Ru(III) complex anchored onto amino-functionalized MIL-101(Cr) framework via post-synthetic modification: an efficient heterogeneous catalyst for ring opening of epoxides

Article abstract of DOI:10.1007/s13738-017-1277-8

In this work, the metallo Schiff base-functionalized metal–organic framework was prepared by post-synthetic method and used as an electron-deficient catalyst for the alcoholysis of epoxides. In this manner, the aminated MIL-101 was modified with 2-pyridine carboxaldehyde and then the prepared Schiff base reacted with RuCl₃. This new catalyst, MIL-101–NH₂–PC–Ru, was characterized by Fourier transform infrared, UV–Vis spectroscopic techniques, X-ray diffraction, BET, inductively coupled plasma atomic emission spectroscopy and field-emission scanning electron microscopy. In the presence of this heterogeneous catalyst, ring opening of epoxides was performed under mild condition to show the significant ability and successful applications of Lewis acid containing catalysts in corporation with metal–organic frameworks. The reusability of the catalyst was also investigated. No noticeable decrease in the catalytic activity was found after four consecutive times.

Full text of DOI:10.1007/s13738-017-1277-8

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-017-1277-8
ORIGINAL PAPER
Ru(III) complex anchored onto amino‑functionalized MIL‑101(Cr)
framework via post‑synthetic modifcation: an efcient heterogeneous
catalyst for ring opening of epoxides
Aneseh Khalatbari Jafari1 · Reihaneh Kardanpour1 · Shahram Tangestaninejad1 · Valiollah Mirkhani1 ·
Majid Moghadam1 · Iraj Mohammadpoor‑Baltork1 · Farnaz Zadehahmadi2
Received: 3 September 2017 / Accepted: 13 December 2017
© Iranian Chemical Society 2017
Abstract
In this work, the metallo Schif base-functionalized metal–organic framework was prepared by post-synthetic method and
used as an electron-defcient catalyst for the alcoholysis of epoxides. In this manner, the aminated MIL-101 was modifed
with 2-pyridine carboxaldehyde and then the prepared Schif base reacted with RuCl3. This new catalyst, MIL-101–NH2–PC–
Ru, was characterized by Fourier transform infrared, UV–Vis spectroscopic techniques, X-ray difraction, BET, inductively
coupled plasma atomic emission spectroscopy and feld-emission scanning electron microscopy. In the presence of this
heterogeneous catalyst, ring opening of epoxides was performed under mild condition to show the signifcant ability and
successful applications of Lewis acid containing catalysts in corporation with metal–organic frameworks. The reusability
of the catalyst was also investigated. No noticeable decrease in the catalytic activity was found after four consecutive times.
Keywords Metal–organic framework · Heterogeneous catalyst · Post-synthetic modifcation · Ring opening · Alcoholysis ·
Epoxides
Introduction
acidity, long reaction times and inconvenient handling. As a
result, the introduction of new methods for the ring opening
of epoxides, which work under mild reaction conditions, is
necessary in synthetic organic chemistry.
Epoxide ring opening represents one of the most funda-
mentally important reactions in organic synthesis [1]. High
regio- and stereoselectivity and specificity reactions of
epoxides frequently constitute crucial process in the trans-
formation of aliphatic compounds [2]. Epoxide ring-opening
reactions generally proceed under basic or acidic conditions.
In recent years, several catalysts have been used, which can
promote ring opening of epoxides [3–8]. Although some of
the reported catalysts sufer from disadvantages such as high
In recent years, the use of transition metal complexes in
diferent synthesis protocols has rapidly increased. Spatially,
Ru complexes known as versatile catalysts for organic syn-
thesis and polymer chemistry because of the widest range
of oxidation states of Ru compared with other elements in
periodic table [9–12]. A number of homogeneous and het-
erogeneous ruthenium complexes have been prepared and
extensively used in a variety of chemical transformations
such as hydration [13–15], hydrogenation [16–21], epoxi-
dation [22, 23], oxidation [24–28], isomerization [29, 30],
decarbonylation [31–33], cyclopropanation [34], olefin
metathesis [35], Diels–Alder reaction [36], Kharasch addi-
tion [37], atom transfer radical polymerization [38, 39] and
enol-ester synthesis [40, 41].
