A porous metal-organic framework as active catalyst for multiple C-N/C-C bond formation reactions

Article abstract of DOI:10.1016/j.inoche.2015.08.010

A 3D porous metal-organic framework {[Cu(4-tba)₂](solvent)}_n (1·S) is assembled via 4-(1H-1,2,4-triazol-1-yl)benzoic acid (Htba) and Cu(II) nodes, which shows the [2 + 2] roto-translational interpenetrating network. Interestingly, 1 displays high CO₂ adsorption selectivity over CH₄/H₂/O₂/Ar/N₂ gases, and acts an efficient catalyst precursor in some C-N/C-C bond formation reactions, including Chan-Lam coupling reaction of phenylboronic acid with imidazole, Suzuki-Miyoura coupling reaction of phenylboronic acids with aryl halides, and Heck coupling reaction of styrene with aryl halides.

Full text of DOI:10.1016/j.inoche.2015.08.010

Inorganic Chemistry Communications 61 (2015) 13–15
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Short communication
A porous metal–organic framework as active catalyst for multiple
C–N/C–C bond formation reactions
Bin Wang, Pei Yang, Zhi-Wei Ge, Cheng-Peng Li ⁎
College of Chemistry, Tianjin Key Laboratory of Structure and Performance for Functional Molecules, MOE Key Laboratory of Inorganic–Organic Hybrid Functional Material Chemistry,
Tianjin Normal University, Tianjin 300387, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 June 2015
Received in revised form 12 August 2015
Accepted 14 August 2015
Available online 20 August 2015
A 3D porous metal–organic framework {[Cu(4-tba) ](solvent)}n (1⋅S) is assembled via 4-(1H-1,2,4-triazol-1-
yl)benzoic acid (Htba) and Cu(II) nodes, which shows the [2 + 2] roto-translational interpenetrating network.
Interestingly, 1 displays high CO adsorption selectivity over CH /H /O /Ar/N gases, and acts an efficient catalyst
2 4 2 2 2
precursor in some C–N/C–C bond formation reactions, including Chan–Lam coupling reaction of phenylboronic
acid with imidazole, Suzuki–Miyoura coupling reaction of phenylboronic acids with aryl halides, and Heck
coupling reaction of styrene with aryl halides.
2
Keywords:
Cu(II) metal–organic framework
©
2015 Elsevier B.V. All rights reserved.
4-(1H-1,2,4-triazol-1-yl)benzoic acid
C–N/C–C bond formation reactions
Catalysis
As a new family of functional materials, metal–organic frameworks
In our previous work [14], we successfully assembled a unique 3D
MOF material, {[Cu(4-tba) ](solvent)} (1⋅S), with the [2 + 2] roto-
(
MOFs) have attracted continuous interests owing to their structural di-
versity and tailorability, as well as high porosity and large surface area
1–3]. MOFs show unique advantages and promises for a wide range
2
n
translational system comprising two sets of normal 2-fold interpen-
etrating dia framework (Fig. 1 left) [15]. Despite interpenetration, the
intersecting 1D open channels are still observed along the crystallo-
[
of applications, such as in gas storage, separation, heterogeneous catal-
ysis, drug delivery, and magnetism [4–7]. In particular, compared with
traditional porous materials (zeolite, active carbon, etc.), many distin-
guished prototypes of MOFs represent multifunctional platforms of
high performance in combination of cooperative functions, such as
MOF-5, ZIFs, and HKUST-1 [8–10]. However, a significantly limited
number of multifunctional MOFs are being reported comparing the
vast number of MOF-related publications each year. Generally, those
MOFs with fine-tuned porosity can be deliberately designed by
selecting geometrically compatible nodes (metals or metal clusters)
and linkers (organic ligands), showing their inherent application in
gas adsorption and heterogeneous catalysis. On one hand, MOFs adsorb
gas through proper pore sizes or coordinatively unsaturated metal sites
to reach stronger physisorption energy. On the other hand, active metal
centers or functionalized organic linkers in MOFs lead to good candidate
of heterogeneous catalysts [11–13]. C–N/C–N bond formation is one of
the most important catalytic reactions in synthetic chemistry, which
can facilitate the creation of more complex molecules from simple pre-
cursors. Heterogeneous catalysts present vast advantages in view of
atom-economy, environmental benignity, and facile separation and re-
cyclability. Thus, it is feasible to integrate multiple functions of selective
gas adsorption and catalytic power within one single MOF.
2
graphic b axis, with pore sizes of ca. 3.0 × 6.0 Å (considering van der
Waals radii of atoms). It is significant that, the desolvated MOF 1
shows high CO
(with IAST selectivity of 41–68 at 273 K, Fig. 1 right). Remarkably, by
using a critical point dryer, the CO molecules can be well sealed in
the 1D channels of 1 for single-crystal X-ray analysis, which are found
2 4 2 2 2
adsorption selectivity over CH /H /O /Ar/N gases
2
δ+
δ−
stabilized by the C –H⋯O interaction between the host framework
δ− δ+
and CO
2
, as well as the quadrupole–quadrupole (CO
molecules.
2
⋯
2
CO ) interac-
tions between the CO
2
Since the homogeneous copper catalysts were proved to be the
efficient catalyst on some C–N/C–C bond formation reactions, the avail-
ability of the copper sites in 1 prompted us to examine its catalytic effi-
ciency. Because C–N bond formation reactions are significant focus of
organic synthesis, and Cu(II) complexes are active catalysts in these
reactions [16–18], the Chan–Lam coupling reaction of phenylboronic
acid with imidazole was carried out to evaluate the catalytic activity of
1. As shown in Table 1, coupling reactions were carried out by using
phenylboronic acid and imidazole as the prototypical substrate combi-
nation. The results show that the catalytic activity of 1 is highly depen-
dent on solvent and temperature. Among the several factors examined,
treatment of phenylboronic acid and imidazole in methanol at 40 °C for
2
4 h in the presence of 1 lead to the formation of N-phenylimidazole in
good yield (see Table 1, entry 2). For comparison, Cu(OAc) was used as
control catalysts to conduct the catalytic experiment. As shown in
⁎
Corresponding author.
2
E-mail address: tjnulicp@163.com (C.-P. Li).
http://dx.doi.org/10.1016/j.inoche.2015.08.010
387-7003/© 2015 Elsevier B.V. All rights reserved.
1

