Palladium nanoparticles supported on a nickel pyrazolate metal organic framework as a catalyst for Suzuki and carbonylative Suzuki couplings

Article abstract of DOI:10.1039/c6dt02242a

Methanolic reduction of [PdCl₂(CH₃CN)₂] on a [Ni(2,5-di(1H-pyrazol-4-yl)benzenesulfonate)₂] metal organic framework gives rise to Pd²⁺/Pd⁰ nanocomposites with Suzuki and carbonylative Suzuki heterogeneous catalytic activities.

Full text of DOI:10.1039/c6dt02242a

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Received 00th January
20xx,
Palladium nanoparticles supported on a nickel pyrazolate metal
organic framework as catalyst for Suzuki and carbonylative Suzuki
couplings
A. W. Augustyniaka, W. Zawartkaa , J. A. R. Navarrob* and A. M. Trzeciaka*
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
ºC, as proven by X-ray powder diffraction.24 Other MOFs,
Methanolic reduction of [PdCl2(CH3CN)2] on [Ni(2,5-di(1H-pyrazol-
4-yl)benzenesulfonate)] metal organic framework gives rise to
Pd2+/Pd0 nanocomposites with Suzuki and carbonylative Suzuki
heterogeneous catalytic activities.
mainly carboxylate systems of the MIL family, were used as
supports for palladium catalysts of the Suzuki-Miyaura
coupling.25-36 Thus, Pd NPs immobilized on MIL-101(Cr) formed
efficient heterogeneous catalyst of the water-mediated
coupling of aryl chlorides at 80 °
C with TBAB additive.25
Palladium supported on amino-functionalized MIL-53(Al)NH2
catalyzed the Suzuki-Miyaura coupling with high activity and
recyclability.26 The effect of palladium loading on the catalytic
performance was studied for Pd NPs immobilized on MIL-
101(Cr)NH2 and the best activity and recyclability were
obtained for 8 wt% of Pd.27 Further studies with this catalyst
indicated that the kind of the base used in the catalytic
reaction has a decisive influence on the stability of the MOF
structure.28 Noteworthy, the MOF catalyst was degraded at
the presence of carbonates, while it remained crystalline with
fluorides.28 Decomposition of Pd-MIL-101(Cr) and leaching of
the active phase were observed.29 A similar catalyst, Pd-MIL-
101, containing well dispersed Pd NPs obtained by a “double
solvent” method acted as the heterogeneous and recyclable
catalyst of bromo- and iodobenzene coupling.30
One of the major challenges in modern catalysis is efficient
separation of the metal catalyst from organic products.1-7 This
is particularly important in palladium catalysed cross-coupling
reactions leading to the products which can be utilized in
pharmaceutical industry. For example, Suzuki-Miyuara
reaction presents an attractive pathway to substituted biaryls,
precursors of anti-inflammatory drugs.8-12 The carbonylative
Suzuki-Miyaura coupling offers easy access to diarylated
ketones used in UV-screens, dyes, agrochemicals and
pharmaceuticals.13-15
Application of heterogeneous catalysts to these reactions
enables to improve the separation step and to minimize
palladium content in the reaction products. In this regard,
metalorganic frameworks, MOFs, have attracted an increasing
attention as potential supports for palladium.16-22
Advantageously, MOFs possess high surface areas with well-
defined pores of modulable shapes. These highly porous
materials can be easily modified by several functional groups
facilitating bonding of a variety of metal ions and metal
nanoparticles (NPs).16-22
Pd-NH2-MIL-125 catalyzed the Suzuki-Miyaura coupling of aryl
chlorides at 100 °
C in methanol with a yield of ca. 80%.31 It was
also successfully recycled and used in four subsequent runs.
The catalyst Pd-UiO-66, obtained by the microwave-assisted
method, exhibited high catalytic activity in the Suzuki-Miyaura
coupling of aryl bromides and chlorides at 30
dispersed on the surface of DUT-67 micro-crystals were used
for coupling of iodobenzene at 70
C in water-ethanol.33
°
C.32 Pd NPs
One of the first reports dealing with application of MOF in the
Suzuki-Miyaura reaction was the palladium(II) based system
[Pd(2-pymo)2]n (2-pymo = 2-hydroxypyrimidinolate)23,24 being
able to stand unaltered under the reaction conditions, at 150
°
Interestingly, Pd(II) complex with 2,2,-bypirydine-5,5,-
dicarboxylate linker incorporated into MOF (UiO-67) showed
remarkably higher activity than the homogeneous Pd
counterparts.34
Noteworthy, while the Pd-MOF catalysts found application in
the Suzuki-Miyaura coupling, this work represents the first
example of their use under CO atmosphere. To the best of our
knowledge, the only example till now was reported for the
Sonogashira carbonylative coupling with Pd(II)-Zr-MOF-BIPY
system.37
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Most of the studies on the Pd-MOF systems in Suzuki-Miyaura nanocrystals compared to traditional reducing agents (Fig. 1D).