* Shahram Tangestaninejad
stanges@sci.ui.ac.ir
* Valiollah Mirkhani
mirkhani@sci.ui.ac.ir
* Majid Moghadam
moghadamm@sci.ui.ac.ir
Different ligands such as hydride, hydrate, carboxy-
lalate, halide, phosphane, oxygen or nitrogen chelating
groups, amine, Schif bases, arenes and carbenes were used
to achieve appropriate ruthenium complexes with particu-
lar structure and properties [42–49]. Among these ligands,
1
2
Catalysis Division, Department of Chemistry, University
of Isfahan, Isfahan 81746-73441, Iran
La Trobe Institute for Molecular Science, La Trobe
University, Bundoora, VIC 3086, Australia
Vol.:(0123456789)
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Schif bases have attracted increasing attention due to steric
and electronic efects of them around the Ru core. Immobi-
lization of Ru complexes bearing bidentate Schif base is of
great current interest in our group.
area, high chemical and hydrothermal stability and large
pores which make it a suitable case for catalytic purposes
[64]. If terephthalic acid replaced with amino-terephthalic
acid as linker, amino-functionalized MIL-101 has been pro-
duced and it is easier to be functionalized.
Metal–organic frameworks (MOFs) known as very inter-
esting class of porous material are combination of inorganic
and organic subunits [50]. Due to their outstanding proper-
ties such as fexible pore size, shape and structure, high sur-
face area, porosity and thermo stability, they are prominent
candidates for a wide range of applications from gas separa-
tion/storage [51, 52], sensing [53], magnetic imaging and
drug delivery systems [54, 55] to catalysis [56–60].
Herein, we wish to report the preparation and charac-
terization of a Ru-anchored metal organic framework. In
this manner, MIL-101 reacted with 2-pyridine carboxalde-
hyde and a bidentate ligand was produced for coordination
to Ru species. This new catalyst, MIL-101–NH2–PC–Ru,
was used as an efcient and highly active catalyst for ring-
opening reactions of epoxides with methanol as nucleophile
(Scheme 1).
Post-synthetic modifcation (PSM) is a very versatile way
for producing MOF-based catalysts. In this way, the organic
linkers of the framework can be functionalized and attached
to the catalytically active sites. So diferent materials with
various physical and chemical properties can be produced
[61]. Usually metal–organic frameworks that undergo PSM
have alcohol and amino groups such as IRMOF-3 (an amino
MOF-5), NH2–DMOF, NH2–UiO-66 and NH2–UMCM-1.
Bhattacharjee et al. reported the immobilization of
manganese(II) acetylacetonate complex on IRMOF-3
via PSM [62]. Recently, Tangestaninejad et al. prepared
metal–organic frameworks (MOFs) containing Mo–Schif
base complexes by post-synthesis method and applied as
efcient catalysts in the epoxidation of alkenes with tert-
BuOOH [57]. They have also succeeded in designing a novel
catalyst by anchoring a Cu(II) Schif base into UiO-66-NH2
based on a post-synthetic strategy [63]. This new immobi-
lized catalyst was successfully applied for synthesis of ben-
zimidazoles and benzothiazoles.
Experimental
Reagents and methods
Chemicals were purchased from Fluka and Merck chemical
companies. The difuse refectance UV–Vis spectra were
recorded by a JASCO V-670 UV–Vis spectrophotometer.
