Postsynthetic metalation of bipyridyl-containing metal-organic frameworks for highly efficient catalytic organic transformations

Article abstract of DOI:10.1021/ja5018267

We have designed highly stable and recyclable single-site solid catalysts via postsynthetic metalation of the 2,2-bipyridyl-derived metal-organic framework (MOF) of the UiO structure (bpy-UiO). The Ir-functionalized MOF (bpy-UiO-Ir) is a highly active catalyst for both borylation of aromatic C-H bonds using B₂(pin)₂ (pin = pinacolate) and ortho-silylation of benzylicsilyl ethers; the ortho-silylation activity of the bpy-UiO-Ir is at least 3 orders of magnitude higher than that of the homogeneous control. The Pd-functionalized MOF (bpy-UiO-Pd) catalyzes the dehydrogenation of substituted cyclohexenones to afford phenol derivatives with oxygen as the oxidant. Most impressively, the bpy-UiO-Ir was recycled and reused 20 times for the borylation reaction without loss of catalytic activity or MOF crystallinity. This work highlights the opportunity in designing highly stable and active catalysts based on MOFs containing nitrogen donor ligands for important organic transformations.

Full text of DOI:10.1021/ja5018267

Communication
pubs.acs.org/JACS
Postsynthetic Metalation of Bipyridyl-Containing Metal−Organic
Frameworks for Highly Efficient Catalytic Organic Transformations
Kuntal Manna,† Teng Zhang,† and Wenbin Lin*
Department of Chemistry, University of Chicago, 929 East 57th Street, Chicago, Illinois 60637, United States
S
* Supporting Information
highly efficient single-site solid catalysts based on UiO-type
ABSTRACT: We have designed highly stable and
recyclable single-site solid catalysts via postsynthetic
metalation of the 2,2′-bipyridyl-derived metal−organic
framework (MOF) of the UiO structure (bpy-UiO). The
Ir-functionalized MOF (bpy-UiO-Ir) is a highly active
catalyst for both borylation of aromatic C−H bonds using
B2(pin)2 (pin = pinacolate) and ortho-silylation of
benzylicsilyl ethers; the ortho-silylation activity of the
bpy-UiO-Ir is at least 3 orders of magnitude higher than
that of the homogeneous control. The Pd-functionalized
MOF (bpy-UiO-Pd) catalyzes the dehydrogenation of
substituted cyclohexenones to afford phenol derivatives
with oxygen as the oxidant. Most impressively, the bpy-
UiO-Ir was recycled and reused 20 times for the borylation
reaction without loss of catalytic activity or MOF
crystallinity. This work highlights the opportunity in
designing highly stable and active catalysts based on
MOFs containing nitrogen donor ligands for important
organic transformations.
MOFs because of their stability under a range of reaction
conditions.25 First reported by Lillerud et al. in 2008,28,29 the
UiO series of MOFs are built from Zr6O4(OH)4(O2CR)12
secondary building units (SBUs) and linear dicarboxylate
bridging ligands and have allowed for the design of novel
functional materials by incorporating a wide variety of
functionalities into the dicarboxylate bridging ligands. Herein,
we report the UiO-type MOF with the 2,2′-bipyridyl moiety
(bpy-UiO) as an orthogonal functional fragment and its
postsynthetic metalation to afford highly robust and active
solid catalysts for a broad scope of organic reactions.30,31
Bpy-UiO was synthesized via a solvothermal reaction between
ZrCl4 and 2,2′-bipyridine-5,5′-dicarboxylic acid in the presence
of DMF and trifluoroacetic acid. The resulting solid showed an
identical powder pattern to that simulated from the single crystal
structure (Figure 1a, 1d).31a Bpy-UiO exhibited a BET surface
area of 2277 m2/g and a pore size of 7.2 Å, consistent with the
single crystal structure (Figures S1 and S2, Supporting
Information [SI]). The postsynthetic metalation of bpy-UiO
