The First C?Cl Activation in Ullmann C?O Coupling by MOFs

Article abstract of DOI:10.1002/cctc.201801111

It was found that introduction of only 0.03 mol % Ag(I) into the framework of Cu₃(BTC)₂ ? xH₂O in maghemite anchored CuBTC activated the inert CuBTC astonishingly to exhibit unexpected high catalytic activity for C?Cl activation in coupling of chloroarenes with phenols without the use of expensive ligands. This is the first application of mixed-metal MOFs in the C?X activation. Putting reusability and activity together, a TON over 15000 was obtained which is the highest TON compared with all its precedents even better than the results by Pd catalysts.

Full text of DOI:10.1002/cctc.201801111

Accepted Article
Title: The First C-Cl Activation in Ullmann C-O Coupling by MOFs
Authors: Mehdi Sheykhan, Asieh Yahyazadeh, and Leila Ramezani
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the VoR from the journal website shown below when it is published
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To be cited as: ChemCatChem 10.1002/cctc.201801111
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The First C-Cl Activation in Ullmann C-O Coupling by MOFs
Leila Ramezani, Asieh Yahyazadeh* and Mehdi Sheykhan*[a]
Abstract: It was found that introduction of only 0.03 mol% Ag(I) into
the framework of Cu3(BTC)2.xH2O in maghemite anchored CuBTC
activated the inert CuBTC astonishingly to exhibit unexpected high
catalytic activity for C-Cl activation in coupling of chloroarenes with
phenols without use of expensive ligands. This is the first application
of mixed-metal MOFs in the C-X activation. Putting reusability and
activity together, a TON over 15000 was obtained which is the
highest TON compared with all its precedents even better than the
results by Pd catalysts.
chloroarenes must be intriguing for both industrial and academic
research because of their low-cost and good availability.[9]
There are also other drawbacks with the methods used up
to now which restrict their usage such as the necessity of the
presence of a ligand (which can be inaccessible at times)[10a]
(Scheme 1Aa) and/or limited scope of the method (those are
applicable only to electron-rich phenols (Scheme 1Ab)).[10b] In
another research N-heterocyclic carbenes were used as ligands
in the presence of the copper source. In this reaction only one
example of chlorobenzenes, which benefitted from an EWG in
its para position was used as
a coupling partner which
successfully managed to lead to the expected product, albeit in
a low yield (Scheme 1Ac).[7] It is worth noting that release of
homogeneous catalytic systems, i.e the copper source, as well
as the ligand used, which both are categorized as toxic
chemicals, into the environment is economically undesirable.
Very recently, catalytic systems which comprised of
heterogeneous copper catalysts supported on graphene,[4g] Zr-
Introduction
Diaryl ethers have emerged as important structural motifs in
numerous natural products and biologically active compounds.[1]
Thus, advancement in the synthesis of diaryl ethers has
received much attention among synthetic organic chemists.
Ullmann C-O coupling reaction of haloarenes with phenols is of
the most credible methods for the synthesis of diaryl ethers.[2] In
the original version of the foregoing method use of stoichiometric
containing MOF UiO-66[2i] and mesoporous manganese oxide
[11-12]
with a surface area of 270 m2.g-1
were introduced to
activate C-X bonds. Although these catalysts were effective for
C-I and C-Br bonds, they were inefficient or completely futile for
activation of C-Cl bonds (Scheme 1B-d-f). Therefore, a novel
Cu-catalyzed C-Cl activation which enables one to take
advantage of chloroarenes as cost-effective starting materials
and circumvents the foregoing limitations is highly demanded.
Metal-organic frameworks (MOFs), frameworks of metal nodes
and organic ligands, have recently emerged as a new category
of highly porous materials.[13] Due to the high surface area,
tunable pore size, easy functionalization and vast area of design,
copper, high temperature and a prolonged reaction time were
inevitable.[3] In recent years, several copper-
and palladium
[4]
[5]
catalyzed
couplings of phenols with haloarenes in the
presence of different ligands have been developed in order to
moderate reaction conditions and improve the efficiency of the
reaction. However, the homogeneous Pd-catalyzed coupling
methods suffer from some drawbacks such as high cost,
contamination of residual Pd in the product and tedious work-up
process.[6] Meanwhile, the Cu-catalyzed coupling reactions show
more interesting advantages especially lower cost of the catalyst
and in pharmaceutical view, higher regulatory limits for Cu than
Pd.[7] Despite all progress in Cu-catalyzed C-O coupling
reactions which stems from using bidentate ligands,[4b-c,8] there
are some remained challenges such as; coupling via
chloroarenes as the most inexpensive haloarenes as well as the
need for a low-loading catalyst/ligand system. Arylation using
MOFs have found various applications in gas storage,[14] sensor
[16]
technology,[15] drug delivery
and catalysis of organic coupling
reactions.[17] They are tunable platforms to provide diverse
characteristics because versatile metal ions as well as organic
linkers in adjustable ratios can be used in their design
depending on what application is needed.
