An Acid Stable Metal-Organic Framework as an Efficient and Recyclable Catalyst for the O?H Insertion Reaction of Carboxylic Acids

Article abstract of DOI:10.1002/cctc.201800597

Although metal-organic frameworks (MOFs) can be used in many reactions, their applications in acid involved reactions are limited due to their instability in acid environment. As a stable MOF, the Ir(III)-porphyrin metal-organic framework of the formula [(Hf₆(μ₃-O)₈(OH)₂(H₂O)₁₀)₂(Ir(TCPP)Cl)₃]?solvents (Ir-PMOF-1(Hf)) can sustain its structure upon treatments in different pH (0–11) aqueous solutions. In this work, Ir-PMOF-1(Hf) has been examined in the O?H insertion reaction of carboxylic acids with diazo compounds. Catalytic results show that as low as 0.042 mol % of Ir-PMOF-1(Hf) can promote the acid O?H insertion with the maximum turn over number (TON) of 1381, and furthermore, it can be recycled and reused for 10 runs, suggesting that Ir-PMOF-1(Hf) is efficient for this acid involved reaction. Ir-PMOF-1(Hf) can also be miniaturized to nano scale (diameter range of 400–500 nm), and a large improvement with regards to TON (8400) can be observed in its catalysis.

Full text of DOI:10.1002/cctc.201800597

Accepted Article
Title: An Acid Stable Metal-Organic Framework as an Efficient and
Recyclable Catalyst for the O-H Insertion Reaction of Carboxylic
Acids
Authors: Li Zhang, Yingxia Wang, Hao Cui, and Cheng-Yong Su
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10.1002/cctc.201800597
ChemCatChem
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An Acid Stable Metal-Organic Framework as an Efficient and
Recyclable Catalyst for the O-H Insertion Reaction of Carboxylic
Acids
Yingxia Wang, Hao Cui, Li Zhang* and Cheng-Yong Su*
Abstract: Although metal-organic frameworks (MOFs) can be used
in many reactions, their applications in acid involved reactions are
limited due to their instability in acid environment. As a stable MOF,
the Ir(III)-porphyrin metal-organic framework of the formula [(Hf6(3-
porphyrin metal-organic framework (Ir-PMOF-
possesses two types of open cavities (1.9 1.9
1
), which

 1.9 and
3.0

3.0

3.0 nm3) crosslinked through orthogonal
1.9 nm2) in three directions.5a,b The smaller
channels (1.9

O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]solvents
(Ir-PMOF-1(Hf))
can
cavity is surrounded by four Ir(TCPP)Cl walls to form a
catalytic coordination space, where the reactions can be
carried out. Chemical stability study has further disclosed
sustain its structure upon treatments in different pH (0-11) aqueous
solutions. In this work, Ir-PMOF-1(Hf) has been examined in the O-H
insertion reaction of carboxylic acids with diazo compounds.
Catalytic results show that as low as 0.042 mol% of Ir-PMOF-1(Hf)
can promote the acid O-H insertion with the maximum turn over
number (TON) of 1381, and furthermore, it can be recycled and
reused for 10 runs, suggesting that Ir-PMOF-1(Hf) is efficient for this
acid involved reaction. Ir-PMOF-1(Hf) can also be miniaturized to
that Ir-PMOF-1(Hf) can sustain its structure in a wide range
of pH values (0-11) for more than 24 h, suggesting that its
framework can resist acids.
nano scale (diameter range of 400-500 nm), and
a large
improvement with regards to TON (8400) can be observed in its
catalysis.
Introduction
Metal-organic frameworks (MOFs) have emerged as a
kind of modern materials for gas storage, drug delivery,
sensing and catalysis, due to their high surface areas,
stability and porosity, and modular design.1 Especially in
catalysis, MOFs have been used in a range of reactions,
including H2 production,2 CO2 conversion,3 multiple
component coupling,4 X-H (X = C, Si, N, O) insertion,5 and
many other reactions.6 However, their applications in acid
involved reactions are underdeveloped and only a few
papers have been published,7,8 but nevertheless, none of
these works were related to the application of MOFs in the
synthesis of bioactive ɑ-acyloxy carbonyls, which can be
prepared through the O-H insertion reaction of carboxylic
acids with diazocarbonyl compounds.9,10
Figure 1. Chemical stability of Ir-PMOF-1(Hf) in different pH (0-11)
media and the application in the reaction of carboxylic acids and
diazocarbonyl compounds.