was performed by treating bpy-UiO with 2.0 equiv of
[Ir(COD)(OMe)]2 in THF to afford bpy-UiO-Ir as a deep
green solid or with 4.0 equiv of [Pd(CH3CN)4][BF4]2 in DMSO
to afford bpy-UiO-Pd as a light yellow solid.32,33 The crystallinity
of bpy-UiO was maintained in both bpy-UiO-Ir and bpy-UiO-Pd
as shown by their PXRD patterns that are the same as that of bpy-
UiO (Figure 1d and 1e). Inductively coupled plasma-mass
spectrometry (ICP-MS) analyses of Zr/Ir and Zr/Pd ratios of the
digested metalated MOFs provided Ir and Pd loadings of 30%
and 24% for bpy-UiO-Ir and bpy-UiO-Pd, respectively. Nitrogen
adsorption measurements indicated that both bpy-UiO-Ir and
bpy-UiO-Pd have much reduced BET surface areas (365.0 and
457.5 m2/g, respectively) and slightly reduced pore sizes of 5.6
and 6.7 Å, respectively (Figures S2, S5, and S9; SI). The smaller
surface areas, pore sizes, and pore volumes of bpy-UiO-Ir and
bpy-UiO-Pd are due to the presence of Ir/Pd cations and
associated ligands in the MOF cavities. TEM images showed that
bpy-UiO has a particle size of ∼300 nm (Figure 1b) and the
particles appear to be highly aggregated.
helating ligands containing pyridyl moieties such as
Cbipyridines, phenanthrolines, and terpyridines are exten-
sively used ligand frameworks in coordination chemistry and
homogeneous catalysis.1−4 Owing to their robust redox stability,
coordinating ability with a wide range of metal ions, and the ease
of functionalization, these pyridyl ligands have offered an
interesting alternative to phosphine-based ligands in developing
catalytic systems for fine chemical synthesis.5−8 Nevertheless,
homogeneous catalysts based on nitrogen donor ligands tend to
have more open coordination environments than their
phosphine counterparts and are thus more prone to deactivation
via intermolecular pathways. Moreover, homogeneous catalysts
based on rigid nitrogen donor ligands can have poor solubility in
typically nonpolar solvents used in many catalytic reactions.
Immobilization of homogeneous catalysts and isolation of
catalytic sites using a solid support provide an interesting
approach to circumvent these potential problems.
Bpy-UiO-Ir exhibited excellent activity in dehydrogenative
borylation of aromatic C−H bonds using B2(pin)2 (pin =
pinacolate) as the borylating agent.34−36 Borylation of aryl C−H
bonds provides aryl boronic esters, which are employed as
reagents in many important reactions for synthesizing organic
compounds.37−42 Bpy-UiO-Ir catalyzed borylation reactions
In this context, metal−organic frameworks (MOFs) have
attracted increasing interest in recent years as a new class of
porous molecular materials for various potential applica-
tions.9−16 In particular, MOFs have provided a highly tunable
platform for designing single-site solid catalysts for a variety of
useful organic transformations.17−24 Importantly, MOFs and
related cross-linked polymers were shown to stabilize highly
active species that could undergo bimolecular deactivation in
solution.25−27 We have been particularly interested in developing
Received: February 20, 2014
Published: April 23, 2014
© 2014 American Chemical Society
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a
Table 1. Bpy-UiO-Ir Catalyzed C−H Borylation of Arenes
Figure 1. (a) X-ray crystal structure and (b) TEM image of the bpy-UiO
MOF. (c) Postsynthetic metalation of bpy-UiO to form bpy-UiO-Ir and
bpy-UiO-Pd. (d) PXRD pattern simulated from the CIF file31a (black)
and PXRD patterns of pristine bpy-UiO (red), freshly prepared bpy-
UiO-Ir (blue), and bpy-UiO-Ir recovered from the 21st run of
borylation of m-xylene (purple). (e) PXRD patterns of pristine bpy-
UiO (black), freshly prepared bpy-UiO-Pd (red), and bpy-UiO-Pd
recovered from dehydrogenation of 3-methylcyclohex-2-enone (blue).