Difuse refectance FTIR spectra were obtained with potas-
sium bromide pellets in the range of 400–4000 cm−1 with
a JASCO 6300 spectrophotometer. The XRD patterns were
recorded using a Bruker D8 ADVANCE X-ray difractom-
eter equipped with nickel monochromatized Cu Kα radiation
(λ = 1.5406 Ǻ). The scanning electron micrographs were
taken on a Hitachi S-4700 feld-emission scanning electron
microscope (FE-SEM). Specifc surface area was measured
by adsorption–desorption of N2 gas at 77 K with ASAP 2000
Micromeritics instrument. The ICP analyses were carried
out by a Jarrell Ash 1100 spectrometer. Gas chromatography
experiments (GC) were performed with a Shimadzu GC-16A
instrument using a 2 m column packed with silicon DC-200
or Carbowax 20 M. In the GC experiments, n-decane was
used as the internal standard.
The chromium terephthalate metal–organic frame-
work, MIL-101(MIL = Matérial Institute Lavoisier),
[(Cr3X(H2O)2O(bdc)3; X = F, OH; and bdc = benzene-
1,4-dicarboxylate)], frst synthesized by Férey et al. [48] is a
highly porous three-dimensional structure with high surface
Preparation of NH2–MIL‑101
NH2–MIL-101(Cr) was synthesized and prepared accord-
ing to the procedure reported by Lin et al. [65]. In brief,
Cr(NO3)3·9H2O (800 mg, 2 mmol), 2-amino-terephthalic
acid (360 mg, 2 mmol) and sodium hydroxide (200 mg,
5 mmol) were dispersed in distilled water (15 ml) and stirred
for 5 min, and then the solution was poured to a 50-ml Tef-
lon-lined stainless steel autoclave and kept at 150 °C for
12 h. After that, autoclave was left to cool down to room
temperature (Scheme 2). Subsequently, the green precipi-
tate was collected by centrifugation and washed with abun-
dant amounts of DMF at room temperature to remove the
excess unreacted 2-amino-terephthalic acid. The precipitate
Scheme 1 Nucleophilic ring opening of epoxides
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Results and discussion
Preparation and characterization of the catalyst,
MIL‑101–NH2–PC–Ru(III)
The amine groups in porous MOF, amino-MIL-101, are not
involved in the framework backbone, so they were easily
modifed with 2-pyridine carboxaldehyde, and a bidentate
Schif base ligand containing nitrogen-donating atoms was
prepared (Scheme 3).
Scheme 2 Synthesis of NH2–MIL-101(Cr)
is washed afterward with hot alcohol at 100 °C for 24 h in
The amount of Ru(III), determined by ICP analysis, was
about 0.0173 mmol/g of catalyst. The prepared catalyst
was also characterized by FTIR (Fig. 1). The characteristic
stretching vibrational bands between 1300 and 1700 cm−1
and bending vibrational bands between 400 and 700 cm−1
refer to COO and C–C bonds and indicate the presence
of dicarboxylate functional groups. The relatively narrow
weak bands in 767 and 970 cm−1 indicate δ and γ vibra-
tional bands of C–H in aromatic ring, and the presence of
them in all spectra confrms the stability of the framework
during post-synthetic modifcation [65] (Fig. 1a–c). Sym-
metric and asymmetric stretching vibrational bands which
can be seen in 3370 cm−1 and 3473 cm−1 are related to NH2
groups. These bands present in all four spectrums shows
that converting of amine functional groups to imine is not
100% during the modifcation. The N–H bending vibrational
bands of NH2 and the C–N stretching vibrational bands of
aromatic amines appear in 1620 and 1338 cm−1, respectively
(Fig. 1a). The C=N vibrational band of imine-functional-
ized framework appears in 1713 cm−1 (Fig. 1b). An obvious
thickening and a slight shift from 1713 to 1668 cm−1 are
seen after attachment of Ru(III) to the framework (Fig. 1c)
which is an evidence of successful synthesis of the catalyst.