[a]
L. Ramezani, Prof. A. Yahyazadeh, Dr. M. Sheykhan
Chemistry Department
University of Guilan
Rasht, Iran.
Fax: +981333367262
E-mail: sheykhan@guilan.ac.ir, yahyazadehlphd@yahoo.com
Supporting information for this article is given via a link at the end of
the document.
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Scheme 1. Various Cu-catalyzed approaches in C-Cl activation
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Nowadays, ever-increasing efforts have been made for merging Results and Discussion
MOFs with magnetic nanoparticles, since magnetization makes
their preparation and applications free from arduous and
inconvenient centrifugation that limited application of MOFs.[18] To
date, a few reports have been concerned with the catalytic
application of magnetic MOFs in organic reactions.[19] Also, as the
newest trend in this area, one can find the synthesis of MOFs
having two different metal ions, namely, “mixed-metal” or “mixed-
node”[20] by introducing a new metal ion into the parent MOF. It
was proved that the generated mixed-metal MOFs have superior
catalytic activities to their parent MOFs.[21] There are some
pioneering examples of improvements of redox-,[22] gas adsorption
capacity-,[23] water adsorption/stability-,[24] photocatalytic-[25] and
catalytic [26] properties of MOFs by the mixed-metal approach.
Catalysis is of most promising applications of MOFs due to the
benefits offered by the node metal centers (i.e. there is no
leaching of metal ions and they have uniform centers).[27] However,
to the best of our knowledge, there are few reports on catalytic
investigations of the mixed-metal MOFs.[26] As to the great
Catalysts Characterization
Nanoparticles of amino-functionalized maghemite were prepared
[28a]
following the previously reported paper
as an interphase
compound. According to the Zhang’s work, the MOF CuBTC was
loaded on the prepared interphase compound.[29] In another
experiment, equimolar amounts of Ni and Cu sources were used
[30]
to produce mixed-metal NiCuBTC
loaded on the magnetic
interphase compound. In addition, maghemite anchored mixed-
metal AgCuBTC nanoparticles were prepared by a post-synthetic
exchange (PSE) of Ag(I) source with the prepared maghemite
anchored
CuBTC.[27]
The prepared compounds
were
characterized by different techniques including XRD, FTIR, SEM,
EDS, ICP-AES, TGA-DTA, N2 adsorption/desorption and BET.
Figure 1 shows the XRD patterns of the synthesized compounds;
maghemite anchored CuBTC, maghemite anchored AgCuBTC
and maghemite anchored NiCuBTC. In the XRD pattern of the
prepared maghemite anchored CuBTC, diffraction patterns at 2Ɵ:
18.7ᵒ, 21.3ᵒ, 22.8ᵒ, 30.2ᵒ, 31.4ᵒ, 35.2ᵒ and 39.2ᵒ can be indexed
to a typical cubic phase of γ-Fe2O3 (JCPDS card 24-0081) in γ-
Fe2O3@SiO2 (Figure 1a). This meant that the structure of γ-Fe2O3
remain intact during the hydrothermal synthesis of MOF. The
other patterns at 2Ɵ: 6.6ᵒ, 9.5ᵒ, 11.6ᵒ and 13.4ᵒ all come from
CuBTC framework which is in agreement with the simulated XRD
of pure CuBTC (Figure 1b). The patterns of mixed-metal
maghemite anchored AgCuBTC and mixed-metal maghemite
anchored NiCuBTC are very similar to their parent (Figure 1c-d)
confirming the maintenance of the framework of CuBTC during
modification as expected from the literature.[27,24b,30-31]
demanding for
a heterogeneous/magnetic reusable copper
catalytic system that enables C-Cl activation, and superior
catalytic activity of mixed-metal MOFs, and in continuation of our
recent research on the novel catalytic methodologies in organic
transformations,[28] herein, we wish to introduce novel mixed-metal
magnetic MOF catalysts namely; maghemite anchored NiCuBTC
and maghemite anchored AgCuBTC, and their application in the
coupling of phenols with chloro-, bromo- and iodoarenes without
any need for using expensive ligands.
