A stable and porous iridium(III)-porphyrin metal-organic framework: Synthesis, structure and catalysis

Article abstract of DOI:10.1039/c6ce00358c

Self-assembly of a new metalloporphyrin tetracarboxylic ligand Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with ZrCl₄ in the presence of benzoic acid leads to the formation of a three-dimensional (3D) iridium(III)-porphyrin metal-organic framework (Ir-PMOF) with the formula of [(Zr₆(μ₃-O)₈(OH)₂(H₂O)₁₀)₂(Ir(TCPP)Cl)₃]·solvents (Ir-PMOF-1(Zr)), which possesses square-shaped channels of 1.9 × 1.9 nm² (atom-to-atom distances across opposite Ir metal atoms) in three orthogonal directions as disclosed by the single-crystal X-ray diffraction analysis. Ir-PMOF-1(Zr) represents the first MOF bearing a self-supporting iridium-porphyrin catalytic framework, featuring high porosity and stability. The catalytic tests disclose that the activated Ir-PMOF-1(Zr) can promote O-H insertion with a turnover frequency (TOF) up to 4260 h^-1. Ir-PMOF-1(Zr) can be recycled and reused for 10 runs without significant loss of catalytic activity, and the total turnover number (TON) for O-H insertion after 10 successive runs reaches 875.