The X-ray difraction patterns of samples are shown in
Fig. 2. Comparison of the XRD pattern of NH2–MIL-101,
MIL-101–NH2–PC and MIL-101–NH2–PC–Ru clearly
shows that the framework structure of amino-MIL-101
remained intact during the post-synthetic modifcation
(Fig. 2). The main peaks in the patterns are in accordance
with the reported patterns for NH2–MIL-101 in the litera-
ture [65]. It is deduced from the UV–Vis spectrum of (A)
and (B) that the exhibited peak at 502 nm can be attributed
to metal–ligand charge transfer (Fig. 3).
an autoclave. Finally, the products were dried at 80 °C in air.
Preparation of MIL‑101–NH2–PC
The Schif base-grafted NH2–MIL-101 was prepared as fol-
lowing: To the solution of NH2–MIL-101 (0.4 g) in 30 ml
toluene, 2-pyridine carboxaldehyde (0.4 ml) was added. The
mixture was stirred for 6 days at room temperature [66–69],
and afterward it was fltrated and washed several times with
ethanol to drive out unreacted 2-pyridine carboxaldehyde.
At last, the imine-functionalized MOF was dried at 353 K
to become suitable for the metalation step.
Preparation of MIL‑101–NH2–PC–Ru(III)
The Ru-grafted MIL-101–NH2–PC was prepared as follow-
ing: The imine-functionalized MOF (0.2 g) was dispersed in
DMF (15 ml). Excess RuCl3∙6H2O (0.2 g) was dissolved in
minimum amount of DMF, added dropwise to the mixture
and refuxed at 343 K for 24 h. Finally, the mixture was
fltrated and washed several times with ethanol and dried at
353 K under vacuum to gain the desired catalyst.
General procedure for the methanolysis of epoxides
To a solution of epoxide (1 mmol) in methanol, the catalyst
MIL-101–NH2–PC–Ru(III) (50 mg) was added. The mix-
ture was stirred for the appropriate time at room tempera-
ture according to Table 1. The progress of the reaction was
monitored by GC.
Recovery and reuse
As shown in Fig. 4, from FE-SEM images of NH2–MIL-
101 and MIL-101–NH2–PC–Ru(III), it is clear that there are
no signifcant changes in the morphology of crystals during
the preparation of the catalyst. Also, the energy-dispersive
X-ray (EDX) results, obtained from SEM analysis, show the
presence of Ru in the prepared catalyst (Fig. 4c).
The methanolysis of styrene oxide was chosen as a
model reaction for checking the reusability of MIL-
101–NH2–PC–Ru(III). At the end of the reaction, the cata-
lyst was recovered by fltration, washed with Et2O and dried.
The catalyst was reused four times without any loss of activ-
ity. After each run, the catalyst was isolated from the reac-
tion mixture, and the amount of Ru leaching was followed
by ICP.
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Table 1 Methanolysis of epoxides catalyzed by MIL-101-NH2-PC-Ru(III)a
Entry
1
Epoxide
Yield (%)b
Time (h)
30
TOF (h−1
2325
)
100
O
2
3
100
94
45
60
1550
1093
O
O
O
4
5
98
95
50
55
1372
1205
O
O
O
6
96
75
895
O
O
aReaction conditions: epoxide (1 mmol), CH3OH (4 ml) and catalyst (50 mg) at room temperature
bGC yield
Scheme 3 Preparation of the
catalyst
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Fig. 1 FTIR spectrum of: A NH2–MIL-101, B imine-functionalized framework, C MIL-101–NH2–PC–Ru(III)
Fig. 2 XRD pattern of: a NH2–MIL-101, b MIL-101–NH2–PC–
Ru(III)
Fig. 3 UV-Vis spectrum of: a NH2–MIL-101, b MIL-101–NH2–PC–
Ru(III)
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Fig. 4 FE-SEM images of: a NH2–MIL-101; b MIL-101–NH2–PC–Ru(III) and c SEM–EDX spectrum of MIL-101–NH2–PC–Ru(III)
The specific surface area and pore volume of MIL-
101–NH2 and MIL-101–NH2–PC–Ru(III) were determined
using nitrogen physisorption measurements (Fig. 5). It shows a
predictable decrease in pore volume from 1.55 to 0.79 cm3 g−1,
and also BET surface area decreased from 1610 to 792 m2 g−1
after complexation of MIL-101–NH2 with Ru. This great
decrease in surface area and pore volume after post-synthetic
modifcation indicates that the cavities of MIL-101–NH2 are
occupied by Ru(III) complexes.