a
b
c
d
Figure 1. X-ray diffraction patterns of a) maghemite anchored CuBTC,b) simulated patterns by extraction of data from single crystal X-ray of pure CuBTC, c)
maghemite anchored AgCuBTC and d) maghemite anchored NiCuBTC
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1650 cm-1 are attributed to the symmetric and asymmetric
stretching of the carboxylate groups of the BTC linkers. The
bands at 807 and 1113 cm-1 can be assigned to symmetric and
asymmetric vibrations of the Si-O-Si group, respectively. The
characteristic peaks around 481 cm-1 can be ascribed to the Fe-
O bonds of γ-Fe2O3. The broad band at 2800-3700 cm-1 is due
to SiO-H moieties. The peaks at 1454 and 2937 cm-1 are related
to C-H bending and stretching modes of the propyl group,
respectively. As expected, the FT-IR spectra of synthesized
mixed-metal MOFs shows that the structure didn’t change
considerably after introducing Ag(I) and Ni(II) into the parent
MOF.
c
b
a
Porous structures of the prepared compounds are clearly shown
in Figure 3. Scanning electron microscopy images of samples
that were obtained with a Tescan Vegall instrument confirmed
that structures of the maghemite anchored MOFs are porous as
expected. The observed porosity can induce vast of prominent
features especially in catalysis. As can be seen from the Figure,
the prepared samples showed spherical shape and the surface
of the samples was not smooth.
Figure 2. FTIR spectra of the prepared maghemite anchored- a) CuBTC, b)
AgCuBTC and c) NiCuBTC.
FT-IR spectra of synthesized maghemite anchored- CuBTC,
AgCuBTC and NiCuBTC are shown in Figure 2. In the FTIR
spectrum of the parent compound prominent bands at 1387 and
a
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b
c
Figure 3. Scanning electron microscopy of maghemite anchored-(a) CuBTC, (b) AgCuBTC and (c) NiCuBTC
Elemental analysis was carried out by the energy dispersive
X-ray spectroscopy (EDS) for more details about the
structures (Figure 4). Analyses indicate the presence of Cu,
Fe, Si, C and N for magnetic interphase CuBTC; Also
quantitative investigation showed the molar ratio of Cu/N is
about 1.8 (~2).
while, for maghemite anchored NiCuBTC, EDS showed
0.16 wt.% Ni (equal to 0.027 mmol Ni/g).
Inductively Coupled Plasma (ICP) was used for more
reliable measurement of metal contents of the synthesized
materials. The ICP analysis indicates that the actual Ag
content of maghemite anchored AgCuBTC is 0.091 wt.%
(equal to 0.0085 mmol Ag/g) and the actual Ni content of
maghemite anchored NiCuBTC is 0.016 wt.% (equal to
0.0028 mmol Ni/g).
EDS also confirmed the presence of Cu, Ag, Fe, Si, C and
N
as main elements in the magnetic mixed-metal
AgCuBTC; and Cu, Ni, Fe, Si, C and N as main
components of magnetic mixed-metal NiCuBTC (Figure 4).
Quantitative elemental analysis of maghemite anchored
AgCuBTC showed 0.77 wt.% Ag (equal to 0.07 mmol Ag/g)
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a
b
c
Figure 4. Energy dispersive X-ray spectroscopy (EDS) of (a) maghemite anchored- CuBTC; (b) AgCuBTC and (c) NiCuBTC.
Ag0.15Cu2.85(BTC)2·xH2O. It meant that about 5% of Cu(II)
centers have been replaced by Ag(I). For the maghemite
anchored NiCuBTC the ratio of Cu/Ni is measured about 11/1
meaning the structural formula of Ni0.25Cu2.75(BTC)2.xH2O. Thus,
in this case the replacement of Ni(II) in Cu(II) positions is
approximately 8%. It can be concluded that entirely CuBTC-like
structures generated.
On the basis of the analyses, the structure proposed for the
parent material is depicted above (Scheme 2). In addition, for
the Ag-exchanged and Ni-exchanged materials it could propose
that they are partially mixed-metal structures containing 90%
and
84%
Cu3(BTC)2.xH2O
together
with
10%
Ag1.5Cu1.5(BTC)2.xH2O
respectively.