Full text of DOI:10.1039/c6ce00358c

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PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
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DOI: 10.1039/C6CE00358C
Journal Name
ARTICLE
A Stable and Porous Iridium(III)-Porphyrin Metal-
Organic Framework: Synthesis, Structure and
Catalysis
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
ab
Hao Cui, Yingxia Wang, Yanhu Wang, Yanzhong Fan, Li Zhang,* and Cheng‐Yong Su*
DOI: 10.1039/x0xx00000x
Self‐assembly of a new metalloporphyrin tetracarboxylic ligand Ir(TCPP)Cl (TCPP = tetrakis(4‐carboxyphenyl)porphyrin)
with ZrCl in the presence of benzoic acid leads to the formation of a three‐dimensional (3D) iridium(III)‐porphyrin metal‐
www.rsc.org/
4
organic framework (Ir‐PMOF) with the formula of [(Zr
6
(
3
‐O)
8
(OH)
2
(H
2
O)10
)
2
(Ir(TCPP)Cl)
3
]solvents (Ir‐PMOF‐1(Zr)), which
2
possesses square‐shaped channels of 1.9  1.9 nm (atom‐to‐atom distances across opposite Ir metal atoms) in three
orthogonal directions as disclosed by the single‐crystal X‐ray diffraction analysis. Ir‐PMOF‐1(Zr) represents the first MOF
bearing the self‐supported iridium‐porphyrin catalytic framework, featuring in high porosity and stability. The catalytic
‐1
tests disclose that the activated Ir‐PMOF‐1(Zr) can promote O‐H insertion with the turnover frequency (TOF) up to 4260 h .
Ir‐PMOF‐1(Zr) can be recycled and reused for 10 runs without significant loss of catalytic activity, and the total turnover
number (TON) for O‐H insertion after 10 successive runs reach 875.
of metalloporphyrin is often challenging and low‐yielding.
Second, metalloporphyrins are prone to oxidative self‐
destruction of the catalyst under very strong oxidizing
INTRODUCTION
Metal‐catalyzed carbene transfer reactions have been widely1
medium. To make better use of metalloporphyrin catalysis,
one approach is to immobilize the metalloporphyrin catalyst
used for the construction of valuable compounds.
2
3
4
Metalloporphyrin complexes of iron, cobalt, ruthenium, and
9
5
onto an organic or inorganic polymer. Immobilization onto a
rhodium, etc. are known to catalyze olefin cyclopropanation,
solid support enables the catalysts to be easily recovered and
reused, and also reduces the metalloporphyrin degradation.
Another alternative immobilization method is to integrate
metalloporphyrin onto the backbones of metal‐organic
and further, X‐H (X = C, N, Si) bond insertion with high
efficiency and selectivity. For example, Rh‐porphyrin
complexes furnish cyclopropanation and C‐H insertion
products with unusual selectivity for cis‐cyclopropanes and
primary insertion products , respectively. Fe‐ and Ru‐
porphyrins can catalyze the N‐H insertion of ammonia and
peptide containing N‐terminal amine, respectively. Compared
to other group 8 and group 9 metals, the reactivity of iridium‐
porphyrins toward carbene transfer has been much less
explored. Recently, intermolecular cyclopropanation and
5
a
1
0
5b
frameworks (MOFs).
Since MOFs possess uniform,
2
continuous and permeable channels, construction of porous
MOFs by using metalloporphyrin ligands can directly install
these active sites on the pore surface and facilitate
transportation of reactants/products to or from inner reactive
vessels. Unlike immobilized metalloporphyrin catalysts onto an
organic/inorganic polymer, porphyrinic MOFs lack non‐
accessible bulk volume and can act as single‐site catalysts with
4
6
7
carbene X‐H bond insertion have been reported by Woo, Che
and Rodríguez‐García using Ir‐porphyrin catalysts.
8
1
1‐29
1
00% utility of active sites.
Nevertheless, there are two major disadvantages
associating with metalloporphyrin catalysis. First, the synthesis
Despite the availability of a large number of porphyrinic
MOFs, none of them has embedded iridium‐porphyrin
complexes as the building blocks, which are known to show
catalytic potentials in carbene transfer reactions such as
a.
6‐8
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of
cyclopropanation and N‐H insertion. We have long been
Functional Materials, School of Chemistry and Chemical Engineering, Sun Yat‐sen
University, Guangzhou 510275, China. E‐mail: zhli99@mail.sysu.edu.cn;
cesscy@mail.sysu.edu.cn
working in the field of carbene/nitrene transfer reactions, and
are interested to develop efficient while recyclable Ir‐
b.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic
30,31
porphyrin catalysts to accomplish such catalysis.
According
Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
†
Electronic supplementary information (ESI) available: Crystal structure data,
to above discussion, we believe that a promising way is to
construct iridium(III)‐porphyrin metal‐organic frameworks (Ir‐
PMOFs) as the self‐supported Ir‐porphyrin catalysts. Herein,
we report, to the best of our knowledge, the first Ir‐porphyrin
physical characterizations, chemical/thermal stability study, and dye adsorption
of porphyrinic MOFs, recycling experiments, ICP spectrometric evaluation of
metal leaching, and NMR data of O‐H insertion products. CIF files giving
crystallographic data. CCDC 1436270. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/x0xx00000x.
MOF, Ir‐PMOF‐
1(Zr), which is highly porous and stable, and is
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ARTICLE
Journal Name
efficient in the carbenoid insertion reactions into O‐H bonds were removed under reduced pressure. The crude product as
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DOI: 10.1039/C6CE00358C
(Scheme 1).
red precipitate was obtained after 1 M HCl was added to the
aqueous suspension. Until no further precipitate was detected
(
(
(
(
pH~2), the crude product was collected, washed with water
60 mL), and dried in vacuum. The yield is 90 mg (81%). H NMR
Scheme 1. Ir‐PMOF‐1(Zr) Synthesis.
1
400 MHz, CD OD)

8.80 (s, 8 H), 8.44 (d, 2 H, J = 8 Hz), 8.33
3
d, 2 H, J = 8 Hz). FT‐IR (KBr) ν 3413 (br), 1698 (s), 1605 (s),
1
1
536 (w), 1407 (m), 1355 (m), 1255 (s), 1175 (m), 1102 (m),
‐
1
016 (s), 792 (s), 711 (m) cm . HRMS (ESI): m/z 981.1522 [M‐
+
+
CO‐Cl] for [C H N O Ir] (Calc. 981.1534). UV‐vis (THF, max
,
48
28
4
8
(
log
Synthesis of [(Zr
PMOF‐1(Zr)). Ir(TCPP)Cl (6 mg, 5.9
)) 409 nm (5.07), 531 nm (3.96).
6
(
3
‐O)
8
5
(OH) (H
2
O)
7
)
2
(Ir(TCPP)Cl)
3
]solvents (Ir‐
‐
3

