Amine-functionalized MIL-101(Cr) embedded with Co(II) phthalocyanine as a durable catalyst for one-pot tandem oxidative A3 coupling reactions of alcohols

Article abstract of DOI:10.1039/c7nj05132h

A novel porous postsynthetic-modified metal-organic framework (MIL-101(Cr)-NH₂) was fabricated via covalent immobilization of cobalt(ii) phthalocyanine and characterized by a variety of techniques, including FTIR, XRD, TGA, SEM, EDS and ICP-OES

Full text of DOI:10.1039/c7nj05132h

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Amine-functionalized MIL-101(Cr) embedded with Co(II) phthalocyanine as a
3
durable catalyst for one-pot tandem oxidative A coupling reactions of alcohols
Ahmad Shaabani,* Reza Mohammadian, Alireza Hashemzadeh, Ronak Afshari, Mostafa M.
Amini,*
Faculty of Chemistry, Shahid Beheshti University, G. C., P. O. Box 19396-4716, Tehran, Iran
*
Corresponding authors: Tel: +982129902800, Fax: +982122431663 Eꢀmail address: aꢀshaabani@sbu.ac.ir; Tel
+982129903109, Fax: +982122431663, Eꢀmail address: mꢀpouramini@sbu.ac.ir
:
1

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Abstract
A newly porous postsynthetic modified metalꢀorganic framework (MILꢀ101(Cr)ꢀNH
2
) was
fabricated via a covalent immobilization of the cobalt(II) phthalocyanine and characterized
by a variety of techniques, including FTꢀIR, XRD, TGA, SEM, EDS and ICPꢀOES analysis.
3
This catalyst was successfully used in a oneꢀpot tandem oxidative A coupling reaction of
alcohols. The main advantages of this protocol are reusability of catalyst, operational
simplicity, mild reaction conditions and high yielding.
Keywords: Metal–organic framework, Postsynthetic modification, Metallophthalocyanines,
3
Heterogeneous catalyst, Tandem oxidation process, A coupling reaction.
1
. Introduction
Design of new synthetic methodologies and strategies requires minimization of the
reaction steps as much as possible with the more efficient and environmentally benign
processes due to environmental concern and timeꢀcost benefits. To this end, tandem reactions
in which sequential transformations take place via two (or more) mechanistically distinct
1
processes suit these demands well. The tandem oxidation process (TOP) as an innovative
and efficient synthetic approach combines the in-situ produced aldehyde intermediates from
the oxidation of alcohols with nucleophilic trapping agents, meets the chemists demands in
2
modern synthetic strategies designation and total syntheses. Although the vast research
3
efforts have been made in the development of TOP processes, its application in some
4
chemical transformations especially multicomponent reactions (MCRs) is less investigated.
The intrinsic complexity of MCRs mechanism and multiple functionalities of these types of
reactions prevent the development of such oneꢀpot oxidation/MCR processes; this is while in
the majority of influential MCRs aldehydes are ubiquitous substrates. Therefore, improving
2

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the novel catalytic system to develop such a synthetic protocol would extend the scope of
aldehydeꢀbased MCRs.
Propargylamines are important building blocks that have been the object of intense
investigations in medicinal chemistry, because of their biological activities and therapeutic
5
properties. They have been identified as one of the most widely prescribed potent drugs for
preventing cell death and also as potential and selective irreversible monoamine oxidase typeꢀ
6
B (MAOꢀB) inhibitors. Consequently, various methods have been developed for the
7
3
synthesis of propargylamine scaffolds. Among these, A coupling reaction (threeꢀcomponent
coupling of aldehyde, amine, and alkyne) is more convenient and general approach towards
propargylamine. In this type of reaction unlike classical methods in which metal acetylide is
produced by applying stoichiometric quantities of the organometallic reagents, only a
catalytic amount of transition metal has been used to create metal acetylide intermediate by
C–H bond activation of terminal alkynes. In recent years, significant progress has been
manifested for expanding the scope of this reaction by applying various homogeneous and
8
9
10
11
12
6
heterogeneous catalysts such as Cu(I), Ag(I), Fe(III), Zn(II), Au(I)/Au(III), Ni(II) and
1
3
14
15
16
In(III) salts, Irꢀcomplexes, Ni–Y–zeolite, copper ferrite nanoparticles, copperꢀ
17
18
19
20
3 4
zeolites, Fe O nanoparticles, Zn dust and nanocrystalline copper(II) oxide. Although
several methods for the synthesis of propargylamine scaffolds have been reported, most of
them have limited scope and require high temperature, long reaction times, inert gas and
expensive catalysts such as Au, Ag and Ir. Thus, development of more efficient, practical,
cheaper, reusable and simple synthetic methods can be beneficial.
Phthalocyanines (Pcs) and metallophthalocyanines (MPcs) have found widespread
applications in diverse areas of material science, including catalysis, electrophotography,
infrared radiation absorption, optical data storage and liquid crystallography because of their
3