and
16% Ni1.5Cu1.5(BTC)2.xH2O,
Thermal stability of the synthesized MOFs was scrutinized using
thermogravimetric analysis (TGA). As shown in Figure 5, the
analysis showed two weight loss steps. The first step at around
100-150 oC is related to the physisorbed water. This followed by
the second step at about 330-380 oC which is attributed to
decomposition of MOF structures.[32]
Scheme 2. The proposed structural motifs in maghemite anchored CuBTC
ICP analysis resulted in Cu/Ag molar ratio of approximately 19/1
in the maghemite anchored AgCuBTC relating to a formula of
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a
b
TGA Curves
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
d
Maghemite anchored CuBTC
c
Maghemite anchored AgCuBTC
Maghemite anchored NiCuBTC
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700
Temperature (oC)
Figure 5. TGA-DTG analyses of maghemite anchored- a)CuBTC, b) AgCuBTC, and c) NiCuBTC, d) Comparison of TGA curves of the MOFs
Catalytic activity
Maghemite anchored
AgCuBTC
2
3
4
5
6
7
8
20
20
15
10
20
20
20
70
According to the importance of invention of a novel Cu-catalyzed
coupling of phenols with haloarenes which enables to be used
for chloroarenes without using a special ligand, the catalytic
performance of novel magnetic mixed-metal MOFs synthesized
was investigated in the Ullmann reaction. Herein, we wish to
report our results.
Maghemite anchored
NiCuBTC
62
Maghemite anchored
AgCuBTC
65
Table 1.Screening the synthesized MOFs as catalysts in the cross-coupling of
phenol with halobenzenesa
Maghemite anchored
AgCuBTC
48
Maghemite anchored
CuBTC
---
Maghemite anchored
NiCuBTC
trace
61
Loading
(mg)
Yield
(%)
entry
1
catalyst
halobenzene
Maghemite anchored
AgCuBTC
Maghemite anchored
CuBTC
20
57
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ligand and DMF as solvent at 130 oC (Table 1, entries 1-3). It
was found that Ag-exchanged material has the best catalytic
activity led to the desired diaryl ether 3 in 70% yield (entry 2).
Then, the amount of catalyst is screened (entries 4-5). All the
synthesized MOFs are tested in the cross-coupling of phenol
and bromobenzene (entries 6-8). The reaction was not
successful in the case of parent material and Ni-containing
mixed-metal MOF but in the case of maghemite anchored
AgCuBTC led to the product in 61% yield (entry 8). Surprisingly,
when the coupling of phenol with chlorobenzene was evaluated
in the presence of the synthesized materials (entries 9-11), the
maghemite anchored AgCuBTC successfully resulted in the
diphenyl ether in 43% yield.
Maghemite anchored
CuBTC
9
20
20
20
---
---
43
Maghemite anchored
NiCuBTC
10
11
Maghemite anchored
AgCuBTC
[a] Reaction conditions: Halobenzene (0.5 mmol), phenol (1 mmol), KOH
(1equiv.), acetyl acetone (10%), DMF (1.5 mL), 130 oC under N2.
In the initial study we evaluated the catalytic activity of prepared
compounds (maghemite anchored- CuBTC, AgCuBTC and
NiCuBTC) in cross-coupling of iodobenzene 1 and phenol 2 in
the presence of 1 equiv. KOH as the base, acetyl acetone as
Table 2. Screening the reaction conditions in the cross-coupling of phenol and iodobenzene.
entry
solvent
base
temperature (ᵒC)
ligand
yield (%)
1
2
3
DMF
DMF
DMF
Cs2CO3
K2CO3
KOtBu
130
130
130
L1
L1
L1
94
54
71
4
5
6
7
Toluene
DMSO
ACN
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
130
130
130
90
L1
L1
L1
L1
75
88
90
45
DMF
8
9
DMF
DMF
Cs2CO3
Cs2CO3
110
130
L1
L2
75
35
10
11
DMF
DMF
Cs2CO3
Cs2CO3
130
130
L3
L4
56
41
Reaction conditions: Iodobenzene (0.5 mmol), phenol (1 mmol), base (1 equiv.), catalyst (20 mg, 0.03%), ligand (10%), solvent (1.5 mL), at the certain
temperature under N2 quenched after 1 h.
Scheme 3. The chemical structure of ligands used.