4
10 mmol), ZrCl (10 mg,
0
.04 mmol), benzoic acid (300 mg, 2.45 mmol) and
dimethylformamide (DMF, 1 mL) were placed in a glass vial,
which was then sealed and heated to 120 °C in an oven. After
4
8 h, red block crystals were obtained (6 mg, 64% yield based
on Ir(TCPP)Cl) and air‐dried. Anal. Calcd. For [(Zr6( 3
O) (OH) (H O) ) (Ir(TCPP)Cl) ] 8(C H COOH) 4DMF
C212H189Cl Ir N O Zr ): C, 41.84 H, 3.38; N, 3.69. Found: C,

‐
8
2
2
10 2
3 16 84 12
3

6 5

(
3
4
1.84; H, 3.12; N, 3.57%. FT‐IR (KBr) ν 3394 (br), 1601 (s), 1551
‐
1
(
s), 1404 (s), 1015 (m), 718 (m), 652 (m) cm .
EXPERIMENTAL SECTION
General Information. All the reagents in the present work were
obtained from the commercial source and used directly
without further purification. The ligand 5,10,15,20‐tetrakis(4‐
methoxycarbonylphenyl)porphyrin
synthesized according to the literature.
Single X‐ray Crystallography. The X‐ray diffraction data was
collected with an Agilent Technologies SuperNova X‐RAY
diffractometer system equipped with Cu‐k
 radiation ( =
1
.54178 Å). The crystal was kept at 150.0(1) K during data
(TCPPCO Me)
was
2
28
collection. The structure was solved with the SIR2004
structure solution program integrated in Olex2 using Direct
Methods, and refined with the XH refinement package using
Cautions! Although we have not experienced any problem in
the handling of the diazo compounds (e.g. ethyl diazoacetate
33a
CGLS minimisation. The final refinement was performed by
(
EDA)), extreme care should be taken when manipulating them
due to their explosive nature.
Synthesis of Ir(TCPPCO Me)(CO)Cl. Iridium porphyrin complex apparent disorder over two closely adjacent positions;
Ir(TCPPCO Me)(CO)Cl was prepared according to a similar however, adequate treatment of this disorder by splitting all
33b
SHELXL‐2014/7 (Sheldrick, 2014) imbedded in WINGX.
The
main coordination framework in the crystal lattice show
2
2
7
,32
procedure:
TCPPCO Me (100 mg, 11.8 mmol) and atoms into two parts seems troublesome due to high crystal
2
[
Ir(COD)Cl] (100 mg, 14.9 mmol) in 1,2,4‐tricholorobenzene symmetry. Therefore, the refinement was restricted to one set
2
(
20 mL) was stirred at 190 C. After 1 day, the solvent was of molecules by using DIFX to constrain porphyrin ligand.
removed under reduced pressure. The crude reaction mixture ISOR/SIMU was applied to all non‐hydrogen atoms to simulate
was purified on silica using a mixture of DCM and EtOAc as the isotropic behaviours. Even though, ADP max/min ratios,
eluent to afford the product as a red solid (106 mg, 82% yield especially for Ir and Zr atoms, are not prevented. All solvent
1
33c
based on TCPPCO Me). H NMR (400 MHz, CDCl )
3

8.90 (m, 8 molecules have been removed by SQUEEZE program. The
H), 8.46 (m, 8 H), 8.33 (m, 8 H), 4.10 (s, 12 H). C NMR (100 positions of the hydrogen atoms are generated geometrically.
MHz, CDCl3) 167.33, 145.70, 140.94, 134.70, 134.40, 132.28, A summary of the crystal structure refinement data and
30.30, 128.45, 128.27, 121.60, 52.75. FT‐IR (KBr) ν 3428 (br), selected bond angles and distances are listed in Table S1 and
058 (s), 1724 (s), 1607 (s), 1537 (w), 1435 (m), 1401 (w), 1278 Table S2.
2
1
3

