Engineering catalytic coordination space in a chemically stable Ir-porphyrin MOF with a confinement effect inverting conventional Si-H insertion chemoselectivity

Article abstract of DOI:10.1039/C6SC03288E

An iridium-porphyrin ligand, Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin), has been utilized to react with HfCl₄ to generate a stable 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)), which possesses two types of open cavities (1.9 × 1.9 × 1.9 and 3.0 × 3.0 × 3.0 nm³) crosslinked through orthogonal channels (1.9 × 1.9 nm²) in three directions. The smaller cavity is surrounded by four catalytic Ir(TCPP)Cl walls to form a confined coordination space as a molecular nanoreactor, while the larger one facilitates reactant/product feeding and release. Therefore, the porous Ir-PMOF-1(Hf) can act as a multi-channel crystalline molecular flask to promote the carbenoid insertion reaction into Si-H bonds, featuring high chemoselectivity towards primary silanes among primary, secondary and tertiary silanes under heterogeneous conditions that are inaccessible by conventional homogeneous catalysts.

Full text of DOI:10.1039/C6SC03288E

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ARTICLE
Engineering Catalytic Coordination Space in a Chemical Stable Ir-
Porphyrin MOF with Confinement Effect Inverting Conventional
Si-H Insertion Chemoselectivity
Received 00th January 20xx,
Accepted 00th January 20xx
Yingxia Wang, Hao Cui, Zhangwen Wei, Hai-Ping Wang, Li Zhang,* and Cheng-Yong Su*
DOI: 10.1039/x0xx00000x
An iridium-porphyrin ligand, Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin), has been utilized to react with HfCl4
www.rsc.org/
to
generate
a
stable
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)), which possesses two types of open cavities (1.9  1.9  1.9 and 3.0
 3.0  3.0 nm3) crosslinked through orthogonal channels (1.9  1.9 nm2) in three directions. The smaller cavity is
surrounded by four catalytic Ir(TCPP)Cl walls to form a confined coordination space as molecular nanoreactor, while the
larger one facilitates reactant/product feeding and release. Therefore, the porous Ir-PMOF-1(Hf) can act as multi-channel
crystalline molecular flasks to promote carbenoid insertion reaction into Si-H bond, featuring high chemoselectivity
towards primary silanes among primary, secondary and tertiary silanes in heterogeneous condition that is inaccessible by
conventional homogeneous catalysts.
have been reported to catalyze Si-H insertion reactions. The
majority of these catalytic reactions prefer tertiary silanes.
Pérez has ever studied the relative reactivity of substituted
Introduction
Crystal engineering of metal-organic frameworks (MOFs)
provides a powerful platform to explore their versatile
potentials correlating to designable porosity and complexity.1
In this regard, functionalization of an MOF may be realized
from coordination space engineering (CSE) in MOF pores via
one-pot synthesis or postmodification.2 Thank to plentiful
reticular chemistry of MOFs, engineering of coordination
spaces (CSs) as the basic functional units for a specific
application becomes feasible by virtue of deliberate selection
of metal ion, organic linker and framework topology.3 For
example, engineering catalytic CSs in an MOF can start from
design of active sites with the selectivity controllable by
confinement effect from framework cavities and pore
windows.
silanes in the presence of a Cu or Ag-based catalyst, and found
that these catalysts display activity order of tertiary >
secondary > primary for ethyl substituted silanes, whereas an
inverted order of secondary > tertiary ≈ primary for phenyl
substituted silanes.7 Nevertheless, none of the reported
catalysts display the prior chemoselectivity for the primary
silanes. The bond dissociation energy (BDE) of the Si-H bond is
increasing along tertiary, secondary and primary silanes, and
thus the primary Si-H bonds are the most inert towards the
insertion reaction with carbenoids.10 However, it was noted
that a considerable steric effect could be aroused by multiply
substituents in secondary and tertiary silanes. Therefore, a
potential selectivity for primary silanes may be achieved if the
reaction takes place in a confined space, where the active sites
become more inaccessible to bulky substrates. In this context,
CSE of confined and catalytic nanoreactors in MOF pores may
offer an ideal whereas easy approach to such purpose owing
to additional selectivity endowed by the channel size, making
it possible to obtain less active primary silanes for further
conversion into diverse secondary silanes with plenty of
practical uses.11
The transition-metal-catalyzed carbenoid insertion into the
Si-H bond is an attractive method to prepare -silyl carbonyl
compounds. Besides dirhodium(II)4 and copper5 complexes
which are generally superior catalysts for the carbene transfer
reactions, only a few examples involving Zn,6 Ag,7 Au8 and Ir9
MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of
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
Herein, we testify this speculation by designing a robust
and self-supported iridium-porphyrinic MOF catalyst, [(Hf6(3
-
O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3] solvents (Ir-PMOF- (Hf), TCPP =