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Various parameters such as solvent, base, ligand and
temperature were screened in the presence of maghemite
anchored AgCuBTC as most efficient catalyst in the reaction of
phenol and iodobenzene (Table 2). The chemical structure of
ligands used is provided in Scheme 3. The best results obtained
in DMF as the solvent, Cs2CO3 as the base and acetyl acetone
L1 as ligand under 130 oC.
the reaction was investigated. Phenolic partners having electron-
donating groups such as p-MeO and p-Me reacted well to the
desired diaryl ethers both for iodo- and bromobenzene (entries
3-6). Using bicyclic 2-naphthol as the reagent led to the
formation of 2-phenoxy naphthalene (entries 7-8). Despite, 2
equiv. of phenol partner used in the reaction, when bi-functional
2-methyl resorcinol reacted with both iodo- and bromobenzene
Under the optimized conditions, the cross-coupling reaction of
various phenols with iodobenzenes as well as bromobenzenes
were studied in presence of maghemite anchored AgCuBTC as
the catalyst (Table 3).
just
the
bis-diaryl
ether
product
((2-methyl-1,3-
phenylene)bis(oxy)dibenzene) was produced (entries 9-10). It is
noteworthy that bis-diaryl ethers are key motifs in widely used
antibiotic drugs such as vancomycin and teicoplanin.[33]
As shown in Table 3, Ag-exchanged material successfully
catalyzed the coupling of phenols with iodobenzenes and even
their less reactive family, bromobenzenes, in its low-loading 0.03
mol% amount (entries 1-2). The effect of various substituents on
Table 3. The synthesis of various diaryl ethers in the present of maghemite anchored AgCuBTC as catalyst a
entry
haloarene
phenol
product
time (h)
yield (%)
1
94
1
3
1
92
90
2
3
1.5
1.5
85
90
4
5
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3
93
6
1
1
95
85
7
8
9
3
93
10
11
4
7
90
74
12
12
68
13
14
15
2
3
90
90
3
95
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16
17
18
19
20
4
95
2
3
90
84
3
4
95
95
21
22
23
3
4
4
88
85
90
24
5
82
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25
26
27
12
75
66
83
12
4
[a] Reaction condition: halobenzene (0.5 mmol.), phenol (1 mmol), catalyst (20 mg, 0.03%), Cs2CO3 (1.0 equiv.), acetylacetone L1 (10 mol%) and DMF (2 mL),
130 ᵒC, N2 atmosphere.
As a more challenging case, the reaction was tested for
electron-poor p-NO2 phenol. Gratifyingly, coupling of such low-
reactive phenol with iodo- and bromobenzene in the reaction
conditions led to the desired product in good yields (entries 11-
12). In addition, when halobenzenes containing mild electron-
donating p-Me group reacted with phenol and p-MeO phenol,
corresponded products were achieved in excellent yields
(entries 13-16). More significantly, the reaction proceeds
smoothly in the case of p-MeO iodo- and bromobenzene as
strong electron-donating halobenzenes (entries 17-20). Bicyclic
1-naphthyl- and 2-naphthyl halobenzenes also coupled with
phenol in excellent yields (entries 21-24).
3-Hydroxypyridine as a heteroaromatic phenol was allowed to
react with iodo- and bromobenzene. The reactions fortunately
resulted in the formation of 3-phenoxypyridine in good yields (75
and 66 %, respectively), despite the fact that 3-hydroxypyridine
is an electron-poor phenolic heterocycle (entries 25-26).In
addition, when 3-bromopyridine as a heterocyclic haloarene
reacted with phenol, 3-phenoxypyridine obtained in 83% yield
(entry 27).
the optimized conditions. The reaction was monitored by TLC
and quenched after 15 h. Pleasingly, the reaction led to the
formation of product 3a in 88% yield (Table 4, entry 1). To
explore the reaction scope, a variety of phenols were reacted
with chlorobenzene. Firstly, the reaction of electron-rich p-MeO
and p-Me phenols were evaluated which readily gave the diaryl
ether products in 93 and 90% yield, respectively (entries 2-3).
When bicyclic 2-naphthol was used the yield dropped to 84%
(entry 4). Similar to the iodo- and bromobenzene, chlorobenzene
reacted with bi-functional 2-methyl resorcinol to produce the
desired bis-diaryl ether in 85% conversion (entry 5). Interestingly,
least-reactive electron-rich p-Me and p-MeO chlorobenzene
reacted with various phenols in excellent yields (entries 6-10).
More importantly, p-NO2 phenol was successfully coupled with
unreactive chlorobenzene led to about 81% yield, despite strong
EWG (entry 11). These experiments confirmed the applicability
of the invented method for C-O coupling of chloroarenes. In
addition, the reaction of bicyclic 2-naphthyl- and 1-naphthyl
chlorobenzene with phenol resulted in the desired products in
good yields (entries 12-13). As another electron-poor phenolic
compound, 3-hydroxypyridine was coupled with unreactive
chlorobenzene in 64% yield (entry 14).