1
2
(
(
s), 1185 (w), 1111 (s), 1020 (s), 965 (w), 867 (w), 823 (w), 797
Typical Procedure for O‐H Insertion. A solution of EDA (34.2 mg,
.3 mmol, 1.0 eq) was added slowly to the solution of
isopropanol (90 mg, 1.5 mmol, 5.0 eq) and activated Ir‐PMOF‐
(Zr) (4.7 mg, 0.003 mmol, 1 mol [Ir]%) in DCM (1 mL). The
‐
1
w), 765 (m), 712 (m) cm . HRMS (ESI): m/z 1037.2142 [M‐CO‐
0
+
+
Cl] for [C H N O Ir] (Calc. 1037.2161). UV‐vis (THF, max
,
5
2
36
4
8
(log)) 419 nm (5.30), 531 nm (4.22).
1
Synthesis of Ir(TCPP)Cl. Ir(TCPP)Cl was prepared via the resulting solution was stirred at room temperature for 10 min
hydrolysis of the obtained Ir(TCPPCO Me)(CO)Cl according to a until EDA was completely consumed. The undissolved catalyst
2
2
8
similar procedure: The obtained ester (120 mg) was stirred in was removed through centrifugation, and washed with DCM (1
a mixture of THF (6 mL) and MeOH (6 mL), to which a solution mL) and acetone (1 mL × 3). The combined supernatant was
of KOH (100 mg) in H O (6 mL) was added. This mixture was evaporated to dryness, and the residue was dissolved in CDCl3
2
1
refluxed for 5 h. After the reaction mixture was cooled down and analysed by H NMR to determine the conversion of EDA
1
to room temperature, the organic solvents (e.g. THF, MeOH) to the alkoxyacetate 2a (94%). H NMR (400 MHz, CDCl ) of
3
2
| J. Name., 2012, 00, 1‐3
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2
2a: δ 4.18 (q, J = 7.2 Hz, 2H), 4.03 (s, 2H), 3.68 (m, 1H), 1.25 (t, each Zr atom is further occupied by two terminal OH (or H O)
DOI: 10.1039/C6CE00358C
J = 7.2 Hz , 3H), 1.22 (d, J = 6.1, 1.3 Hz, 6H).
and each Zr face is capped by a 3‐O atom. As shown in Figure
3
1
a, six edges of the Zr octahedron are bridged by carboxylates
6
from six different 4‐connecting Ir(TCPP)Cl ligands (Figure 1b),
imposing a D3d symmetry to furnish the 3D framework of Ir‐
RESULTS AND DISCUSSION
PMOF‐
channels of 1.9
opposite Ir metal atoms) intercross in three orthogonal
directions. It is worthy to mention that, due to high crystal and
molecular symmetry, exactly identifying O , OH and H O
1
(Zr) (Figure 1c, d), in which the same square‐like
The general synthesis methods of Ir‐porphyrins start from the

1.9 nm (atom‐to‐atom distances across
reaction of [Ir(COD)Cl] and porphyrin ligands, and offer the
2
product Ir(Por)(CO)Cl of which the central Ir(III) atom shows
6‐8,32
saturated six‐coordination mode.
The presence of a
2‐
‐
kinetically inert CO ligand bound to the Ir atom reduces the
activities of Ir(Por)(CO)Cl. Through the reaction of a 1:1.2
2
groups involved in coordination with Zr cluster is impossible
6
solely depending on the single‐crystal analysis, because the
statistical nature of the diffraction result averages the
distances between difference Zr‐O bonds. Nevertheless, based
on the chemical compositions and metal charges determined
from EDS, XPS and elemental analyses, we speculate a formula
molar ratio of TCPPCO Me and [Ir(COD)Cl]2 in 1,2,4‐
tricholorobenzene at 190C for 1 day, Ir(TCPPCO Me)(CO)Cl
2
can be prepared. To our delight, hydrolysis of
2
Ir(TCPPCO Me)(CO)Cl in a solution of KOH led to the formation
2
of Ir(TCPP)Cl in which the bound CO was removed (Scheme 2).
As a new class of Ir‐porphyrins, the coordinatively unsaturated
Ir(Por)Cl has an potential to exhibit excellent catalytic activities.
The absence of CO in Ir(TCPP)Cl is evident from the
of [Zr6(3‐O) (OH) (H O) ) (Ir(TCPP)Cl) ] for the coordination
8
2
2
10 2
3
framework, in which the 3‐O oxygen atoms are most probably
2
‐
O
(Zr‐O, 2.058‐2.154 Å), while terminal 1‐O oxygen atoms
‐
are statistically distributed OH and H O which are
disappearance of