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21
excellent optical and electrical properties. Appropriate structural modifications on MPcs by
incorporating a variety of catalytically active metals in the phthalocyanine ligand can lead to
22
fundamental changes in the catalytic properties corresponding to the used metals. Up to
now, diverse chemical transformations including oxidation, reduction, and various C−C bond
23
formation reactions were efficiently catalyzed by MPcs. However, application of MPcs as
catalysts has some drawbacks such as the tendency of these compounds to aggregation and
agglomeration which subsequently reduce their catalytic activity; in addition, homogeneous
MPc catalysts are separated from the reaction media with difficulty. To overcome these
problems, covalently attachment of the MPcs on the insoluble supports can provide
recyclable catalysts that prevent aggregation and agglomeration of the MPc complexes,
simplify the homogeneous MPcs separation process and increase the heterogeneous MPcs
23ꢀ24
effective surface area.
Therefore, with these features in mind, designing novel
heterogeneous catalysts based on MPcs would develop efficient catalysts that seem to be
promising candidates in many reactions.
Metalꢀorganic frameworks (MOFs) as a kind of crystalline porous materials constructed
from metalꢀion containing nodes and multitopic organic linkers have gathered considerable
attention due to their promising applications in gas and chemical storage, separation, drug
2
5
delivery, conductivity, and catalysis. Although novel applications are added to an already
above impressive list as the chemistry of MOFs progresses, one of the challenges in the area
of material sciences is the emergence of new applications which emphasizes the requirement
2
6
of new types of materials. In this regard, postsynthetic modification (PSM) of MOFs are
known convert MOFs to a series of new materials which bears different chemical
functionalities with the same basic structure of MOF. It has been shown this approach is
27
general and practical for incorporating a wide range of functional groups into MOFs. The
resulted new MOF materials are entirely different from those of the parent MOF in catalytic
4

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behavior and can be used as a novel heterogeneous catalyst in chemical reactions. In this
aspect and in continuation of our interest in developing catalytic systems based on MPcs for
28
29
synthetic methodologies and multicomponent reactions, herein, we report the synthesis of
MILꢀ101ꢀNH MOF covalently anchored to cobalt(II) phthalocyanine by postsynthetic
2
3
modification process and investigation of its catalytic activity in the tandem oxidative A
couplingꢀthree component reaction in oneꢀpot (Scheme 1). To the best of our knowledge,
covalent binding of cobalt(II) phthalocyanine to MOF which is presented here has not yet
been described in the literature.
3
Scheme 1. MILꢀ101ꢀNH
2
ꢀCo(II)Pcꢀcatalyzed tandem oxidative A coupling reaction.
2
. Results and Discussion
MILꢀ101 MOF based on chromium and containing amine functional groups
30
previously synthesized by Kong and coꢀworkers. Since the amine moieties are present in the
linker (2ꢀaminoterephthalic acid) of the MOFs, functionalization of the material is available
using chemical transformations. Therefore, postsynthetic modified MOFs can be prepared by
covalent modification via nucleophilic attack of NH groups on the fairly positive carbon
2
atom of acyl chloride moieties present in tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II),
producing an amide group between MOF and MPc (Scheme 2).
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2
Scheme 2. Preparation of MILꢀ101ꢀNH ꢀCo(II)Pc.
The synthesized catalyst was characterized by FTꢀIR, XRD, TGA, SEM, EDS and
ICPꢀOES analysis. Covalent immobilization of the cobalt(II) phthalocyanine on MILꢀ101ꢀ
2
NH was supported by FTꢀIR spectroscopy based on diminution of stretching band at 1708
ꢀ1
cm
related
to
C=O
bond
of
acyl
chloride
moieties
present
in
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) and enhancement of stretching band at
ꢀ1
1
627 cm in agreement with the formation of amide group. Also, in confirming the desired
catalyst formation, two stretching bands related to tetrakis(chlorocarbonyl)phthalocyaninato
ꢀ1
cobalt(II) exhibited at 1029 and 1078 cm distinctly appeared in IR spectrum of MILꢀ101ꢀ
NH ꢀCo(II)Pc (Figure 1).
2
6