Metalloporphyrin complexes of iron, ruthenium, and
rhodium, etc. are known to catalyze X-H (X = C, N, Si) bond
insertion with high efficiency and selectivity.5,11 Our group
has recently discovered that irridium(III) porphyrin
complexes can efficiently promote the O-H insertion of
alcohols and phenols. The incorporation of Ir(TCPP)Cl
Herein, we report the catalytic activities of Ir-PMOF-1(Hf)
in carbene insertion reactions into carboxylic acids, another
important group of compounds containing O-H bonds
(Figure 1). Catalytic results show that Ir-PMOF-1(Hf) is a
(TCPP
=
tetrakis(4-carboxyphenyl)porphyrin) into the
powerful catalyst for the reactions of diazo compounds and
carboxylic acids, which is efficient with as low as 0.04 mol
framework of PCN-224 results in a porous iridium(III)-
[Ir]% of Ir-PMOF-1(Hf) being required in the acid O-H
insertion with the maximum TON of 1381 and recyclable for
ten runs. Remarkably, the catalyst amount can be cut down
to 0.005 mol [Ir]%, and the TON can be increased by 6
[a]
Miss Y. Wang, Dr. H. Cui, Prof. L. Zhang, Prof. C.-Y. Su,
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn
Institute of Functional Materials, School of Chemistry
Sun Yat-Sen University
times, reaching 8400, when the crystallite of Ir-PMOF-1(Hf)
Guangzhou 510275, China
E-mail: zhli99@mail.sysu.edu.cn; cesscy@mail.sysu.edu.cn
is in nano scale (diameter range of 400-500 nm). For
comparison, most of the acid involved reactions are
catalyzed by Uio-667b,g,h or MOF-199 (HKUST-1)7e, in which
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cctc.201800597
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the MOF catalyst amount was more than 10 mol%, the
catalysts can be reused for less than 5 runs.
oxoethyl benzoate (1a) has been produced (Table 1, entries
1 and 2). It is found that in nonpolar solvent n-hexane, no
product can be detected even after 12 h (entry 3). To our
delight, the reaction in toluene can give rise to 60% yield
after 10 min (entry 4). We then explored halogenated
solvents such as DCE and DCM, and found that the
reaction in DCE has moderate yield (31%) in 1.5 h whereas
the reaction in DCM can be largely promoted and the yield
is up to 73% in 10 min (entries 5 and 6). When the catalyst
amount was decreased to 0.4 and 0.042 [Ir] mol%, the yield
is cut down to 68 and 58%, respectively, whereas the
reaction time is much longer (entries 7 and 8). For
comparison, when the catalyst amount is increased to 2.4
mol [Ir] %, the reaction can be finished in 8 minutes, but
however, the yield hasn’t increased (68%, entry 10). Based
on these data, the maximum turn over number (TON) is
calculated to be 1381. Tuning the molar ratio of benzoic
acid and EDA from 1:1, 2:1, 3:1 to 4:1, the best yield of 80%
can be obtained with the 4 times excess of benzoic acid
(entries 6, 10-12). A scale up reaction (up to 1.14 g of EDA)
Results and Discussion
Reaction of benzoic acid and ethyl diazoacetate (EDA)
with the molar ratio of 2:1 and in the presence of 0.8 mol [Ir]%
of Ir-PMOF-
solvent optimization.
dichloromethane (DCM),
1
(Hf) was chosen as the model reaction for
range of solvents, including
1,2-dichloroethane (DCE),
A
acetonitrile (CH3CN), toluene, n-hexane and acetone, have
been examined. Before test, the chemical stability of Ir-
PMOF-
PMOF-
1
1
(Hf) in these solvents has been studied. After Ir-
(Hf) was immersed in these solvents for 3-5 days,
the solvents are still colourless and the powder X-ray
patterns of the catalyst samples remain (Figures S1 and
S2), suggesting that Ir-PMOF-1(Hf) can be used as a
heterogeneous catalyst in these solvents.