(C=O) in its FT‐IR spectrum, whereas the
2
‐
indistinguishable (Zr‐O, 2.263 Å). For Ir centers, half of axial
spectrum of Ir(TCPPCO Me)(CO)Cl shows this peak (~ 2058 cm
2
‐
1
34
positions are vacant while the rest are coordinated by Cl
)
due to the presence of Ir‐CO bond (Figure S1).
anions. The powder X‐ray diffraction (PXRD) patterns of bulk
samples of Ir‐PMOF‐1(Zr) closely match the simulated one
from its single‐crystal data (Figure S5), indicative of
satisfactory phase purity of the product.
Scheme 2. Ir‐Porphyrin Ligand Synthesis.
Reaction of ZrCl and Ir(TCPP)Cl in the presence of benzoic
4
acid in DMF at 120

C for 48 h yielded red block crystals of
solvents (Ir‐PMOF‐ (Zr)).
Both of EDS and XPS analyses suggested that the atomic ratio
of Zr : Ir : Cl is around 4 : 1 : 1 in Ir‐PMOF‐ (Zr) (Figures S2 and
[
Zr6(3‐O) (OH) (H O) ) (Ir(TCPP)Cl) ]
3

1
8
5
2
7 2
Figure 1. Crystal structures of Ir‐PMOF‐1(Zr): (a) the 6‐connected Zr
6
1
cluster; (b) the 4‐connected Ir‐porphyrin ligand Ir(TCPP)Cl; (c) and (d)
the 3D framework showing open channels (the axial Cl atoms are
removed for clarity). Ir (dark red), Zr (teal), N (blue), O (red), Cl
S3; Tables S3 and S4). XPS spectrum displayed two intense
peaks at 62.4 and 65.4 eV, assignable to Ir 4f7/2 and Ir 4f5/2,
35
respectively, indicative of the +3 valence nature of Ir. In the
(bright green) and C (gray).
‐
1
range of 1900‐2200 cm in its FT‐IR spectrum, there is no
characteristic peak of the carbonyl stretching, confirming the
absence of CO in the axial position of the Ir(III) atom (Figure
It has been discovered that the coordination environment
3
4,35
around the Zr6 cluster could be tuned by adjusting the
reactions conditions such as the ratio of Zr(IV) salt to porphyrin
ligand and the amount of modulating reagent such as benzoic
S4).
Single‐crystal X‐ray diffraction studies reveal that Ir‐PMOF‐
1
(Zr) crystallizes in cubic space group Im‐3m, and is an
13,24,25,28
2
8a
acid and acetic acid (Table S5).
So far, several typical
isostructure of PCN‐224. Six Zr(IV) atoms connect eight 3
‐
topology nets containing Zr6 clusters, including (4,12)‐
oxygen atoms to form a Zr O octahedron cluster, in which
6
8
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ARTICLE
connected ftw‐a net in PCN‐228 (or CPM‐99 , FJI‐H6 ), (4‐
Journal Name
(Zr), N adsorption
2
8c
8b
13
24
To evaluate the porosity of Ir‐PMOF‐
1
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2
2
25
DOI: 10.1039/C6CE00358C
8
)‐connected csq net in PCN‐222 (or MOF‐545 ) and (4,6)‐ isotherms at 77 K were measured (Figure 3). Prior to sorption
28a
connected she net in PCN‐224 , have been constructed examination, the samples are subjected to solvent exchange
based on tetracarboxylated porphyrin ligands. It should be with acetone for 5 days and activated by heating at 120 °C
noted that the 12‐connected Zr clusters and TCPP ligands are under vacuum for 18 h. The N adsorption of Ir‐PMOF‐1(Zr)
6
2
difficult to form ftw‐a network due to the steric effect shows typical type‐I isotherm, in accord with micro‐porosity
between the porphyrin ring and the phenyl ring. Alternatively, identified by the single‐crystal analysis. The N uptake is 705