Catalytic experiments
The ability of the prepared catalyst was investigated in the ring
opening of styrene oxide with methanol as model reaction.
First, the amount of catalyst was optimized. The best results
were obtained with 50 mg of the catalyst at room temperature
(Fig. 6).
In the similar conditions, a blank experiment in the pres-
ence of primary framework, NH2–MIL-101 and methanol,
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Fig. 5 N2 adsorption/desorption isotherm of: a NH2–MIL-101 and b MIL-101–NH2–PC–Ru(III)
present. However, a plausible explanation is that epoxide is
frst activated by catalyst to aford 1. Alcohol attacks 1 to give
2 which in turn converts to the fnal product and releases the
catalyst for the next catalytic cycle (Scheme 4).
Catalyst reuse and stability
From economical point of view, the stability and reusability of
a heterogeneous catalyst are very important. The reusability
of the prepared catalyst was investigated using methanolysis
of styrene oxide as model reaction. At the end of reaction, the
catalyst was separated by simple fltration and washed several
times with Et2O and dried in oven before using in the next run.
The results showed that the catalyst could be reused for four
consecutive cycles without substantial reduction in its activity
(Table 2). The Ru(III) ion leaching was determined by analyz-
ing the collected fltrates by ICP method. The results showed
that only small amounts of Ru catalyst were leached (less than
1.3% in the two frst runs). No Ru was detected after the sec-
ond run in the reaction mixture. So it is clear that the catalyst
is stable under the reaction conditions, can be recovered and
reused. The nature of the recovered catalyst was monitored
by FTIR and XRD analysis. The XRD patterns indicated that
the basic lattice structure of MIL-101–NH2–PC–Ru(III) was
Fig. 6 Optimization of the catalyst amount in the methanolysis of sty-
rene oxide at room temperature in 45 min
was also done. The results from GC analysis showed that
only 6% of styrene oxide was converted to the related alcohol
after 24 h, so these experiments revealed that the active site
of the catalyst is the intercalated Ru species. The reaction was
performed in the presence of diferent epoxides, and the cor-
responding β-alkoxy alcohols were obtained. The results are
summarized in Table 1. The actual mechanism is not clear at
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Scheme 4 Proposed mechanism
for the ring opening of epoxides
Table 2 Recyclability of
run
Yield (%)a
Ru
MIL-101–NH2–PC–Ru(III) in
methanolysis of styrene oxide
leached
(%)b
1
2
3
4
100
98
95
1.1
0.2
0
95
0
Reaction conditions: styrene
oxide (1 mmol), CH3OH (4 ml)
and catalyst (50 mg)
T room temperature
Fig. 7 XRD pattern of the recovered catalyst
a
GC yield based on the starting
epoxide
b Determined by ICP
Conclusion
not altered after three cycles (Fig. 7). Also, by considering
the FTIR spectra, it is proved that the catalyst has retained its
nature during the reaction (Fig. 8).
In conclusion, we have succeeded in designing a heteroge-
neous Ru(III) Schif base catalytic system by post-synthetic
modifcation of MIL-101–NH2 metal organic framework via
2-pyridine carboxaldehyde as support. The prepared hybrid
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Fig. 8 FTIR spectrum of the recovered catalyst
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material was used as an efcient and highly active catalyst
for ring-opening reactions of epoxides with methanol as
nucleophile. This novel catalyst can be recovered and reused
four consecutive times without signifcant loss of its initial
activity and mass. High activity, selectivity, extremely mild
reaction conditions and easy workup are other advantages
of this new catalytic system.
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Acknowledgements The support of this work by the Research Council
of the University of Isfahan is acknowledged.
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