14
B. Wang et al. / Inorganic Chemistry Communications 61 (2015) 13–15
2 4 2 2 2
Fig. 1. (left) Perspective view of the 2-fold interpenetrating dia framework of 1. (right) Gas adsorption isotherms of 1 for CO /CH /H /O /Ar/N gases.
Table 1, its catalytic efficiency is largely inferior to that of 1 under iden-
tical conditions (entry 3). This result demonstrates that the very high
catalytic activity of 1 on Chan–Lam coupling reaction should be due to
its porous open framework. Of great interest, catalyst 1 in the reaction
can be recycled by simple centrifugation from the reaction mixture,
which at least was reused in six runs (Table S1). PXRD patterns for the
recovered material reveal the structural integrity of the catalyst during
the catalytic reaction (Fig. 2).
To further demonstrate the efficiency and versatility of catalyst 1, the
C–C bond formation reaction of Suzuki–Miyaura cross-coupling
was also performed (see Scheme 1a). Treatments of phenylboronic
acids with aryl halides with catalyst 1 gave normal product yield
under pertinent reaction condition (see Table S2). Regarding the reac-
tion of phenylboronic acids with bromobenzene, delicate choices of
Fig. 2. Comparison of PXRD patterns for 1 and 1 catalyst after sixth cycle of cross-coupling
reaction.
2 3
solvent (MeOH), base (Na CO ), and reaction temperature (40 °C)
provided the most effective catalytic activity (product yield: 89%). On
the other hand, the coupling reaction of phenylboronic acids with
iodobenzene could be achieved in excellent yield (88%) under room
temperature in MeOH. Whereas for the Heck coupling reaction of sty-
rene with bromobenzene or iodobenzene (see Scheme 1b), the moder-
ate yields of coupling products can be achieved with the optimized
reaction conditions (see Table S3).
shows top-rank CO2 adsorption selectivity over a variety of gases,
but also efficiently prompts Chan–Lam coupling reaction, Suzuki–
Miyoura coupling reaction, and Heck coupling reaction, which sug-
gests that such porous MOF material provides a facile choice as the
potential high-efficiency catalysts.
In conclusion, we have assembled a porous 3D MOF {[Cu(4-
tba)
2
](solvent)}
n
(1⋅S) by 4-(1H-1,2,4-triazol-1-yl)benzoic acid
Acknowledgments
(
Htba) and Cu(II) nodes. Upon desolvation, compound 1 not only
This work was financially supported by the National Natural
Science Foundation of China (No. 21101116 and 21102101), Innova-
tion Foundation of Tianjin Normal University (No. 52XC1402), and
Tianjin Normal University.
Table 1
Screening the reaction conditions for the Chan–Lam coupling reaction of phenylboronic
acid with imidazole with compound 1 as catalyst.
Entrya
Solvent
Base
Temp (°C)
Yield (%)b
1
2
3
4
5
6
7
8
9
1
1
1
1
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
–
–
–
–
–
–
Na
–
–
–
r.t.
40
40
40
60
80
40
40
40
40
40
40
40
81
98
66
c
d
94
89
68
76
67
39
34
47
25
34
2 3
CO
CHCl
CH Cl
DMF
3
0
1
2
3
2
2
–
–
–
H
2
O
CH
3
CN
a
Phenylboronic acid (1.2 mmol), imidazole (1.0 mmol) and solid 1 (0.01 mmol) were
stirred for 24 h.
b
Isolated yields of homogenous samples after chromatographic purification.
Catalyzed by Cu(OAc) .
2
The sixth cycle.
Scheme 1. Catalytic behaviors of solid 1 in (a) Suzuki–Miyoura coupling reaction of
phenylboronic acids with aryl halides, and (b) Heck coupling reaction of styrene with
aryl halides.
c
d

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