with B2(pin)2 were first screened in several solvents and in neat
arenes (without using a solvent) to obtain the best conditions of
100 °C in heptane or in neat arenes (Table S1, SI). At 0.5 mol %
catalyst loading, bpy-UiO-Ir gave complete conversions and
afforded the borylated arenes in 85−96% isolated yields (Table
1). MOF-catalyzed borylation reactions have a broad substrate
scope, allowing the borylation of a wide range of activated and
unactivated arenes, including halogenated-, alkyl-, and alkoxy-
arenes. The regioselectivities of the borylated products are the
same as those reported for the homogeneous catalysts by
functionalizing the α-C centers in heteroarenes and the least
sterically hindered carbon centers in unactivated arenes.36 The
C−H borylation of rigid and larger substrates required longer
reaction times due to the slower diffusion of substrates and
products through the MOF channels (Table 1, entries 1, 3, and
4). Time-dependent GC conversion curves indicated that, in
spite of the slower diffusion of reactants through MOF channels
than in homogeneous solution, bpy-UiO-Ir was at least twice as
active as the homogeneous control [(CO2Me)2bpy]Ir(COD)-
(OMe) in terms of turnover frequency (Figure 2a). At 0.5 mol %
catalyst loading, the borylation of m-xylene was completed in 8
and 17 h for bpy-UiO-Ir and [(CO2Me)2bpy]Ir(COD)(OMe),
respectively (Figure 2a). The higher activity of bpy-UiO-Ir is
likely due to active site isolation which prevents any
intermolecular deactivation pathways.
a
Reaction conditions: 0.5 mol % bpy-UiO-Ir, 81.9 μmol B2pin2, 163.9
b
μmol of arene, 2.0 mL of heptane, 100 °C. 0.1 mol % bpy-UiO-Ir.
c
Neat arene was used.
S14) or MOF crystallinity (Figures 1d and S13). Excellent yields
(87−95%) of the borylated product, 5-(4,4,5,5-tetramethyl-
1,3,2-dioxaborolan-2-yl)-m-xylene, were obtained consistently in
the reuse experiments. B2(pin)2 was completely consumed
within 4 h during the first 9 runs, but the reaction took
progressively longer time to complete starting from the 13th run
(Figure 2b). The reaction took 6 h to complete in the 13th run
and 8 h in the 21st run. The slightly longer reaction time needed
for the later runs is presumably due to the accidental loss of the
MOF catalyst during the workup step (due to the small reaction
scale). The bpy-UiO-Ir catalyst thus gives a much higher total
turnover number (at least 20 times) as a result of catalyst
recycling and reuse. Importantly, the borylation product was
obtained in high purity simply by removing the solid catalyst and
the organic volatiles. The heterogeneous nature of bpy-UiO-Ir
was further confirmed by several experiments. The PXRD
patterns of bpy-UiO-Ir recovered from the 5th, 9th, and 21st run
remained essentially unchanged from that of freshly prepared
bpy-UiO-Ir (Figures 1d and S15), indicating that the MOF
catalyst is very stable under the catalytic conditions. Additionally,
ICP-MS analyses showed that the amounts of Ir and Zr leaching
into the supernatant after the first run were <0.03% and <0.003%,
respectively, and the amounts of leached Ir and Zr after the ninth
Remarkably, at a 2 mol % catalyst loading, bpy-UiO-Ir could be
recovered and reused for the borylation of m-xylene for at least 20
times without significant loss of catalytic activity (Figures 2b and
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Table 2. Bpy-UiO-Ir Catalyzed Intramolecular ortho-
a
Silylation of Benzylicsilyl Ethers to Benzoxasiloles
b
entry
R1
R2
time
yield
94
1
2
3
4
5
6
7
H
Me
Me
Me
Me
Me
Me
Ph
30 h
6 d
c
H
90
Me
Me
OMe
Cl
30 h
6 d
92
c
91
50 h
44 h
72 h
85
92
83
H
a
Reaction conditions: 1.0 mol % bpy-UiO-Ir, 2.0 mL of n-heptane, 100
b
c
°C. Isolated yield. 0.1 mol % bpy-UiO-Ir.