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Figure 1. FTꢀIR spectra of tetrakis(carboxy)phthalocyaninato cobalt(II) (A),
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) (B), MILꢀ101ꢀNH (C), and MILꢀ101ꢀNH ꢀCo(II)Pc (D).
2
2
Powder
Xꢀray
diffraction
(PXRD)
patterns
of
2
MILꢀ101ꢀNH ,
2
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) and MILꢀ101ꢀNH ꢀCo(II)Pc were
recorded and employed to investigate the structure of the synthetic catalysts. As shown in
Figure 2, the characteristic diffractions of tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II)
o
o
o
o
appeared at 2θ values of 28 , 40.5 , 50.1 and 66.3 as four sharp diffractions and the PXRD
o
o
o
o
2
pattern of MILꢀ101ꢀNH show characteristic diffractions at 2θ = 3.3 , 5.1 , 8.9 and 16.6 .
The Xꢀray diffraction patterns of synthetic catalyst reveal that almost all the diffractions are
maintained even after the postꢀsynthetic reaction indicating that the structure of the materials
is not changed during the functionalization process.
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Figure 2. XRD patterns of MILꢀ101ꢀNH
2
(A), tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) (B) and MILꢀ
01ꢀNH ꢀCo(II)Pc (C).
1
2
Thermal gravimetric analysis (TGA) was performed on MILꢀ101ꢀNH
ꢀCo(II)Pc in the air to investigate the thermal stability of catalysts and the results are
illustrated in Figure 3. Thermogravimetric curves of MILꢀ101ꢀNH and MILꢀ101ꢀNH
2
, and MILꢀ101ꢀ
NH
2
2
2
ꢀ
Co(II)Pc revealed initial loss of adsorbed water and volatile materials in the temperature
o
range of 76ꢀ129 and 86ꢀ138 C, respectively. The thermogram of MILꢀ101ꢀNH
2
and MILꢀ
2
101ꢀNH ꢀCo(II)Pc also show a weight loss of about 78% and 67% at the temperature higher
o
than 600 C, respectively. Thus, 11% difference between residual weight losses is attributed
to the simultaneous presence of the chromium and cobalt metals which are stable at this
temperature. Also, the results proved that the functionalization of MILꢀ101ꢀNH with
2
o
Co(II)Pc caused the thermal stability of final composite to be enhanced to around of 200 C.
8

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2 2
Figure 3. TGA curves of MILꢀ101ꢀNH (A) and MILꢀ101ꢀNH ꢀCo(II)Pc (B).
The SEM analyses carried out to study the structure and morphology of the obtained
catalyst, and the result is illustrated in Figure 4. Since
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) has the bulky structure and covalently
supported on the surface of the MILꢀ101ꢀNH , loading of the Co(II)Pc functionality should
2
affect the nanomorphology of MOF. As shown in Figure 4 (right), the synthesized catalyst
almost affected the morphology of parent MOF; however, in some areas initial morphology
has been retained. Finally, the energy dispersive spectroscopy (EDS) analysis determined the
2
chemical composition of MILꢀ101ꢀNH ꢀCo(II)Pc and revealed that the chromium and cobalt
metals are present in the catalyst (Figure 5). Furthermore, to determine the loading of cobalt
in the catalyst, the inductively coupled plasmaꢀoptical emission spectroscopy (ICPꢀOES)
analysis of MILꢀ101ꢀNH
2
ꢀCo(II)Pc was carried out. The results showed 0.15 mmol/gr cobalt
loading in the final catalyst.
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Figure 4. SEM images of MILꢀ101ꢀNH (left) and MILꢀ101ꢀNH ꢀCo(II)Pc (right).
2
2
Figure 5. EDS result for MILꢀ101ꢀNH
2
ꢀCo(II)Pc.
1
0