2
3
‐1
3
the 12‐connected Zr clusters behave as the building units in cm g (STP), and the calculated total pore volume is 1.09 cm
or the elongated g . The Brunauer‐Emmet‐Teller (BET) surface area is estimated
porphyrinic TCBPP (tetrakis(4‐carboxybiphenyl)porphyrin) to be 2637 m g , which is comparable with the value of
ligands are used to construct ftw‐a net as in PCN‐228 (or CPM‐ isostructural PCN‐224(Ni) (2600 m g ). The theoretical BET
9, FJI‐H6). Ir‐PMOF‐ (Zr) has the same (4,6)‐connected surface and pore volume of Ir‐PMOF‐ (Zr) are calculated to be
topology as PCN‐224, and the lower connectivity is resulted 2625 m g and 1.40 cm g , respectively, by Materials Studio
8
2
8d
‐1
ftw‐a net as represented in PCN‐221,
2
‐1
2
‐1 28
9
1
1
2
‐1
3
‐1
3
6
from the relatively high ZrCl / Ir(TCPP)Cl ratio, i.e. 7.2:1. When 6.1.
4
this Zr/porphyrin ratio was decreased to 4.4:1, red cubic
crystals of Ir‐PMOF‐
poor crystal data, its crystal structure couldn’t be well refined.
Single‐crystal study shows that Ir‐PMOF‐ (Zr) crystallizes in
space group Pm‐3m, and is an isostructure of PCN‐221 (Figure
S6). It should be noted that Ir‐PMOF‐ (Zr) has been obtained
in much shorter reaction time (8‐12 h for Ir‐PMOF‐ (Zr) vs. 48
h for Ir‐PMOF‐ (Zr)), which might indicate that Ir‐PMOF‐ (Zr)
(Zr) was
2(Zr) were obtained (Table S5). Due to the
2
2
2
1
2
was kinetically favoured phase, whereas Ir‐PMOF‐
thermodynamically favoured phase.
1
2
Figure 3. N and CO gas adsorption‐desorption isotherms of Ir‐
PMOF‐1(Zr) at 77 K.
Capturing or adsorbing carbon monoxide is of importance
due to its high toxicity and poison effect in catalysis and fuel
cells. A high affinity to CO was rarely observed for metal‐
Figure 2. Thermal and chemical stability study of Ir‐PMOF‐1(Zr): (a)
the variable‐temperature PXRD patterns from 30 to 250C; (b) the
PXRD patterns upon treatments in different solvents.
37
organic materials. It has been reported that a rhodium‐based
MOF DUT‐82 (DUT = Dresden University of Technology) has an
especially high CO adsorption capability, which can adsorb as
3
‐1
high as 800 cm g of CO at 77 K (0.59 bar). The CO storage
capability of Ir‐PMOF‐ (Zr) has been examined (Figure 3). At 77
1
Ir‐PMOF‐
thermal gravimetric (TG) curve of the air‐dried Ir‐PMOF‐
sample displays a gradual weight loss up to 370 C, indicating
that the solvated molecules are evacuated slowly upon heating
Figure S7). The thermal stability of Ir‐PMOF‐ (Zr) has been
1(Zr) crystals exhibit high thermal stability. The
3
‐1
K and 0.57 bar, the CO uptake reaches 1029 cm g ,
corresponding to about 73 CO molecules adsorbed per subunit
of (Ir(TCPP)Cl).
1(Zr)

(
1
The transportation ability through the large channels in Ir‐
further testified by the variable temperature PXRD PMOF‐
measurements, indicating that the framework can sustain organic dyes, i.e. orange gelb (OG, 15.6
heating up to 240C (Figure 2a). Moreover, Ir‐PMOF‐1(Zr) methylene blue (MB, 16.3  7.9  4.0 Å ), are chosen for the
possesses excellent chemical stability. The PXRD monitoring of adsorption measurements. MB and OG have similar size but
1(Zr) has been evaluated by the dye uptake test. Two
3