Table 3. Bpy-UiO-Pd Catalyzed Dehydrogenation of
Substituted Cyclohexenones to Phenols
Figure 2. (a) Plots of GC conversion (%) vs time (h) for C−H
borylation of m-xylene using bpy-UiO-Ir (0.5 mol %) and
[(CO2Me)2bpy]Ir(COD)(OMe) (0.5 mol %) as catalysts under
identical conditions. (b) Plots of GC conversion (%) vs time (h) for
various runs in the recycle and reuse of bpy-UiO-Ir for borylation of m-
xylene. (c) Plots of GC conversion (%) vs time (d) for ortho-silylation of
3a using bpy-UiO-Ir (0.1 mol %) and [(CO2Me)2bpy]Ir(COD)(OMe)
(5 mol %) as catalysts under identical conditions. (d) PXRD patterns of
pristine bpy-UiO (black), freshly prepared bpy-UiO-Ir (red), and bpy-
UiO-Ir recovered from ortho-silylation of 3a (blue).
a
bc
,
entry
R
solvent
temp (°C)
time
conv (%)
1
2
3
4
5
6
7
8
H
toluene
DMSO
m-xylene
DMSO
DMF
80
80
3 d
55 h
3 d
80
H
100
39
H
100
100
100
100
100
100
H
32 h
3 d
100 (93)
82
run were <0.01% and <0.001%, respectively. Moreover, no
further conversion was detected after removal of bpy-UiO-Ir
during the course of the borylation reaction (Scheme S2).
Bpy-UiO-Ir is also active in catalyzing intramolecular ortho-
silylation of benzylicsilyl ethers to give benzoxasiloles (Table
2).6,43 Benzoxasiloles are important in organic synthesis and can
be converted to phenol by Tamao−Fleming oxidation44 or to
biaryl derivatives by Hiyama cross-coupling reactions.45 Screen-
ing experiments of solvents and reaction conditions revealed that
the silylation reaction gave the highest turnover frequency when
performed in n-heptane at 100 °C (Table S2, SI). At 1.0 mol %
catalyst loading and under these optimized conditions, bpy-UiO-
Ir provided benzoxasiloles (4a−4e) in good isolated yields (83−
94%). Importantly, no H-acceptor is needed for the silylation
reaction, which is a significant improvement over the
corresponding homogeneous silylation reaction in terms of
atom efficiency. The catalyst loading could be decreased to 0.1
mol % albeit at the cost of increasing the reaction time from 30 h
to 6 days (entries 2 and 4, Table 2). Additionally, longer reaction
times were required for larger substrates, presumably because of
the slower substrate diffusion through the MOF channels (Table
2, entries 5−7). Notably, the homogeneous control [(CO2Me)2-
bpy]Ir(COD)(OMe) had a very low activity for the silylation
reaction. Under identical conditions, 5.0 mol % of [(CO2Me)2-
bpy]Ir(COD)(OMe) afforded 4a in only 4% conversion in a day,
after which no further conversion was observed with prolonged
heating. In contrast, the conversion of 4a proceeded linearly with
time until completion in the presence of at 0.1 mol % of the bpy-
UiO-Ir catalyst (Figure 2c). This result indicates that bpy-UiO-Ir
is at least 1250 times more active than the homogeneous control
for the silylation reaction, strongly supporting the beneficial
effect of active site isolation in an MOF catalyst. The PXRD of
bpy-UiO-Ir recovered from the silylation reaction remained the
same as that of freshly prepared bpy-UiO-Ir (Figure 2d). Bpy-
H
Me
Et
Ph
DMSO
DMSO
DMSO
35 h
44 h
100 (86)
100 (91)
100 (83)
70 h
a
b
Reaction conditions: 1.0 mol % bpy-UiO-Pd. Conversions were
c
determined by GC. Isolated yield in the parentheses.
