a
uniform mesoporous structure (Fig. 2a). The hysteresis loops
do not resemble H1-type, indicating the presence of some
pore blocking and/or pore distortion.[15] The BET surface area
and pore volume of NMCI-1 are 900 m2g-1 and 0.9 cm3g-1,
respectively, whereas NMCI-2 possesses specific surface area
1026 m2g-1 and pore volume 1.02 cm3g-1.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
H2O/i-PrOH (1:1)
DMF
H2O/DMF (1:1)
CH3CN/DMF (3:1)
CH3CN/DMF (1:3)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
H2O/EtOH (4:1)
-
-
-
29
-
Au@NMCI-2
Fig. 2. a) N2 adsorption-desorption (main diagram) and BJH pore-size distribution
NMCI-2
-
(inset diagram) of NMCI-2, Au-Pd@NMCI-2, and recycled Au-Pd@NMCI-2; b)
Au-Pd@NMCI-2
Au-Pd@NMCI-2
Au-Pd@NMCI-2
95[d]
6[c]
3[c]
a
Reaction conditions: 0.25 mmol of aryl halide, 1 mol% of catalyst (with respect to
c
b
Pd) K2CO3 (0.5 mmol), and 3 mL of solvent at room temperature. Isolated yield
GC Yield using standard addition method. d The reaction was conducted within 6 h.
.
Interestingly, similar reaction using Au-Pd@CMK-3 proved to
be considerably less efficient, resulting in the formation of 38%
of biphenyl (Table 1, entry 2). While these initial experiments
supported our hypothesis that the nitrogen content in IFMC
might indeed enhance the catalytic activity of Au-Pd
nanoparticles in Ullmann coupling, the result was still
unsatisfactory. Therefore, in the next stage we were
committed to unambiguously determine the impact of
nitrogen concentration. Recently, Antonietti and et al. have
elegantly shown that the use of nucleobases in direct
carbonization of cyno/nitrile containing aprotic ionic liquids
results in N-doped carbon materials with enhanced nitrogen
content up to 12.6%.14 Inspired by this finding, we next
proceeded to prepare two novel nitrogen-riched ordered
mesoporous carbon with different nitrogen loading by direct
TEM image of IMCI-1; c) TEM image of IMCI-2, d) TEM image of Au-Pd@IMCI-2
(Scale bars for all TEM images, 100nm)
The Barrett-Joyner-Halenda (BJH) pore size distribution of
NMCI-1 and NMCI-2 calculated from the desorption branch of
N2 soprtion isotherm are quite narrow with maxima at 2.4 and
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3.3 nm, respectively, confirming high uniformity of during the course of reaction as a reducing agent. Further
mesoporous structure in both materials (Fig. 2a, inset). investigations were established in order to gain more insight
Transmission electron microscopy (TEM) of both mesoporous into the synergistic interplay between Au and Pd. Inefficient
carbons in the direction perpendicular to their axis, display a Ullmann coupling of chlorobenzene in the presence
regular pattern (Fig. 2b, c). Deconvoluted XPS spectrum in the Au@NMCI-2, Pd@NMCI-2 and also physical mixture of these
region of N1s demonstrated the presence of four distinctive catalysts showed the critical importance of formation of Au-Pd
nitrogen species including pyridinic (398.3 eV), pyrrolic (399.8 alloy structure for obtaining highly active catalyst in the
eV), graphitic (401.1 eV), and oxidized N (N-O) (403.3 eV). Also present coupling reaction (Table 1, entries 19-20). Moreover,
the data corresponding the atomic percent of each nitrogen no catalytic activity was observed from NMCI-2 under optimal
type indicated that the major nitrogen types in our support reaction conditions (Table 1, entry 21). The investigations also
material are pyridinic N (37.82 %) and graphitic N (28.61%). showed that using Au-Pd@NMCI-2 (1mol%), the coupling
The corresponding supported Au-Pd catalyst was then reaction of chlorobenzene was completed even after 6 h under
prepared by a similar impregnation metnod to Au-Pd@IFMC.13 otherwise the same reaction conditions (Table 1, entry 22).