Table 1. Reaction Optimation.a
in the presence of 0.16 [Ir] mol% of Ir-PMOF-1(Hf) has
been set up, and the yield is 55% in 5 h (entry 13). It is
noted that, in addition to the O–H insertion products, the
self-coupling reaction products of EDA, i.e. diethyl fumarate
and maleate, accounted for all initial EDA.9
Entry
Molar Ratio of
acid / EDA
Catalyst
Solvent
Time
Yield
(%)
([Ir] mol%)
1
2
2:1
2:1
2:1
2:1
2:1
2:1
2:1
2:1
2:1
1:1
3:1
4:1
2:1
0.8
0.8
acetone
CH3CN
n-hexane
toluene
DCE
3 h
12 h
trace
trace
0
3
0.8
12 h
4
0.8
10 min
1.5 h
10 min
0.5 h
20 h
60
5
0.8
31
6
0.8
DCM
73
7
0.4
DCM
68
8
0.042
2.4
DCM
58
9
DCM
8 min
15 min
9 min
9 min
5 h
66
10
11
12
13b
0.8
DCM
45
0.8
DCM
72
0.8
DCM
80
0.16
DCM
55
Figure 2. Catalytic results with different catalysts.
[a] In each reaction, the amount of EDA is 22.8 mg, and EDA has been
completely consumed. The yields are based on the conversions of
diazoacetates to the O-H insertion products. [b] The amount of EDA is
enlarged to 1.14 g.
Catalytic results of the model reactions in the presence of
different isostructural MOF catalysts such as Ir-PMOF-
1(Hf),
Ir-PMOF- (Zr), Ru-PMOF- (Hf), Rh-PMOF- (Zr), PCN-
1
1
1
224(Hf) and PCN-224(Zr) are shown in Figure 2 and Table
S1.3,5,12 In PCN-224(Hf) and PCN-224(Zr), there is no metal
in the center of the porphyrin ring. The reactions can be
Catalytic results show that, in polar solvents such as
acetone and CH3CN, the reactions were sluggish and only
a trace amount of O-H insertion product 2-ethoxy-2-
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10.1002/cctc.201800597
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accomplished in around 10 min using Ir-porphyrin-based
This protocol can be further applied to other carboxylic
acids (Table 2). As for functionalized benzoic acids, the
yields of the reactions with 4-methylbenzoic acid and 2-
hydroxybenzoic acid are 79 and 57%, respectively (entries
2 and 3). It is noted that the substrate 2-hydroxybenzoic
acid contains two kinds of O-H groups, i.e., from phenols
and carboxylic acids, whereas the insertion reaction
selectively occurs with carboxyl group rather than phenol
group. Similar to benzoic acid, the aromatic acid of
thiophene-2-carboxylic acid can give rise to 74% yield,
although the reaction need much longer time (50 min, Table
2, entry 4). As for the reactions with alkyl acids such as
trifluoroacetic acid (TFA), propionic acid and hexa-2,4-
dienoic acid, they are efficient and the yields are up to 91,
60 and 64%, respectively (entries 6-7). The fast rate (6 min)
and an excellent yield (91%) with regards to TFA may be
due to the electron withdrawing effect of fluorine atom
which makes it more easily for O-H insertion. When the
diazocarbonyl compound was changed from EDA to propyl
diazoacetate (PDA), tert-butyl diazoacetate (BDA), or
benzyl diazoacetate (BnDA), the reactions with benzoic
acid can also occur easily and the yields were in the range
of 63-69% (entries 8-10). These results show a good
MOF catalysts (e.g. Ir-PMOF-1(Hf) and Ir-PMOF-1(Zr)),
which are competent to the corresponding homogeneous
.
catalyst of IrCl(TPP)(CO) and much better than IrCl3 3H2O.
For comparison, Ru-PMOF-1(Hf), Rh-PMOF-1(Zr) and
PCN-224 are all inefficient for this reaction, and the yields
are less than 20% even after 16 h. This group of catalytic
data confirm that the active centers are mainly based on
Ir(III) porphyrins.
Table 2. Substrate Scope.a
Entry
1
Product
Time (min)
Yield (%)
10
15
10
73
79
57
1a
1b
2
3
tolerance of Ir-PMOF-
acyloxy carbonyls through the O-H insertion reaction of
carboxylic acids with diazocarbonyl compounds.
1(Hf) in the synthesis of bioactive ɑ-
1c
1d
1e
1f
Preliminary attempts to expand this catalysis to chiral acids
such as N-sulfonyl prolines and thiazolidine-4-carboxylic
acids have been carried out, and catalytic results disclose
that these chiral acids derived from natural amino acids can
4
5
6
7
8
50
6
74
91
60
64
63
react with EDA in the presence of Ir-PMOF-1(Hf), but
unfortunately, the yields are very low (around 10%, Table
S2).
A plausible reaction mechanism is shown in Figure 3.