UiO-Ir is thus a robust, reusable, and active single-site solid
catalyst for important organic transformations.
We next examined the applicability of bpy-UiO in other metal
catalyzed reactions. We turned our attention to the catalytic
activity of bpy-UiO-Pd because [(6,6′-dmbpy)Pd(CH3CN)4]-
[BF4]2 (6,6′-dmbpy = 6,6′-dimethyl-2,2′-bipyridine) was
recently shown by Stahl et al. to be a highly active catalyst for
dehydrogenation of substituted cyclohexenones.46,47 Bpy-UiO-
Pd is active in the dehydrogenation of substituted cyclo-
hexenones to phenol under 1 atm of O2. The reaction conditions
were optimized by monitoring the conversion of cyclohexenone
to phenol (6a) with 1.0 mol % bpy-UiO-Pd by GC analysis.
Phenol could be obtained in moderate yields (39−80%) in DMF
and aromatic solvents such as toluene and m-xylene at 80−100
°C. The highest yield (93%) was obtained when the reaction was
performed in DMSO at 100 °C. However, the yield of phenol
dropped significantly in DMSO at 120 °C even though the MOF
catalyst remained crystalline (Figure S16), presumably due to the
decomposition of the bpy-UiO-Pd catalyst. Under 1 atm of O2,
1.0 mol % bpy-UiO-Pd afforded 3-substituted phenols 6b, 6c,
and 6d (entries 6−8, Table 3) in DMSO at 100 °C in 83−91%
isolated yields. Bpy-UiO-Pd also compares favorably to its
homogeneous counterpart, with at least three times as high
activity as the homogeneous control. The homogeneous catalyst
[{(CO2Me)2bpy}Pd(CH3CN)4][BF4]2 that was prepared in situ
from (CO2Me)2bpy and [Pd(CH3CN)4][BF4]2 (1:1 equiv; 3
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(13) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.;
mol % Pd) afforded phenol quantitatively from cyclohexenone in
36 h in DMSO at 100 °C. During the course of this reaction, a
black precipitate formed due to the degradation of the catalyst.
After removal of all the volatiles in vacuo, the remaining residue
from the homogeneous reaction did not exhibit any catalytic
activity for the dehydrogenation of cyclohexenone. In contrast,
bpy-UiO-Pd was recycled and reused twice in this reaction (first
run, 93%; second run, 91%; third run, 79%). The bpy-UiO-Pd
catalyst recovered from the dehydrogenation showed the same
PXRD pattern as the as-prepared bpy-UiO-Pd (Figure 1e),
indicating that the bpy-UiO-Pd catalyst is stable under the
catalytic conditions.
In summary, we have developed a straightforward post-
synthetic metalation strategy to prepare highly active single-site
solid catalysts based on a UiO-type MOF bearing the bipyridyl
moiety. The bpy-UiO-Ir and bpy-UiO-Pd catalysts not only show
much enhanced (up to at least 1250 times) catalytic activities
compared to their homogeneous analogues but also exhibit
higher stability and can be readily reused for a broad scope of
important organic transformations. Our current work is focused
on extending this method to develop other bpy-UiO based
transition metal catalysts that can potentially be used in the
practical synthesis of fine chemicals.
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ASSOCIATED CONTENT
* Supporting Information
■
S
General experimental section; synthesis and characterization of
MOFs; procedures for catalytic reactions; GC analysis
conditions for all products. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
wenbinlin@uchicago.edu
■
Author Contributions
†Z.M. and T.Z. contributed equally.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
This work was supported by the NSF (CHE-1111490) and
startup funds from the University of Chicago. We thank Dr.
Cheng Wang, Carter W. Abney, Christopher Poon, and Kuangda
Lu for experimental help.
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