reaction are based on carboxylate MOFs of the MIL/UiO Moreover, analysis of X-ray photoelectron spectroscopy (XPS)
families. In this regard, testing of other MOFs materials of high spectra confirmed the presence of both Pd(0) (334.0, 339.3 eV)
chemical stability as the supports for palladium could be and Pd2+ (336.9, 342.6 eV) in a 15:85 ratio. On the other hand,
beneficial. To this aim, MOFs containing strong donor azolate XPS lines of Pd2+ are shifted towards lower binding energies, as
ligands like imidazolates or pyrazolates could be considered.38, compared to pristine [PdCl2(CH3CN)2] indicating a change of
39 Following this idea, we decided to choose pyrazolato based palladium environment. In fact, FT-IR analysis exhibited that
MOF containing sulfonate functionalities, [Ni(H2BDP-SO3)2], for the characteristic absorbance band for a C≡N bond at ca.
palladium immobilization.40 We expected that the system, 2340 cm−1 was absent (Fig. S4), suggesting that CH3CN is
built from the assembly of Ni(II) cations and 2,5-di(1H-pyrazol- removed from coordination sphere of palladium during
4-yl)benzenesulfonate linkers might be a suitable MOF support immobilization. The FT-IR region 600–100 cm−1 was also
for Pd2+ and Pd NPs since both palladium forms are present in studied. There is a strong absorption band centred at 352 cm−1
the Suzuki-Miyaura catalytic cycle.4, 6, 7
which can unequivocally be assigned to ν(Pd–Cl).44
Additionally, EDX analysis shows a ca. 1:1 atomic ratio of Pd:Cl.
These results suggests that PdCl+ cations might be anchored to
the outer surface of the Pd NPs and further stabilized in the
[Ni(H2BDP-SO3)2] structure by interactions with sulfonate
oxygen atoms of the organic linkers. Indeed, two additional
bands centred at 420 and 455 cm−1 might be assigned to ν(Pd–
O), supporting the plausible interaction of the core shell NPs
with the sulfonate groups of the organic spacers. Alternatively,
additional stabilizing interactions between Pd-Cl cations and
NH groups of pyrazole could also be considered.
The low-angle XPRD pattern of the as-prepared [Ni(H2BDP-
SO3)2] (Fig. 2 top) is in agreement with the simulated pattern
reported by Colombo et al.40 In addition, the structure of
[Ni(H2BDP-SO3)2] remains intact after palladium uploading and
no changes in the XPRD patterns were detected, which
supports that [Ni(H2BDP-SO3)2] was chemically stable during
the palladium reducing process and ulterior catalytic reaction.
We have also evaluated the effect of palladium incorporation
in the [Ni(H2BDP-SO3)2] system by means of N2 adsorption
isotherms at 77 K (see Fig. 2 (down), and Table 1). Noteworthy,
the porous structure in Pd@[Ni(H2BDP-SO3)2] is still highly
accessible, although a diminution of aprox. 45 % in the specific
surface area (SA) and pore volume are noticed. On the other
hand, the TGA analysis reveals that the [Ni(H2BDP-SO3)2]
Scheme 1. Green preparation of Pd@[Ni(H2BDP-SO3)2] catalyst.
Noteworthy, the impregnation at room temperature of the
[Ni(H2BDP-SO3)2] system with a methanolic solution of
[PdCI2(CH3CN)2] gave rise to the straightforward formation of
Pd@[Ni(H2BDP-SO3)2] containing both Pd2+ ions and Pd NPs
embedded in the MOF material. The uploaded amount of Pd,
as determined by induced coupling plasma (ICP) analysis, is up
to 5.6 wt %. TEM images indicated that the Pd NPs are
homogeneously distributed on the MOF microparticles (Fig. 1).