The diazocompound EDA firstly reacted with the iridium(III)-
30
40
25
porphyrin within the MOF catalyst of Ir-PMOF-
generate iridium carbene A 13a
which then inserted into the
O-H bonds of carboxylic acids through the ylide
intermediates or
followed by a 1,2-H shift process.13b
1(Hf) to
,
1g
B
C
1h
1i
9
30
20
69
65
10
1j
[a] Reaction conditions: 0.8 mol [Ir]% of the catalyst, 2 mL DCM, and 2:1
molar ration of acid and diazocarbonyl compounds. The yields are based
on the conversions of diazocarbonyl compounds to the O-H insertion
products. In each reaction, diazocarbonyl compounds have been
completely consumed.
Figure 3. A plausible reaction mechanism.
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One of the biggest advantages for Ir-PMOF-
1
(Hf)
experiments confirm the heterogeneous nature of Ir-PMOF-
catalyzed O-H insertion of carboxylic acids lies in that the
catalyst can be isolated easily and reused for more than 10
runs with little loss of its catalytic activity (Figure 4). Before
being reused for the next run, the catalyst only need be
washed with DCM for several times and dried under air.
The longer reaction time after the 7th run is needed (Table
S2), which may due to the residue of benzoic acid or
products in the pores, preventing the approach of reactants
to the active sites and the transmission of products through
the crossing channels. As a result, the smaller substrate
1
(Hf)-catalyzed reactions.
The charming advantages (e.g. high external surfaces
and fast diffusion rate) of nanoscale MOFs inspire us to
reduce the sizes of Ir-PMOF- (Hf) into nano scale, and then
employ the nanocrystalline PMOF in the O-H insertion of
acids.15 The purity and crystallinity of nano Ir-PMOF-
(Hf)
1
1
are related to the concentration of the modulator (e.g.
benzoic acid) and the reaction temperature. When the
molar amount of benzoic acid is 467 (or bigger than 467)
times higher than that of the metalloporphyrin ligand
Ir(TCPP)Cl, microcrystals in the diameter range of 30-50
µm were obtained. On the other hand, when the
EDA transferred easier into the cavities of Ir-PMOF-1(Hf)
and carried out the the unpleasant dimerisation reaction
there. This hypothesis has been confirmed by the smaller
N2 uptake (328 cm3 g-1) and reduced BET surface area
(1162 m2g-1) of Ir-PMOF-
1(Hf) after catalysis (Figures S3
temperatures are in the range of 100-120
℃
,
only
microcrystals can be gotten. Through the optimization, we
found that a 435 : 1 molar ratio of benzoic acid and
and S4). The integrity of the catalyst after catalysis was
showed by the similarity of the PXRD patterns with the
simulated ones of the as-synthesized samples (Figures S5
and S6).
Ir(TCPP)Cl as well as 90
conditions for the formation of nano Ir-PMOF-
scanning electron microscopy (SEM) (Figure 5a, b)
discloses that the prepared Ir-PMOF- (Hf) nanocrystals are
℃
are the optimized reaction
1
(Hf). The
1
block-shaped, whose diameters are in the range of 400-500
nm. The powder X-ray patterns of the as-synthesized
nanocrystals match with those of the simulated ones,
confirming the phase purity (Figure S1). In the presence of
0.005 mol% of the nanoscale Ir-PMOF-1(Hf) (400-500 nm),
the yield for the reaction of benzoic acid and EDA can be
42% after 47 h. Based on this, the turn over number (TON)
can be calculated to be 8400, which is much higher than
the maximum TON (1380) of normal Ir-PMOF-
catalyzed reaction. The morphology and crystallinity of
nano Ir-PMOF- (Hf) can be maintained during catalysis,
1(Hf)-
1
which can be confirmed by SEM (Figure 5), PXRD pattern
(Figure S5) and IR spectra (Figure S8) before and after the
catalytic reaction.
Figure 4. Recycling experiments.