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2
Catalytic activity of MIL-101-NH -Co(II)Pc
2
At the outset, the catalytic activity of the newly synthesized MILꢀ101ꢀNH ꢀCo(II)Pc
3
was evaluated in the tandem oxidative A coupling reaction. Initially, the model tandem
reaction between benzyl alcohol, phenylacetylene and piperidine were investigated under
o
various conditions (Table 1). In the absence of the catalyst at 100 C for 24 h in toluene, no
desired product was obtained, and most of starting material was recovered (Table 1, Entry 1).
When the reaction was run in the presence of MILꢀ101ꢀNH
2
ꢀCo(II)Pc (20 mg) at room
o
temperature, the desired product was not obtained, but by raising the temperature to 80 C,
6
1
2% yields were obtained within 12 h (Table 1, Entry 3). The optimal amount of the MILꢀ
01ꢀNH ꢀCo(II)Pc was found to be 40 mg due to higher yield and shorter reaction time than
2
the other amount of catalyst loading (Table 1, Entry 4). In order to confirm the catalytic
efficiency of MILꢀ101ꢀNH ꢀCo(II)Pc in the model tandem reaction, the catalytic activity of
2
the aforementioned catalyst was compared with a number of other catalysts such as MILꢀ101ꢀ
NH and tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) individually and the results
2
2
reveal that MILꢀ101ꢀNH ꢀCo(II)Pc has superior catalytic efficiency than the two other
catalysts in the model reaction (Table 1, Entry 6ꢀ7). The reaction of benzyl alcohol,
piperidine and phenylacetylene was also tested in the absence and presence of various bases.
Considering the obtained results, the most appropriate and optimal amount of base in this
reaction is 10 mol% KOH. The model reaction was also examined in various solvents (Table
1, Entry 11ꢀ13). Results showed that the toluene was the most appropriate reaction medium
due to the highest yield (91%) of the product. Finally, the turnover number (TON) and
turnover frequency (TOF) of the catalyst for the model reaction were determined to be 151
ꢀ1
and 19 h , respectively.
1
1