The results encouraged us to extend the reaction to the
chloroarenes as least-reactive haloarenes. To this end, the
reaction of chlorobenzene 4 and phenol 2 was conducted under
Table 4. C-Cl Activation in cross-coupling of phenols with chloroarenes catalyzed by maghemite anchored AgCuBTC a
entry
chloroarene
phenol
product
time(h
yield(%)
TON
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1
15
14
88
93
2933 (15960)b
2
3100
3
15
90
3000
4
5
14
14
84
85
2800
2833
6
7
14
14
89
91
2966
3033
8
9
17
18
85
80
2833
2666
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10
18
24
78
81
2600
2700
11
12
13
18
20
70
60
2333
2000
14
24
64
2133
[a] Reaction condition: Chlorobenzene (0.5 mmol), phenol (1 mmol), catalyst (20 mg, 0.03 mol%), Cs2CO3 (1.0 equiv.), acetylacetone L1 (10 mol%) and DMF (2
mL), 130 ᵒC, N2 atmosphere. [b] Total turnover number after 6 consecutive runs.
It is worth mentioning that although Cu ions have the key role in
promoting this reaction but since the catalytic activity of the
catalyst was appropriately improved by introducing a very low
amount of Ag(I) (0.0085 mmol Ag/g of the structure by ICP
analysis), herein we assumed that the Cu centers adjacent to
Ag(I) ions (in 10% Ag1.5Cu1.5(BTC)2.xH2O), but not the Cu
centers surrounded by Cu (in 90% Cu3(BTC)2.xH2O), were the
actual catalyst of this reaction and this phenomenon is bound to
agreement with BJH measurement. The specific surface area
was measured 125 m2/g which was found lower than the values
reported for CuBTC (above 1000 m2/g) and equals the minimum
values of γ-Fe2O3@SiO2- filled CuBTC in literature[18b] (180 m2/g
- 850 m2/g). It seems that filling the pores of CuBTC by the
amino-functionalized maghemite sharply decreased the specific
surface area of the whole structure. In addition, it was reported
that mixed-metal ZnCuBTC, has a lower surface area relative to
its parent CuBTC due to the possible defects around inserted Zn
nodes which stop the entire 3D porosity of the structure.[34]
Kleist et al. in 2015 reported the synthesis of a bimetallic
RuCuBTC which has much lower specific surface area (about
570 m2/g) than CuBTC.[35] They proposed increased disorder of
the framework due to the higher size difference of Ru(III) and
Cu(II) ions (relative to Zn and Cu) might be the reason for the
reduced porosity of RuCuBTC. By replacing Ru(III) in Cu(II)
positions, the structure of framework does not change
fundamentally, as depicted by the authors. Simply, coordination
is complete around Ru(III) (by four carboxylate ions, one Cu(II)
and one water) with a little replacing hydroxide ion instead of
water.
happen through
a synergistic electronic effect. However,
determination of the effective Cu adjacent to Ag was somehow
impossible, so we had to find another way to gain the amount of
these ions and discriminate between two kinds of Cu ions (Cu
ions surrounded by Ag ions; and Cu ions surrounded by Cu
ions). Therefore, since the amount of effective Cu ions (in
Ag1.5Cu1.5(BTC)2.xH2O) is equal to their adjacent Ag ions, we
found that the amount of Ag ions is a suitable criterion to
measure the effective Cu ions. So, the amount of Ag was
determined by ICP and used instead of ‘effective Cu ions’ in
calculation of TON.
To uncover the reason of such an unprecedented catalytic
activity, the specific surface area and the accessibility of the
pores were analyzed using N2 adsorption-desorption (see
supporting information). BET method was used to determine the
specific surface area and BJH was used to measure the size of
pores in the structure. Analysis showed in the case of the
maghemite anchored AgCuBTC, the pore sizes are about 2.2
nm showing the mesoporous structure of the compound. N2
adsorption-desorption confirm a type IV isotherm that is in
Herein, larger sized Ag(I) is introduced into the Cu(II) positions
that has linear/square planar coordination geometry in its
complexes. Therefore, it is expectable that Ag(I) ions affect the
coordination geometry of their neighbors, i.e Cu(II), and more
large defects are generated by such huge changes in
coordination number and geometry which undoubtedly influence
the porosity of the framework (Scheme 4a). Such large defects
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in the structure around Ag(I) centers together with small pore
diameters might explain unexpected high catalytic activity of
maghemite anchored AgCuBTC in comparison with other similar
structures.