To make sure whether the valence state of Ir in Ir-PMOF-
1
(Hf) has remained after the catalytic reaction, we have
measured the energy-dispersive X-ray spectroscopy (XPS)
of Ir-PMOF- (Hf) before and after catalysis. Two intense
1
peaks around 65.3 and 62.3 eV, which are assignable to Ir
4f5/2 and Ir 4f7/2, respectively, appear in the XPS spectrum
of Ir-PMOF-1
(Hf) after the reaction (Figure S7).14 It
suggests that the valence of Ir is still +3. The XPS result
shows the atomic ratio of Hf : Ir : Cl after catalysis is 0.96 :
0.25 : 0.27 (Table S4), which closely matches the ratio of 4 :
1 : 1 determined from the single-crystal data. Moreover, a
negligible amount of iridium (less than 0.18% of the total Ir
Figure 5. SEM of nano Ir-PMOF-1(Hf) before catalysis (a, b) and after
content in Ir-PMOF-1(Hf)) leaching into the reaction solution
catalysis (c, d).
was detected by inductively coupled plasma optical
emission spectroscopy (ICP-OES) analysis. These
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10.1002/cctc.201800597
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Conclusions
was stirring in DCM (1 mL), and then EDA (22.8 mg, 0.2 mmol, 1 eq)
was added slowly into the above mixture through syringe. The
resulting reaction mixture was stirring at room temperature for 10
min, until no EDA was detected by TLC. The catalyst was
centrifuged, washed with DCM (5 mL × 5), and dried under air
before being reused in the consecutive runs. The combined
supernatant was evaporated to dryness and the conversion (73%)
of the reaction was tested by 1H NMR spectroscopy. The crude
residue was purified by flash chromatography to afford pure product
2-ethoxy-2-oxoethyl benzoate (1a), 1H NMR (400 MHz, CDCl3) δ
8.13 (d, 2H, J = 7.5 Hz), 7.62 (t, 1H, J = 7.4 Hz), 7.49 (t, 2H, J = 7.7
Hz), 4.87 (s, 2H), 4.29 (q, 2H, J = 7.1 Hz), 1.31 (m, 3H). HRMS
([M+Na]) Calcd. for C11H12O4: 231.0627; Found: 231.0628.
In summary, we have discovered an acid stable MOF
catalyst, Ir-PMOF-
carboxylic acids with diazo compounds. Catalytic results
show that Ir-PMOF- (Hf) can be simply recycled and
1(Hf), for the O-H insertion reaction of
1
reused for at least 10 runs. Furthermore, it can sustain its
framework after the catalytic reactions. We have further
prepared nanoscale crystallite Ir-PMOF-1(Hf) with
diameters in the range of 400-500 nm and employed it into
the O-H insertion reaction, finding that as high as 8400 of
TON was achieved. The further researches to explore the
properties and catalytic applications of nanoscale PMOFs
are in the process.
Recycling experiments
EDA (182.4 mg, 1.6 mmol, 1 eq) was added slowly to the
mixture of benzoic acid (390.4 g, 3.2 mmol, 2 eq) and activated Ir-
Experimental Section
PMOF-1(Hf) (24.8 mg, 0.013 mmol, 0.8 mol [Ir]%) in DCM (16 mL).
The resulting suspension was stirred at room temperature until all
EDA was completely consumed. The undissolved catalyst was
removed through centrifugation, and washed with fresh DCM (8 mL
× 4). The combined supernatant was evaporated to dryness, and
the residue was dissolved in CDCl3 and analyzed by 1H NMR to
determine the yield of 1a. The recycled catalyst was collected, air-
dried and then used for the successive runs.
General.
All the reagents in the present work were obtained from
commercial sources and used directly without further purification.
Synthesis of (Hf6(
3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3solvents (Ir-
PMOF- (Hf)) was according to the procedure of our published work
1
(Figure S1).5 1H NMR were recorded on Bruker AVANCE III
400MHz. 13C NMR were recorded on Bruker AVANCE III 101MHz.
HRESI-MS was performed by using a Bruker Daltonics ESI-Q-TOF
maxis4G. PXRD patterns were recorded on Smartlab X-ray powder
diffractometer (Rigaku Co.) at 40 kV and 30 mA with a Cu target
tube. Thermogravimetric (TG) analyses were performed under an
ICP Spectrometric Evaluation
After the catalytic reaction was complete, the catalyst was
separated by centrifugation and washed with fresh DCM (5 mL × 5).