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a
3
Table 1. Optimization of reaction conditions for the synthesis of propargylamine via a tandem oxidative A
a
coupling reaction of benzyl alcohol
o
b
Entry
Catalyst (mg)
Base (mol%)
KOH (10)
KOH (10)
KOH (10)
KOH (10)
KOH (10)
KOH (10)
KOH (10)
ꢀ
Solvent
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
water
Temperature ( C) Time (h)
Yield (%)
1
2
3
4
5
6
7
8
9
ꢀ
100
r.t.
80
80
80
80
80
80
80
80
80
80
80
24
24
12
8
ꢀ
ꢀ
MILꢀ101ꢀNH
2
2
2
2
ꢀCo(II)Pc (20)
MILꢀ101ꢀNH
MIL-101-NH
MILꢀ101ꢀNH
ꢀCo(II)Pc (20)
-Co(II)Pc (40)
ꢀCo(II)Pc (50)
62
91
8
94
MILꢀ101ꢀNH2 (40)
Co(II)Pc (40)
8
Trace
43
8
MILꢀ101ꢀNH
ꢀCo(II)Pc (40)
8
37
2
2
2
2
2
2
MILꢀ101ꢀNH
MILꢀ101ꢀNH
MILꢀ101ꢀNH
MILꢀ101ꢀNH
MILꢀ101ꢀNH
ꢀCo(II)Pc (40)
ꢀCo(II)Pc (40)
ꢀCo(II)Pc (40)
ꢀCo(II)Pc (40)
ꢀCo(II)Pc (40)
KOH (5)
8
81
10
11
12
13
K
2
CO
3
(10)
8
54
KOH (10)
KOH (10)
KOH (10)
8
Trace
12
acetonitrile
xylene
8
8
85
a
Reaction conditions: benzylalcohol (1.3 mmol), piperidine (1.00 mmol), phenylacetylene (1.00 mmol), base, air and catalyst
Isolated yield
b
Following the aforementioned promising results, the optimized conditions were used
for the synthesis of different propargylamines by using a series of benzyl alcohols bearing
various substituents such as H, OMe, Me, Cl and NO , various amines and phenylacetylene
2
derivatives. It can be seen that all the reactions gave products in moderate to good yields.
3
Table 2. Synthesis of propargylamines via tandem oxidative A coupling reaction of benzyl alcohols using
a
2
MILꢀ101ꢀNH ꢀCo(II)Pc
1
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b
Entry
Alcohol
Amine
Alkyne
PhCCH
PhCCH
PhCCH
PhCCH
PhCCH
PhCCH
PhCCH
PhCCH
Time (h)
Yield (%) Product
1
2
3
4
5
6
7
8
9
PhCH
2
2
OH
OH
Piperidine
Pyrrolidine
Piperidine
Pyrrolidine
Morpholine
Piperidine
Pyrrolidine
Piperidine
Piperidine
Piperidine
8
8
91
93
90
86
83
84
87
89
92
85
5a
5b
5c
5d
5e
5f
PhCH
4ꢀClC
6
H
4
CH
2
OH
7.5
9
4ꢀMeC
H
CH
CH
OH
OH
6
6
4
4
2
4ꢀMeC
H
2
9
4ꢀMeOC
6
6
H
4
4
CH
CH
2
2
OH
OH
9
4ꢀMeOC
H
9
5g
5h
5i
4ꢀNO
PhCH
4ꢀMeC
C
H
CH
OH
CH
OH
8
2
6
4
2
2
4ꢀMeC
4ꢀMeC
6
6
H
H
4
4
CCH
CCH
8
1
0
6
H
4
2
OH
9
5j
a
Reaction conditions: benzylalcohol (1.3 mmol), secondary amine (1.00 mmol), phenylacetylene (1.00 mmol), KOH (10
mol%), air and 40 mg MILꢀ101ꢀNH
Isolated yield
2
ꢀCo(II)Pc
b
Based on literature reports of catalytic applications of Co(II)Pc in the oxidation of
31
alcohols, a proposed mechanism for the first stage of the reaction (oxidation process)
proceeds through the adsorption of oxygen atom in benzyl alcohol on Co(II) which increases
the rate of hydrogen elimination by KOH. Then, the transition complex formed between
cobalt and benzyl alcohol underwent removal of a hydrogen atom from the carbon attached to
the hydroxyl group of alcohols by KOH and aldehyde products were obtained (Scheme 3).
3
There are two plausible mechanisms for the second stage of the reaction (A coupling
32
process). One mechanism is based on Co(I)ꢀCo(III)ꢀCo(I) cycle in which Co(II) species
were reduced by alkyne and Co(I) can be generated. Next, nucleophilic attack of acetylide ion
from alkynyl–Co(III) complex to the immonium ion which generated from aldehydes and
secondary amines produces the corresponding propargylamine, and the Co(I) species can be
regenerated by a reductive elimination. The second possible mechanism proceeds through
32a
Co(II) species without any change in oxidative state of the catalyst. In this mechanism,
Co(II) species can activate the terminal alkyne and increase its acidity. Subsequently, the
1
3