10.1
 5.4 Å ) and
3
3
8
the fresh crystals immersed in common organic solvents such different charges. MB is a cationic dye, whereas OG is an
i
as isopropanol ( PrOH), acetonitrile (CH CN), hexane, toluene, anionic dye. The adsorption amounts of the dye per gram of Ir‐
3
dichloromethane (DCM), and water (H O) for several days PMOF‐1(Zr) for OG and MB are estimated to be 7.2 and 58.4
2
‐
1
confirmed that the coordination framework was intact (Figures mg g , respectively (Figure S9), suggesting that the large
2
2
b and S8a‐f).
channels (19  19 Å ) of Ir‐PMOF‐1(Zr) are permeable and able
to transport bulky organic molecules. The difference in
4
| J. Name., 2012, 00, 1‐3
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Journal Name
adsorbed amounts of these two dyes might partly be explained
ARTICLE
View Article Online
DOI: 10.1039/C6CE00358C
39
by the acidity of the node –OH and –OH sites.
Table 1. Catalytic O‐H Insertion.
2
The insertion into polar X‐H bonds (X = N, O, S) has attracted
a lot of interests since Merck’s commercial synthesis of the
antibiotic thienamycin using dirhodium complex to catalyze
4
0
the carbenoid insertion into the N‐H bonds of
‐lactams.
Copper and dirhodium complexes are the most common
catalysts, whereas a few other metals (e.g. Fe, Ru, Pd, In, Re)
a
Entry
Catalyst
Substrate
Product
Yield
%)
88
4
1
(
have been occasionally used in X‐H insertion reactions. To
our surprise, no Ir‐based catalysts have been reported in the
insertion reaction of a carbene into the O‐H bond, while there
i
1
2
3
Ir(TPP)(CO)Cl
PrOH
2a
2a
2a
2a
2a
2a
i
Rh
2
(OAc)
4
PrOH
83
94
33
71
77
80
87
56
6,42
are two examples of Ir‐catalyzed N‐H insertions.
i
Ir‐PMOF‐1(Zr)
Ir(TPP)(CO)Cl
Ir‐PMOF‐1(Zr)
Ir‐PMOF‐1(Zr)
Ir‐PMOF‐1(Zr)
Ir‐PMOF‐1(Zr)
Ir‐PMOF‐1(Zr)
PrOH
To examine the catalytic capability of iridium(III) porphyrins
in O‐H insertion reactions, a homogeneous catalyst of
Ir(TPP)(CO)Cl (TPP = tetraphenylporphyrin) was prepared and
b
i
4
PrOH
b
i
5
c
PrOH
i
then employed in the O‐H insertion reaction of isopropanol
6
PrOH
i
(
PrOH) with ethyl diazoacetate (EDA), where the molar ratio of
7
8
9
MeOH
EtOH
2b
2c
3a
catalyst : EDA : iPrOH is 0.01 : 1 : 5. After the reaction
proceeded in DCM at room temperature for 10 min, all of EDA
was consumed and the conversion of EDA into alkoxyacetate
2
a
was 88% (Table 1, entry 1). Under the similar reaction
condition but using dirhodium acetate (Rh (OAc) ) as the
2
4
10
Ir‐PMOF‐1(Zr)
Ir‐PMOF‐1(Zr)
3b
3c
63
70
catalyst instead of Ir(TPP)(CO)Cl, the conversion of EDA to 2a
was 83% (entry 2). These catalytic results suggest that
iridium(III) porphyrins have compatible capability as the
acknowledged powerful O‐H insertion catalysts, i,e. Rh (OAc) .
11
2
4
a
Reaction conditions: 1 mol [Ir]% of the catalyst, 10 min. The
yields are based on the conversions of EDA to the O‐H
insertion products. Reaction time: 1min. Catalyst amount:
To our delight, the self‐supported MOF catalyst Ir‐PMOF‐
(Zr) can even increase the conversion up to 94% (entry 3)
1
b
c
under the heterogeneous reaction condition. In the first 1 min,
the conversions into 2a in the presence of Ir(TPP)(CO)Cl and Ir‐
0
.1 mol [Ir]%.
PMOF‐
indicating the heterogeneous catalyst Ir‐PMOF‐
excellent initial rate. The superior activity of Ir‐PMOF‐
may be ascribed to the vacant coordination sites on the axial before and after catalytic reactions (Figure S7), the crystal
positions of the central Ir atoms. Moreover, the large and framework of Ir‐PMOF‐ (Zr) remains stable after the catalytic
1(Zr) were 33% and 71%, respectively (entries 4 and 5),
1(Zr) has an
The high stability of Ir‐PMOF‐1(Zr) makes it a robust
1
(Zr) heterogeneous catalyst. As testified by the PXRD monitoring
1
uniform pores of the framework enable each active Ir‐site reactions. Inductively coupled plasma optical emission
accessible for catalytic purpose. Based on our catalytic results, spectrometer (ICP‐OES) analysis of the reaction filtrate
‐
1
the turnover frequency (TOF) of Ir‐PMOF‐
When decreasing the molar percent of [Ir] to 0.1%, the mixture was less than 0.06% of the total Ir content in Ir‐PMOF‐
reaction in the presence of Ir‐PMOF‐ (Zr) still achieved 77%
(Zr). The crystalline catalysts can be easily isolated by
conversion, although a much longer reaction time of 2.5 h was centrifugation, and can be reused at least nine times without
1
(Zr) is up to 4260 h . indicated that the amount of the Ir leaching into the reaction
1
1
required (entry 6).
significant loss of activity (Figure 3). Before each repeating run,
Ir‐PMOF‐ (Zr) catalyst was washed with DCM (3 5 mL) to
remove the adsorbed organic compounds in the interior and
exterior surfaces. During the nine reaction runs, the yields of
1