The combined solution was further filtered with membrane filter
(0.22 μm) for 3 times, and then the filtrate was concentrated to
around 1 mL by heating. Afterwards, 30 mL of aqua regia was
added, and the resulting solution stayed at room temperature for 1
air atmosphere at a heating rate of 2
℃
min-1 by using a NETZSCH
TG 209 system. X-ray photoelectron spectroscopy (XPS) was
performed on a ULVAC PHI Quantera microprobe. Binding energies
(BE) were calibrated by setting the measured BE of C 1s to 284.65
eV. ICP spectroscopy was conducted on a Spectro Ciros Vision
ICP-OES spectrometer that is equipped with vacuum optics
covering the spectral range from 175-777 nm, plasma power, 1300
w; coolant flow, 15.00 L/min; auxiliary flow, 0.80 L/min; nebulizer
0.70 L/min. The sorption isotherms for N2 (77K) gas were measured
with an Autosorb-iQ2-MP gas sorption analyzer (Quantachrome
USA).
day. After that, the mixture was heated at 150
℃ to remove most of
the solvent, and the residue was treated with hydrochloric acid (21
mL) and nitric acid (7 mL). After standing at room temperature for
another 4 h, the resulting solution was heated at 150
℃ again until
only 1 mL mixture was left. This digestion procedure was repeated
until the residue solution was transparent after H2O was added. The
resulting mixture was diluted volumetrically with an aqueous
solution of nitric acid (2%) to 25 mL, to obtain a colorless solution,
which was then measured by inductively coupled plasma optical
emission spectrometer (ICP-OES) for the Ir and Hf contents. The
measured Ir and Hf contents were 0.09 ppm and 0.16 ppm,
corresponding to 0.18% and 0.07% leaching, respectively.
Caution! Although we have not experienced any problem in the
handling of the diazo compounds, extreme care should be taken
when manipulating them due to their explosive nature.
Typical procedure for the reaction of carboxylic acid and
diazocarbonyl compound
Synthesis of nanoscale Ir-PMOF-1(Hf)
Ir(TCPP)Cl (5 mg, 4.9

10-2 mmol), benzoic acid (260 mg, 2.12 mmol) and

10-3 mmol), HfCl4 (15 mg,
Prior to gas adsorption or catalysis, Ir-PMOF-1(Hf) was
4.7
activated via the following procedure: The as-synthesized crystals
were immersed in acetone for 2 days, and then the solvent was
changed with fresh solvent for 3 times. Afterwards, the sample was
dimethylformamide (DMF, 3 mL) were placed in a 20 mL glass vial,
which was then sealed and stirred at 90 °C for 14 h, after that the
suspension was cooled to room temperature and centrifuged at
12000 rpm for 15 minutes. Afterwards, the upper transparent
solvent was transferred to another 10 mL glass vial and heated at
120°C in an oven. After 3 h, red block crystallites of 400-500 nm
heated at 120
℃ under vacuum for 12 h to remove the adsorbed
solvents in the cavities.
A mixture of benzoic acid (48.8 mg, 0.4 mmol, 2 eq) and
activated Ir-PMOF-1(Hf) (3.1 mg, 0.0016 mmol [Ir], 0.8 mol [Ir]%)
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A. R. Oveisi, ChemCatChem 2017, 9, 1992-2000.
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(KBr) ν 3402 (br), 1710 (w), 1634 (w), 1604(s), 1549 (s), 1422 (s),
1371 (m), 1354 (m), 1176 (w), 1016 (s), 821 (w), 791 (m), 774 (m),
715 (s), 668 (m), 597 (w), 550 (w), 503 (w) cm-1.
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Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21773314, 21720102007), Natural
Science Foundation of Guangdong Province (S2013030013474)
and the Fundamental Research Funds for the Central
Universities (16lgjc68, 17lgjc12).
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Keywords: Iridium Porphyrin Metal-Organic Framework •
Heterogeneous Catalysis • O-H Insertion • Nano Crystallite
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10.1002/cctc.201800597
ChemCatChem
FULL PAPER
FULL PAPER
Yingxia Wang, Hao Cui, Li Zhang* and Cheng-Yong Su*
Page 1. – Page 6.
An Acid Stable Metal-Organic Framework as an Efficient and
Recyclable Catalyst for the O-H Insertion Reaction of
Carboxylic Acids
Acid-Resistant MOF Catalyst: As a stable MOF in different pH (0-11) aqueous solutions, the Ir(III)-porphyrin metal-organic
framework of the formula [(Hf6(3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]solvents (Ir-PMOF-1(Hf)) can promote the O-H insertion reaction of
carboxylic acids with diazo compounds with the maximum turn over number (TON) of 1381. Furthermore, Ir-PMOF-1(Hf) can be
miniaturized to nano scale (diameter range of 400-500 nm), and a much higher TON (8400) can be achieved in the catalysis.
This article is protected by copyright. All rights reserved.