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coupling of Co(II) acetylide intermediate which is generated in the presence of a base to the
iminium ion leads to desired products and regenerates the Co(II) catalyst for further cycles.
To investigate these two tentative mechanisms, three component reactions of
benzaldehyde, piperidine and phenylacetylene were tested in the absence and presence of the
base, and results are represented in Table 3. Screening different conditions revealed that by
increasing the amount of the base, the reaction time could be decreased to 3 h and the yield
can be increased to 95%. These results show that the second mechanism could be more
probable due to the greater role of the base in the second proposed mechanism.
3
Table 3. Screening of the base amount in the synthesis of propargylamines via A coupling reaction of
a
benzaldehyde, piperidine and phenylacetylene using MILꢀ101ꢀNH
2
ꢀCo(II)Pc
b
Entry
Base (mol%)
KOH (0)
Time (h)
Yield (%)
1
2
3
4
6
5
40
82
93
95
KOH (5)
KOH (10)
KOH (15)
4.5
3
a
Reaction conditions: benzyladehyde (1.00 mmol), piperidine (1.00 mmol), phenylacetylene (1.00 mmol), base and 40 mg
MILꢀ101ꢀNH ꢀCo(II)Pc
2
b
Isolated yield
1
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3
2
Scheme 3. Proposed mechanism for the oneꢀpot tandem oxidation/A coupling reaction using MILꢀ101ꢀNH ꢀ
Co(II)Pc.
2
The reusability and activity potential of MILꢀ101ꢀNH ꢀCo(II)Pc were investigated to
three consecutive cycles for the model reaction using benzyl alcohol, phenylacetylene, and
piperidine. After completion of the reaction, the catalyst was separated from the reaction
mixture by filtration, washed with chloroform, ethanol, and acetone, dried and reused in the
next run. The recycled catalyst was efficiently used in the next five consecutive cycles
without significant loss of catalytic activity as shown in Figure 6.
1
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2
Figure 6. Recycle of the MILꢀ101ꢀNH ꢀCo(II)pc nanocatalyst for the synthesis of the propargylamine.
2
In order to confirm the reusability and stability of MILꢀ101ꢀNH ꢀCo(II)Pc during the
reaction, the recovered catalyst was analyzed by powder Xꢀray diffraction (PXRD) and ICPꢀ
OES and results compared to that of the fresh one. No significant changes were observed in
PXRD (Figure 7). The trivial differences between some of the reflection intensities of
recovered and the fresh catalyst patterns could be due to the variation in the orientation of
2
powder samples during PXRD patterns recording. The PXRD patterns of the MILꢀ101ꢀNH ꢀ
Co(II)Pc are same before and after several consecutive use; this revealed that the structure of
catalyst remained intact during the reaction. Furthermore, less than 5% leaching of cobalt in
the recovered catalyst after several runs, according to the ICPꢀOES analysis, clearly indicates
stability of the catalyst.
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2
Figure 7. PXRD patterns of MILꢀ101ꢀNH ꢀCo(II)Pc before (A), after using (B)
3
. Conclusions
In summary, postsynthetic modified MILꢀ101ꢀNH
2
was prepared via covalent
immobilization of the tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) and used in a oneꢀ
3
pot tandem oxidative A coupling reaction to afford propargylamines with fairly good yields.
Notably, ease of synthetic procedure and the simple preparation of the catalyst will present
novel material for the development of new types of organic reactions. In addition, short
reaction time, high product yield, reusability of the catalyst which can be efficiently recycled
with no significant loss of catalytic activity are the other advantages of this newly catalytic
system.
4
. Experimental
4.1. Materials and Methods
All reagents were purchased from SigmaꢀAldrich and used without further purification.
The Xꢀray powder diffraction (XRD) patterns were recorded on a STOE diffractometer with
CuꢀKα radiation (λ=1.5418 Å). The FTꢀIR spectra were recorded on a Bomem MBꢀSeries
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1
FTꢀIR spectrometer. The H NMR spectra were recorded on a BRUKER DRXꢀ300
AVANCE spectrometer at 300.13 MHz using CDCl as solvent and tetramethylsilane (TMS)
as an internal standard. Thermogravimetric analysis (TGA) was carried out using STA 1500
3
ꢀ1
instrument at a heating rate of 10 °C min in the air. The loading of cobalt was measured
using an inductively coupled plasma optical emission spectrometer (ICPꢀOES; Varian Vista
PRO Radial). Scanning electron microscopy (SEM) observations were carried out on an
electron microscopy Philips XLꢀ30 ESEM. All samples were sputtered with gold before
observation.
4.2. Preparation of the MIL-101-NH
2
30
2
The MILꢀ101ꢀNH was synthesized according to the previously reported method.