(for details see ESI†). Remarkably, MeOH acted as both a
solvent and a reductant.41 Indeed, we have observed a quick
change of the colour of the [PdCI2(CH3CN)2] solution from
yellow to dark brown, while the MOF micropowder changed
from yellow to dark red, indicating that the palladium
precursor was reduced to Pd NPs. The as-prepared Pd NPs
were characterized by transmission electron microscopy (TEM)
(see Fig. 1C-D) and elemental mapping images (Fig. 1E). The
corresponding electron diffraction pattern (SAED) for the
selected area is shown in Fig. 1B demonstrating that Pd NPs
are crystalline. In the SAED pattern we observe the diffraction
rings matched with (111), (200), (220), and (311)
crystallographic planes of Pd nanocrystals, respectively. The
TEM images also established that the palladium nanocrystals
are in the 4–8 nm size distribution (Fig. 1A). It should also be
noted that Pd NPs exhibit very-well defined geometrical
shapes even though the synthesis conditions were very mild.
This is unusual since the production of Pd NPs typically
involves the addition of a reducing agent (i.e. N2H4, NaBH4, H2)
leading to less defined shapes in most cases.42-43 In this regard,
the use of methanol as reducing agent, under the reported
mild conditions, seems to be advantageous since it leads to a
higher control over the shape and size of palladium
material possesses a notable thermal stability of up 350
(Fig. S1).
°C
Table 1 N2 sorption isotherm data of [Ni(H2BDP-SO3)2] and
Pd@[Ni(H2BDP-SO3)2]
Samplea
SBET(m2g-1)
Vpore (cm3g-
1
)
[Ni(H2BDP-SO3)2]
1082(2)
583(2)
246(0)
1.11
0.58
0.26
Pd@[Ni(H2BDP-SO3)2]
Pd@[Ni(H2BDP-SO3)2]b
a Desolvated under Reduced Pressure at 180
°
C for 12 h.
b
Reused Pd@[Ni(H2BDP-SO3)2]
Once the physicochemical features of the Pd@[Ni(H2BDP-
SO3)2] composites were established we proceed to evaluate
their plausible catalytic properties.
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Fig. 1 A) histogram of Pd particles size, B) SAED pattern of Pd nanocrystals, C-D) TEM images of Pd NPs with different shapes found in
Pd@[Ni(H2BDP-SO3)2] nanocrystals, E) EDX elemental mappings of Pd@[Ni(H2BDP-SO3)2.
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Table
2
Pd@[Ni(H2BDP-SO3)2] catalyzed Suzuki-Miyaura
coupling showing the effect of substituents in aryl halides.a
Entry
1
Aryl halide
Yield (%)a*
85
Yield (%)a**
99
2
3
58
75
94
76
88
69
4
5
91
98
6
7
91
-
97
24***
aReaction conditions: aryl halide (1 mmol), phenylboronic acid
(1.5 mmol), K2CO3 (1.5 mmol), iPrOH (2.5 mL), H2O (2.5 mL),
Fig.2 A) XPRD patterns of [Ni(H2BDP-SO3)2] as synthesized
(black), Pd@[Ni(H2BDP-SO3)2] (red), 4-use catalytic cycle (blue),
simulated (grey)40; B) N2 adsorption isotherms measured at
77 K for [Ni(H2BDP-SO3)2] (red), Pd@[Ni(H2BDP-SO3)2] (blue)
and reused Pd@[Ni(H2BDP-SO3)2] (grey). Filled and empty
symbols represent adsorption and desorption, respectively.
Pd@[Ni(H2BDP-SO3)2] (0.5 mol% of Pd), *8h at 25
C,***20h at 100
C.
°
C, **4h at 60
°
°
The reaction did not proceed either in the absence of a
catalyst (Table S1, entry 1) or in the presence of pristine
[Ni(H2BDP-SO3)2] (Table S1, entry 2), which confirms the
catalytic activity of Pd@[Ni(H2BDP-SO3)2].
Pd@[Ni(H2BDP-SO3)2] was active, in 1:1 2-propanol and water
solvent mixtures at 25 C forming up to 91 % of the coupling
product. In these conditions (25 C) reactions of different aryl
Indeed,
The C-C coupling reactions between aryl halides (-Br, -Cl) and
phenylboronic acid were selected as model reactions for
testing the catalytic activity of Pd@[Ni(H2BDP-SO3)2]. With this
aim, the reaction parameters were optimized using 4-
bromoanisole as a screening substrate, and the results are
summarized in Table 2 and Table S1 (see ESI.†).
°
°
halides with phenylboronic acid showed conversions from 30
% for 2-chlorotoluene to 91 % for 4-bromoanisole and 4-
bromotoluene. The highest conversions, up to 97-99 %, were
obtained for 2-bromotoluene, 4-bromotoluene and 4-
bromoanisole at 60 °C after 4 h reaction (Table 2). Kinetic
profiles of Suzuki-Miyaura reactions of 4-bromoanisole,
illustrating a positive effect of a higher temperature on the
reaction course, are shown on Fig. 3. By contrast, in the
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reaction of 2-chlorotoluene at 100 oC only 24 % of the (1.2 mmol), K2CO3 (1.5 mmol), Pd@[Ni(H2BDP-SO3)2]. (0.5 mol
corresponding coupling product was formed as a result of % of Pd) H2O/iPrOH (5 mL), 60
C, 4 h.