1
† Electronic supplementary information (ESI) available: Physical characterizations
of metalloporphyrin ligands, crystal structure data, physical characterizations,
chemical/thermal stability study, and gas adsorption of porphyrinic MOFs,
recycling experiments, and NMR data of Si-H insertion products. CIF files giving
crystallographic data. CCDC 1491233. For ESI and crystallographic data in CIF or
other electronic format see DOI: 10.1039/x0xx00000x.
tetrakis(4-carboxyphenyl)porphyrin), through incorporating
Ir(III)-porphyrin active sites on the pore surface to generate
catalytic CSs. Owing to its continuous and permeable channels
crosslinking the catalytic CSs, Ir-PMOF-
1(Hf) behaves as multi-
channel crystalline molecular flasks12 featuring effective
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an Autosorb-iQ2-MP gas sorption analyzer (Quantachrome,
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DOI: 10.1039/C6SC03288E
USA).
Cautions! 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.
Synthesis of (Hf6(3-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3solvents (Ir-
PMOF-1(Hf)). Ir(TCPP)Cl (5 mg, 4.9

10-3 mmol), HfCl4 (15 mg,
4.7
10-2 mmol), benzoic acid (400 mg, 3.27 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
48 h, red block crystals were obtained (7 mg, 77% yield based
on Ir(TCPP)Cl) and air-dried. Anal. Calcd. For (Hf6(3
-
O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3 9(C6H5COOH) 2H2O