Evidently, Au-Pd@NMCI-2 exhibited much superior activity
than Pd@NMCI-1 could under the conditions demonstrated in
Table 1 (entries 3, 4). This promted us to focuse on further in
dept characterization of Au-Pd@NMCI-2. The N2 sorption
analysis showed that the isotherm shape of the pristine NMCI-
2 was preserved after modification, and during the process of
impregnation possible blockage or alteration did not happen in
the meso channels. In this case, owing to the presence of Au-
Pd alloy structures within the interior nanospaces of the NMCI-
2, as expected, the specific surface area of the compound was
Fig. 3. High angle annular dark field (HAADF) image of Au-Pd@NMCI-2 and line-scan
reduced (Fig. 2a and Fig. S9-S10 vs. S15). As it is demonstrated
energy dispersive X-ray spectroscopy (EDAX) in the selected region
in the TEM analysis (Figure 2d), the metal particles are
distributed uniformly over the NMCI-2 and there is no
For a better understanding of the reaction conditions, the
evidence of agglomeration of the particles. Furthermore, the
chlorobenzene coupling was examined either under O2
unique structure of this catalyst was elegantly confirmed by 3D
tomography video.13 Also, survey of XPS spectum for Pd and Au
condition (Table 1, entry 24). These results imply the
in NMCI-2 demonstrated that both metals are almost in the
atmosphere (Table 1, entry 23) or under the base free
importance of neutral atmosphere and the presence of the
form of zero oxidation state (Fig. S20). These initial results
base. These trends evidenced the simultaneous interaction
suggest that nitrogen content may be indeed provided a
between NMCI-2 and Au-Pd nanoparticles together, and also
significant impact on electronic properties of the supported
synergism between them led to the creation of this significant
catalytic species, thereby allowing Au-Pd@NMCI-2 to acquire
catalytic activity. High angle annular dark field (HAADF) image
superior activity in comparison to Au-Pd@NMCI-1, Au-
of the Au-Pd@NMCI-2 catalyst has been also obtained and the
Pd@IFMC, and Au-Pd@CMK-3 (Table 2, entries 1-4). Although
measured particles composition is displayed in Figure 3. It is
it is not easy to exactly say how the nitrogen sites influence
apparent that the particles comprise of uniform distribution of
the catalytic activity of Au-Pd nanoparticles, it may be
Au and Pd elements with a ratio of approximately (~4:1). In
proposed that the nitrogen sites (e. g. pyridinic N which is the
major type of nitrogen based on XPS) can act as a stabilizing
and ligand by complexing to the metallic centers thus
improving their catalytic performance. Otherwise noted, the
ratio as well as the loading of Au-Pd bimetallic systems were
kept approximately the same in all catalysts in order to better
visualize the role of support. We next studied the impact of
solvent in the homocoupling reaction of chlorobenzene with
the use of Au-Pd@NMCI-2 under otherwise the same reaction
conditions. In this way, a mixture of H2O/EtOH (4:1) was shown
to be the best solvent (Table 1, entries 4-12). Both pure water
and a 1:1 mixture of H2O/i-PrOH were poor solvent for this
transformation and resulted in only 3 and 24% of coupled
product, respectively (Table 1, entries 13, 14). In addition, the
solvents such as DMF, DMF/H2O, and DMF/CH3CN were found
to be incompatible with this protocol (Table 1, entries 15-18).
This might be attributed to the fact that EtOH is a kinetically
better proton source than DMF or i-PrOH under ambient
conditions and thus it can regenerate metal nanoparticles
addition, the absence of any surface plasmon absorption peak
related to pure Au nanoparticles in DRIFT-UV spectrum of Au-
Pd@IMCI-2 clearly shows that the nanoparticles in our catalyst
are consisted of Au-Pd alloy and not a mixture of Au and Pd
species.16
One of the major feature of this protocol is its ability to
tolerate the starting aryl chlorides that contain wide range of
functional groups (Table 2, entries 1-9). All reactions were
proceeded with high efficiency and without producing
appreciable amounts of the byproduct arising from
hydrodechlorination. In particular, effective coupling of aryl
chlorides containing ortho, meta and para functionalities
showed the superior activity of the catalyst (entries 7-9).