°
higher strength of C-Cl bond compared to C-Br (Table 2). The Furthermore, TEM images of the recovered catalyst indicate
recyclability of Pd@[Ni(H2BDP-SO3)2] catalyst was tested over that the Pd NPs are homogeneously dispersed even after the
Suzuki-Miyaura reaction (Fig. 4). After each run, the solid catalytic reactions (Fig 5 a,b).
catalyst was easily collected by centrifugation, washed with
MeOH, and used for a further run up to four consecutive runs
under the same conditions.
100
90
A
80
70
60
50
40
25 °C
30
60 °C
20
10
0
B
0
1
2
3
4
5
6
7
8
9
Time (h)
Fig.
5
Pd@[Ni(H2BDP-SO3)2] catalyst after reaction.
A) Histogram of Pd NPs; B) TEM images of
Fig. 3 Time conversion plot for the Suzuki-Miyaura coupling of
4-bromoanisole with phenylboronic acid.
Moreover, agglomeration of Pd NPs was not appreciated but
some decrease of an average size was noted. The morphology
was also changed and Pd NPs became more round. These
observations support the suggestion that Pd NPs do actively
participate in the catalytic reaction taking place on their
surface. The Pd amount found in the reused Pd@[Ni(H2BDP-
SO3)2], as determined by ICP analysis, was 5.3 wt %. The
specific area determined by N2 adsorption decreased to 246
m2g-1, probably as a result of incorporation of organic products
into pores (Table 1). As the leaching of palladium was not
significant, it can be assumed that decrease of the catalytic
activity during recycling is caused by lower availability of active
palladium centres blocked by organic products.
The results show a relatively small conversion decrease, from
98 to 80 %, highlighting the good stability of the
Pd@[Ni(H2BDP-SO3)2] catalyst. After the 4th use, the catalyst
was examined by XPRD (Fig. 2A) and TEM (Fig. S3) showing a
certain degree of MOF crystallinity loss. Noteworthy, the
amount of Pd(0) increased from the original 15 % to 39 %
similarly to other heterogenized palladium systems in Suzuki-
Miyaura reactions45-47 (Fig S2). To estimate the role of soluble
palladium forms leached from the solid support, in the
catalytic process, the activity of the liquid phase was
investigated. However, the filtrate obtained after separation
of the Pd@[Ni(H2BDP-SO3)2] catalyst showed no activity (Table
Once we proved that the Pd@[Ni(H2BDP-SO3)2] system was
catalytically active in the Suzuki–Miyaura coupling, we decided
to test it in a more demanding reaction, like carbonylative
Suzuki-Miyaura coupling. It was interesting to check whether
the catalytic activity can be switched from standard coupling
to the carbonylative coupling by a simple change of the
reaction conditions. The carbonylative coupling of iodoanisole
with phenylboronic acid was selected as the model reaction,
and the results are summarized in Table 3 and Table S2 (see
ESI). Anisole, toluene and DMF were chosen as solvents, while
K2CO3, KHCO3 and KOH were selected as bases. At 1 bar of CO
only 21% of diarylketone was formed, however, its yield
increased to 51% after pressure increase to 5 bar. At 10 bar of
CO diarylketone was obtained as the only product.
Consequently, this pressure was used in further experiments
S1 entry 7)
liquid phase was 0.035 ppm evidencing insignificant palladium
leaching. Consequently, it can be proposed the
. According to ICP analysis, palladium content in the
heterogeneous reaction pathway as the main one, with
catalytic activity taking place on the Pd NPs surface.
98
97
100
80
60
40
20
0
87
80
performed in
anisole as solvent with
1 mol % of
1
2
3
4
Pd@[Ni(H2BDP-SO3)2]. Reactions of different aryliodides with
phenylboronic acid show conversions from 33 % to 71 % (Table
3). The highest conversion, up to 71 %, was obtained for 3-
No. of Cycle
Fig. 4 Recycling catalytic test of Pd@[Ni(H2BDP-SO3)2]. Reaction
conditions: 4-bromoanisole (1 mmol), phenylboronic acid
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**
C .* CO balloon, CO (5
iodoanisole. Typically, the correlation between conversion and solvent (anisole) 5 mL, CO (10 bar) at 105
position of the substituent in the aryl ring is observed.