According to all reports to date, it is Cu(I) complexes (either
added manually or formed in situ from Cu(II) or metallic Cu) that
acts as the main catalytic center in Ullmann couplings.[36] It was
reported that phenoxide ion can reduce Cu(II) to Cu(I) in the
Ullmann reaction.[37] Because here there is not a macrocyclic
ligand to stabilize the Cu(III) intermediate, oxidative
addition/reductive elimination pathway of Cu(I)/Cu(III) is
refused.[38]
Meanwhile, it was reported that Halogen Atom Transfer (HAT)
governed the mechanism in the C-O and C-S coupling
reactions.[38-39]
A plausible mechanism for the Ullmann reaction catalyzed by
maghemite anchored AgCuBTC is depicted in Scheme 4b based
on inner-sphere electron transfer mechanism. It can be
proposed that the electron transfer process of Cu(I) to haloarene
leading to the formation of aryl radical (the rate-determining
step) is promoted by the synergistic effect of Ag. As it is shown
in the Scheme, deprotonation of acetylacetone ligand, generates
acetylacetonate (acac) that promotes the rate-determinig step by
chelating the Cu(I) and converting neutral Cu(I) catalyst to a
cuprate ion that is susceptible to do SET more efficient.40
a
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b
Scheme 4. (a) The proposed defects formed in the structure of maghemite anchored AgCuBTC in Ag(I) positions in approximately 10% of the whole material that
having formula of Ag1.5Cu1.5(BTC)2.xH2O based on ICP. (b) Plausible mechanism of C-Cl activation on bimetallic catalytic centers.
Leaching of catalyst decreases its lifetime. To rule out
participation of the homogeneous catalysis, the catalyst was
decanted by a magnet after 2 h in the model reaction of phenol
and chlorobenzene (18% conversion) and the supernatant was
allowed to stir for further 20 h. Analysis showed that the reaction
conversion after 22 h was about 20%. This confirms that the
reaction does not proceed by the leached homogeneous catalyst
but rather through the surface of heterogeneous catalyst. The
supernatant was also analyzed by the ICP. Neither Ag nor Cu
ions were detected in the solution that is expected from the MOF
structure of the catalyst used. Experiment showed loss of activity
does not matter at least during five reusing of the catalyst.
79.8% Average yield was obtained in the consecutive 6 runs
that is highly suitable for C-Cl activation by 0.03 mol% Ag
as catalyst.
Efficient recoverability of the catalyst to prevent the loss of
mass as well as to gain products free from contaminates of
the catalyst is of important issues in large-scale application
of heterogeneous catalysts. This will be more dominant in
the case of smaller particles e.g. nanometer-sized catalysts.
So, using magnetically responsive materials has been
introduced as a good solution for this story.[41]
To confirm that the structure of the catalyst does not
changed through the reaction, after completion of the
reaction the catalyst was removed by an external magnet
and its XRD pattern and FTIR were recorded (Figure 6). As
shown in Figure 7, the XRD pattern and FTIR of the
recovered catalyst is similar to the fresh ones, confirming
no structural change was happened during the reaction.
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Figure 6. Magnetic recovery of the catalyst from the reaction medium
A
comparison between some previously reported catalytic
systems in cross coupling of phenol and chlorobenzene is
provided in Table 5. The TON obtained by the maghemite
anchored mixed-metal MOF showed even better results of Pd
catalysts in different supports, mesoporous iron catalyst and
different copper catalysts/ligand couples.
1.2
a
b
1
0.8
0.6
0.4
0.2
0
fresh
recovered
3900
3400
2900
2400
1900
1400
900
400
Wavenumber (cm-1)
Figure 7. Comparison of fresh and recovered catalyst; a) XRD and b) FTIR
Table 5. Comparison of the magnetic mixed-metal MOF and other catalysts in cross-coupling of phenol and chloroenzene.
entry
1
catalytic system
Fe3O4@SiO2@PPh2@Pd
AT-Nano CP-Pd
Pd(dba)2
center (loading)
Pd (1.5%)
Pd (0.06%)
Pd (2%)
yield (%)
83
TON
55
reference
[42]
2
80
1333
45
[5g]
3
90
[43]
4
GO-Pd17Se15
Pd (1%)
73
73
[44]
5
Fe3O4@mesoporous PANI
CuI/Oxalamide
Fe (4.7%)
Cu (5%)
56
11.9
18
[45]
6
90
[10a]
[10b]
[46]
7
CuBr
Cu (10%)
81
8.1
8
CuI nanoparticles
CuI/Raney Ni-Al alloy
Cu2O/graphene
Cu (1.25%)
Cu/Ni (10%)
Cu (0.05%a)
Cu(10%)
47
3.6
9
32
3.2
[47]
10
11
12
13
14
5
100a
1.7
[4g]
Nano CuO
17
[48]
CuO NPs into UiO-66-NH2
AgOAc
Cu (3.5%)
Ag (100%)
Ag (0.03%)
30
8.6
[2i]
81
0.81
2933
[49]
Maghemite anchored AgCuBTC
88
current
[a] Based on Cu(I).