Chromic nitrate hydrate (2.40 g, 6.00 mmol), 2ꢀaminoterephthalic acid (1.08 mg, 6.00 mmol)
and sodium hydroxide (0.59 g, 15.00 mmol) were sonicated in deionized water (45 ml) and
thoroughly stirred. The suspension was transferred in an autoclave and kept at 150 °C for 12
h. After the autoclave was cooled, the green precipitate was filtered off and washed with
DMF to remove unreacted ligands. Finally, the solid was further purified by alcohol at 100
°C for 24 h in an autoclave, filtered off, and dried at 80 °C in air.
4.3. Preparation of the tetrakis(carboxy)phthalocyaninato cobalt(II)
The tetrakis(carboxy)phthalocyaninato cobalt(II) was prepared according to the
3
3
procedure reported in the literature. Trimellitic anhydride 3.18 g (16.60 mmol), urea 8 g
130 mmol), ammonium molybdate tetrahydrate 0.0618 g (5.00 mmol), ammonium chloride
.4029 g (7.50 mmol), and 5 mmol of CoCl were mixed together until homogeneous powder
(
0
2
resulted. The obtained powder was placed in a beaker and heated for 5 h at 220 °C. The
produced mixture was cooled to room temperature, washed with aqueous HCl (1 N, 20 mL),
H O (50 mL) filtrated and dried. The product was mixed and heated at 90 °C for 2 days in
2
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100 mL of 5 N NaOH and supersaturated NaCl solution. After cooling, the mixture was
diluted with distilled water until no residual could be detected. The solution was filtered, and
the dark blue filtrate was acidified by 6 N HCl until tetrakis(carboxy)phthalocyaninato
cobalt(II) complexes were precipitated. The product was separated by centrifugation. The
residue was redissolved in 0.1 N NaOH solution and filtered to separate the insoluble
materials. The compound was reprecipitated with 1.0 N HCl and centrifuged to obtain the
solid material. Dissolution and precipitation steps were repeated twice. The product was
washed with distilled water until the filtrate became neutral. The product was dried at 70 °C.
4.4. Preparation of the tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II)
The tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) was prepared according to the
3
4
previously reported method
by converting the carboxylic acid groups of
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) to formyl chloride via a reaction with
thionyl chloride (SOCl ). In a roundꢀbottomed flask, an excess amount of SOCl (30 mL) was
2
2
added to tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) (0.100 g). The mixture was
o
refluxed at 75 C for 48 h. Subsequently, the sample was evaporated under reduced pressure,
2
followed by the complete removal of unreacted SOCl on a rotary evaporator with a vacuum
pump. The remaining solid was washed three times with anhydrous tetrahydrofuran and dried
o
in an oven for 5 h at 60 C.
4.5. Preparation of the MIL-101-NH
2
-Co(II) phthalocyanine
In a roundꢀbottomed flask, the prepared MILꢀ101ꢀNH 0.764 gr (1.00 mmol),
2
tetrakis(chlorocarbonyl)phthalocyaninato cobalt(II) 0.821 gr (1.00 mmol) and anhydrous
o
DMF (5 mL) were added and stirred for 3 days at 50 C. The resulted dark green solution was
cooled to room temperature, and then the obtained solid was isolated by centrifugation,
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washed with anhydrous DMF and ethanol three times. Finally, the collected solid was dried
in vacuum at 80 °C for 24 h.
4.6. General catalytic procedure for the synthesis of propargylamines
In a typical procedure, a mixture of benzyl alcohol (1.30 mmol,), KOH (10 mol%) and
2
MILꢀ101ꢀNH ꢀCo(II)Pc (40 mg) in dry toluene (5 mL) were added to a 25 mL roundꢀ
ꢀ1
bottomed flask. Then, the resulting solution was heated under air with the 400 mL.min flow
o
rate at 80 C for 3 h. Afterwards, secondary amine (1.00 mmol) and phenylacetylene (1.00
o
mmol) were added to above mixture and reaction was stirred at 80 C for an appropriate time
(Tables 2). After completion of the reaction (monitored by TLC), the reaction mixture was
cooled to the room temperature, and the catalyst was separated by filtration and washed with
chloroform, ethanol, and acetone followed by drying at 60 °C for 3 h. The crude product was
purified by column chromatography on silica gel using nꢀhexane/EtOAc as elution solution to
afford the corresponding pure product.
Acknowledgement
We gratefully acknowledge financial support from the Shahid Beheshti University
and the Iran National Elites Foundation (INEF).
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Table of contents
In this study, we have reported the postsynthetic modified metal-organic framework (MIL-
01(Cr)-NH ) via a covalent immobilization of the cobalt(II) phthalocyanine as an efficient and
1
2
mild catalytic system.