bar),*** CO (10 bar)
Table 3 Pd@[Ni(H2BDP-SO3)2] catalyzed carbonylative Suzuki– b 0.5 mol% of Pd at 105
Miyaura coupling of aryl iodides with arylboronic acid.a
°
°C
The much higher reactivity of 3-iodoanisole, as compared to 4-
iodoanisole and 2-iodoanisole, may be attributed to the
reduced pore availability of Pd@[Ni(H2BDP-SO3)2] for 3-
iodoanisole molecule facilitating the reaction on the surface of
Pd@[Ni(H2BDP-SO3)2]. Reactions with substituted boronic
acids showed conversions ranging from 59% for 3,5-
dimethoxyboronic acid to 35 % for 4-acetylphenylboronic
acid. Interestingly the best yield was observed for bulky 3,5-
dimethoxyboronic acid. In all reactions at 10 bar of CO
Entry
1
Aryl
halides
Boronic acid
Conv.
(%)
A(%) B(%)
Pd@[Ni(H2BDP-SO3)2] catalyst gave exceptionally 100
selectivity.
%
80*,b
21
51
50
58
59
15
0
Conclusions
A new green synthetic method leading to Pd@[Ni(H2BDP-
SO3)2] containing Pd2+ and Pd NPs in a Ni(II) pyrazolate MOF
has been presented. Noteworthy, the obtained crystalline Pd
NPs supported on the [Ni(H2BDP-SO3)2] MOF material can be
regarded as a highly active heterogeneous catalyst for the
Suzuki–Miyaura coupling in an environmentally friendly
mixture of solvents (2-propanol/water). The catalyst can be
recovered and reused for at least four runs without a
significant loss in its activity. At 25oC our catalyst converted 4-
bromotoluene and 4-bromoanisole in 91% to the coupling
products. As far as we know, only for Zn-free MOF-5-NPC-Pd
catalyst very good results were obtained at 25oC [36]. In other
MOF systems higher temperature (40-200oC) was applied. The
catalytic activity reported by us at 60oC with 0.5 mol% of Pd is
similar to that found for Pd/MIL-53-NH2 [30] and Pd-MCM-41
[51]. On the other hand, higher activity in Suzuki-Miyaura
reaction was showed by Pd/MOF which produced 92% of
coupling product at 40oC in 0.5 h [35]. In the same conditions
this catalyst converted other bromoarenes to appropriate
products in 87-95% [35].
2
66**,b
3
4
50***,b
58
0
5
6
33
54
33
54
0
0
7
8
9
The activity of the Pd@[Ni(H2BDP-SO3)2] catalyst can be easily
switched to carbonylative coupling by introduction of CO and
the excellent selectivity to diarylketone was noted at 10 bar of
CO. According to the best of our knowledge we reported for
the first time results of carbonylative coupling with the MOF
supported Pd catalyst. At 1 bar of CO our catalyst produced
21% of ketone, showing lower activity than Pd nanoparticles
supported on dopamine-functionalized magnetite [49].
Palladium nanoparticles immobilized onto SILLP formed
diarylketones with the yield 60-87% in 12 h at 30 atm of CO at
120oC [50]. These conditions are significantly harsher than
used by us. The Pd catalyst supported on amino-modified silica
microspheres used at 5 atm of CO in an amount 0.05 mol%
gave better results, up to 90% conversion, in 5h [47].
71
59
71
59
0
0
53
35
53
35
0
0
10
Further work on exploring new catalytic reactions with such
Pd@MOF system is currently underway.
aReaction conditions: aryl halide (1 mmol), phenylboronic acid
(1.2 mmol), Pd@[Ni(H2BDP-SO3)2] (1.0 mol% of Pd), K2CO3 (3 mmol),
Acknowledgment
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35 L. Zhang, Z. Su, F. Jiang, Y. Zhou, W. Xu, Tetrahedron, 2013,
69, 9237.
36 W. Dong, L. Zhang, Ch. Wang, Ch. Feng, N. Shang, S. Gao and
Ch. Wang. RSC Adv. 2016, 6, 37118.
37 C. Bai, S. Jian, X. Yao and Y. Li. Catal. Sci. Technol. 2014, 4,
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(NCN, Poland) with grant 2014/15/B/ST5/02101 (A.A., W.Z., A.M.T.),
Spanish MINECO (CTQ2014-53486-R) and EU FEDER Funding (JARN).
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38 V. Colombo, S. Galli, H.J. Choi, G.D. Han, A. Maspero,
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DOI: 10.1039/C6DT02242A