Similarly, the Ullmann reaction of varied aryl bromides with
either electron-donating and electron-withdrawing groups
afforded the corresponding biaryls in excellent yields at room
temperature under standard conditions (entries 10-15).
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Table 2. Ullmann coupling of various aryl halides using Au-Pd@NMCI-2.a
chlorobenzene using the catalysis was initiated and before the
substrates were completely consumed (2 h, at 35%
conversion) was filtered. The filtrates were then rapidly
transferred to another reaction vessel at room temperature.
The catalyst-free solution displayed a 44% conversion even
after 10 h. While it was demonstrated that our catalyst system
is recyclable, the result of filtration test clearly points to the
fact that Au-Pd@NMCI-2 might be indeed a source of in-situ
generating a trace amount of soluble catalytic species, which
could react trough a homogeneous reaction pathway. Work
focuses on more detailed studies of the exact mechanism of
these processes to clarify the synergism between NMCI-2 and
supported Au-Pd nanoparticles is currently ongoing in our
laboratory.
Entry
R
X
Y
t (h)
Yield (%)[b]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
H
Cl
1
1
1
1.2
1.2
1.2
1.2
1.2
1.2
6
6
8
95
97
4-Me
4-OMe
4-CN
4-COCH3
4-NO2
3-NO2
3-CN
2-OH
H
4-Me
4-OMe
4-CN
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
96 (3)[c]
95 (4)[c]
90 (2)[c]
94
12
12
12
12
12
12
12
12
12
12
12
12
12
12
91
92
91
100
98
95
93
91
92
Br 0.7
Br 0.7
Br 0.7
Br 0.7
Br 0.7
Br 0.7
The financial support by IASBS research council and INSF was
greatly appreciated
Notes and references
4-NO2
4-COCH3
2-bromothiophene
3-bromothiophene
1
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1
1
72
73
aThe total loading of Au and Pd in the catalyst were 0.085 and 0.238 mmol.g-1
,
2
3
a) P. E. Fanta, Chem. Rev 1964, 64, 613.
respectively (Au/Pd ratio = 2.8/1). This ratio is more or less very close to the ratio of
Au/Pd estimated by line-scan energy dispersive X-ray spectroscopy (EDAX) of Au-Pd
alloy nanoparticles in the Au-Pd@NMCI-2 (Au/Pd ratio ≅ 4/1) (Fig. 3). Reaction
Conditions: aryl halide (0.25 mmol), catalyst (1 mol%, with respect to Pd), K2CO3 (0.5
mmol), solvent (3 mL) at room temperature. bIsolated yield. cThe number in
parenthesis refer to the yield of hydro-dechlorination product determined by GC
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4
5
6
In the same manner, the Ullmann coupling reactions of
challenging compounds containing hetero atoms such as
thiophenes were conducted, furnishing the respected biaryls in
good yields (Table 2, entry 16-17). To our knowledge, this
catalyst is the first example of heterogeneous system that
could promote the Ullman reaction of aryl chlorides and
bromides in room temperature. In comparison with Dhital et
al. who conducted the similar reaction with the Au-Pd@PVP,8
the current catalyst is also active for aryl bromides and
obviously more efficient and recyclable than similar catalytic
systems. Stability, durability and reusability of the
heterogeneous catalysts are hallmarks. Therefore, to
demonstrate the remarkable recyclability aspects of the Au-
Pd@NMCI-2, the performance of this catalyst in the recycling
reaction of Chlorobenzene was studied. After completion of
the reaction in the first run, the catalyst was recovered by
simple filtration, followed by washing with excess of EtOAc.
The recovered catalyst was then reused directly for the next
run with an average of 92% yields. After the 5th reaction cycle
(Yields: 95%, 95%, 93%, 92% and 88%), the total metals loading
were reduced to 85% of the original value in Au-Pd@NMCI-2.
However, the TEM analysis of recycled catalyst demonstrates
remarkable consistency in nanoparticles size distribution and
no conclusive evidence of agglomeration was observed (Fig.
S23). To determine whether Au-Pd@NMCI-2 is functioning in a
heterogeneous pathway, or whether it is merely a pre-catalyst
for active soluble species, a room-temperature-filtration test
was conducted. In this way, the homo-coupling reaction of
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8
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4 | J. Name., 2012, 00, 1-3
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