In addition to isopropanol, other alcohols such as methanol
and ethanol can take part in the Ir‐PMOF‐1(Zr) catalyzed O‐H
insertion reactions, and the alkoxyacetate products 2b and 2c
are produced with 80% and 87% yields, respectively (Table 1,
entries 7 and 8). Phenols are another important group of
compounds containing O‐H bonds. We have examined the O‐H
insertion reactions for phenol, 4‐methoxyphenol and 4‐
2
a
were in the range of 88‐94%, whereas in the tenth run, the
yield was reduced to 64%. To sum up, the turnover number
TON) is up to 875 after ten successive runs (Table S6). The
(
PXRD patterns of the recycled catalyst after the tenth run still
show comparable diffraction profile with the as‐synthesized
sample (Figure S10).
bromophenol. In the presence of 1 mol [Ir]% of Ir‐PMOF‐
all of EDA was consumed in 10 min, whereas phenoxyacetate
products 3a 3b and 3c were obtained with 56%, 63% and 70%
1(Zr),
,
CONCLUSION
yields, respectively (Table 1, entries 9‐11). In addition to the O‐
H insertion products, the self‐coupling reaction products of
I
n conclusion, we have successfully embedded the versatile
EDA, i.e. diethyl fumarate and maleate accounted for all initial homogeneous iridium(III)‐porphyrin catalyst into a stable and
EDA.
porous zirconium metal‐organic framework, and the resulting
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ARTICLE
Journal Name
1
1
1
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Ir‐PMOF‐1(Zr) carries coordinatively unsaturated Ir active sites
DOI: 10.1039/C6CE00358C
and shows high stability against organic solvents, water, as
well as heating (up to 240 C). As self‐supported
heterogeneous catalyst, Ir‐PMOF‐ (Zr) is efficient in O‐H
º
a
2
1
insertion reaction of alcohols and phenols, displaying superior
capabilities to the related homogenous catalysts. In the
reaction system, Ir‐PMOF‐1(Zr) manifests advantages in easy
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implying a promising application by developing and improving
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