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10.1002/cctc.201801111
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mixed with a solution containing 0.315 g H3BTC (1.5 mmol) in 9 mL
ethanol. Magnetic NiCuBTC was synthesized by following the same
procedure.[30]
Conclusions
Preparation of maghemite anchored AgCuBTC
In conclusion, novel mixed-metal AgCuBTC and NiCuBTC
MOFs were successfully prepared. The maghemite anchored
AgCuBTC nanomaterial efficiently played as a heterogeneous
and reusable catalyst for the Ullmann C-O coupling reaction of
various kinds of phenols with iodo- and bromobenzenes. A
broad range of substrates including arenes, ethers, nitroarenes
and bicyclic arenes were tolerated. More importantly, the
catalyst showed excellent reactivity in the C-Cl activation of
chlorobenzenes in the coupling with phenols without using any
complicated, expensive ligand. The C-Cl activation proceeds
well even with electron-poor phenols. Astonishingly, applying
only 0.03 mol% Ag (based on ICP) the highest TON till now was
achieved by the invented catalyst in the coupling of phenols with
chloroarenes which exceeds 2900. Reusability of the catalyst led
to a total TON about 16000 which was gained in C-Cl activation
during 6 runs. To the best of our knowledge, thus far neither
synergistic effect of Ag in Ullmann coupling nor C-Cl activation
by MOFs has been reported. The low costs associated with Cu-
based MOF catalyst, stability/magnetic reusability and using
inexpensive/accessible acetyl acetone as ligand, make this
method more attractive for the large-scale synthesis of diaryl
ethers through C-Cl activation.
AgNO3 (0.064 g) was dissolved in the mixture of 48 mL deionized water
and 48 mL ethanol. This solution was added to the prepared magnetic
CuBTC (0.4 g) in 125 mL Teflon-lined autoclave and the autoclave was
put in an 85 ᵒC oven. The ion exchange was carried out for 1 day. The
obtained product was collected by a magnet and washed several times
with water and ethanol, and then dried overnight at 100 ᵒC.[27]
General procedure for the cross-coupling of phenols with
haloarenes
0.03 mol% (20 mg) of maghemite anchored AgCuBTC was added to the
mixture of haloarene (0.5 equiv.), phenol (1.0 equiv.), Cs2CO3 (1.0
equiv.), acetylacetone L1 (10 mol%), and DMF (2 mL) in a two-necked
flask. The reaction mixture was heated at 130 ᵒC under nitrogen
atmosphere for
a specified time. At the end, the catalyst was
magnetically recovered after addition of ethyl acetate. The cooled mixture
was partitioned between ethyl acetate and water. The organic layer was
separated, and the aqueous layer was extracted with ethyl acetate. The
combined organic layers were dried over Na2SO4, and concentrated to
yield product which was purified by silica gel chromatography to produce
the corresponding diaryl ether.
Acknowledgements
Experimental Section
This work was partially supported by research council of the
University of Guilan.
Preparation of amino-functionalized maghemite
To a solution of ferric chloride (5.0 mmol) and ferrous chloride (2.5 mmol)
in water (20 mL), 40 mL ammonia (25%) was added under vigorous
stirring. Then, to the resulted suspension, TEOS was added at 90 oC,
and the mixture stirred overnight. The resulting Fe3O4@SiO2 colloid was
separated and washed with water and EtOH. The powder obtained was
dried at 200 oC (led to 86% yield γ-Fe2O3@SiO2). To suspension of γ-
Fe2O3@SiO2 (1g) in dry toluene, 3-Aminopropyltrimethoxysilane (4.0 mL)
was added and refluxed for 10 h. Finally, the product was collected by
using an external magnet, washed with water and DCM several times,
and dried at 60 oC. The resulting material was denoted as amino-
functionalized maghemite.
Keywords: Mixed-metal MOF • Maghemite anchored AgCuBTC
• C-Cl Activation • Ullmann coupling • Diaryl ethers.
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The first application of mixed-metal MOFs in the C-X activation was reported. Unexpected catalytic activity for C-Cl
activation in coupling of chloroarenes with phenols was obtained without use of expensive ligands. The maghemite
anchored AgCuBTC (0.03 mol% Ag in Cu3(BTC)2.xH2O) showed a TON over 15000 which is the highest TON compared with
all its precedents even better than the results by Pd catalysts.
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