(C207H176Cl3Ir3N12O85Hf12): C, 35.43; H, 2.53; N, 2.40. Found: C,
35.01; H, 3.01; N, 2.28%. FT-IR (KBr) ν 3402 (br), 1658 (s), 1601
(s), 1552 (s), 1418 (s), 1075 (m), 1015 (m), 718 (m), 664 (m) cm-
1
.
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 ( =
Scheme 1. Heterogeneous chemoselectivity of primary Si-H
insertion induced by confined coordination space in Ir-PMOF-1(Hf)
showing opposite reactivity order to conventional homogeneous
catalysis.
1.54178 Å). The crystal was kept at 150(10) K during data
collection. The structure was solved with the ShelXS structure
solution program integrated in Olex232 using Direct Methods,
and refined with the ShelXL refinement package using CGLS
minimisation.25a The refinement was restricted to one set of
molecules by using DIFX and FLAT to constrain porphyrin
ligand. ISOR/SIMU was applied to all non-hydrogen atoms to
simulate isotropic behaviors. All solvent molecules have been
removed by SQUEEZE program.25b The positions of the
hydrogen atoms are generated geometrically. A summary of
the crystal structure refinement data and selected bond angles
and distances are listed in Table S1 and S2. CCDC 1491233.
confinement
effect
and
easy
transportation
of
reactant/product into/from inner reactive vessels.13-24 The
prior selectivity and reactivity for primary Si-H insertion
reaction (Scheme 1) has been successfully established,
supplementing alternative chemoselective choice in contrast
to conventional homogeneous catalysts. To the best of our
knowledge, this is the first report about the inverted selectivity
order, i.e., primary > secondary > tertiary, for Si-H insertion
induced by a metal catalyst.
Typical Procedure for Si-H Insertion. A solution of ethyl 2-
diazoacetate (EDA, 45.6 mg, 0.4 mmol, 1.0 eq) in DCM (1.0 mL)
was added slowly to the mixture of phenylsilane (PhSiH3, 216.4
EXPERIMENTAL
mg, 2.0 mmol, 5.0 eq) and activated Ir-PMOF-1(Hf) (6.4 mg,
0.0032 mmol, 0.8 mol [Ir]%) in dicholoromethane (DCM, 1 mL).
The resulting suspension was stirred at room temperature for
3 min until EDA was completely consumed. The undissolved
catalyst was removed through centrifugation, and washed
General Information. All the reagents in the present work were
obtained from the commercial source and used directly
without further purification. The metalloporphyrin ligands
Ir(TCPPCO2Me)(CO)Cl and Ir(TCPP)Cl were synthesized
according to our recent work.14 The elemental analyses were
performed with Perkin-Elmer 240 elemental analyzer. HRESI-
MS was performed by using a Bruker Daltonics ESI-Q-TOF
maXis4G. Infrared spectra on KBr pellets were collected with a
Nicolet/Nexus-670 FT-IR spectrometer in the region of 4000-
400 cm-1. UV-vis spectra were tested on a Shimadzu/UV-3600
spectrophotometer. 1H and 13C NMR were recorded on Bruker
AVANCE III 400MHz. PXRD patterns were recorded on
with DCM (3
 8 mL). The combined supernatant was
evaporated to dryness, and the residue was dissolved in CDCl3
1
and analyzed by H NMR to determine the conversion of EDA
to ethyl 2-(phenylsilyl)acetate (2a, 93%).
RESULTS AND DISCUSSION
Solvothermal reaction of Ir(TCPP)Cl and HfCl4 in the
SmartLab X-ray powder diffractometer (Rigaku Co.) at 40 kV presence of benzoic acid in DMF at 120
and 30 mA with a Cu target tube. Thermogravimetric (TG) block crystals of Ir-PMOF-
(Hf). Single-crystal X-ray diffraction
analyses were performed under an air atmosphere at a studies reveal that Ir-PMOF-
(Hf) crystallizes in cubic space
heating rate of 2
C min-1 by using a NETZSCH TG 209 system. group Im-3m as an isostructure of Ir-PMOF-
(Zr)14 and PCN-
X-ray photoelectron spectroscopy (XPS) was performed on a 224,24 whereas based on Hf6-clusters (Figure 1). The basic Hf-
C for 48 h yielded red
1
1

1
ULVAC PHI Quantera microprobe. Binding energies (BE) were oxide node may consist of a core Hf6(
3-O)8 octahedron and 12
calibrated by setting the measured BE of C 1s to 284.65 eV. terminal H2O/OH- groups, in which each vertex of Hf6-
The sorption isotherms for N2 (77 K) gas were measured with octahedron is occupied by a Hf(IV) atom and each face is
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C6SC03288E
Figure 2. Stability test of Ir-PMOF-1(Hf) in different solvents.
recycled samples still retain the prominent peak profile and
crystallinity (Figure 2), verifying that the porous Ir-PMOF- (Hf)
crystals are competent for heterogeneous catalysis in these
solvent. After soaking the samples of Ir-PMOF- (Hf) in pH = 0-
11 and inorganic salts aqueous solution for 24 h, the PXRD
patterns show comparable diffraction profiles with the as-
synthesized sample (Figure S6).
Figure 1. Assembly of 3D Ir-PMOF-1(Hf) based on 6-connected
Hf6(3-O)8(OH)2(H2O)10 cluster and 4-connected Ir(TCPP)Cl ligand,
showing two types of cavities interconnected to generate open
channels in three directions.
1
1
capped by one
3-oxygen atom. Six edges of the Hf6-
octahedron are bridged by carboxylates from six different 4-
connecting Ir(TCPP)Cl ligands, thus leading to the formation of
three-dimensional (3D) framework of (4,6)-connected she net.
There are two types of cavities having open windows in such
The porosity of Ir-PMOF-1(Hf) has been evaluated by N2
adsorption isotherms at 77 K (Figure S7). Prior to sorption
measurement, the samples were subjected to solvent
exchange with acetone for 10 h and then activated by heating
at 120 °C under vacuum for 12 h. The N2 adsorption of Ir-
topological framework. One is bigger surrounded by 8 Hf6(3
O)8 clusters (3.0 3.0
3.0 nm3) while the other is smaller
enclosed by 4 Ir(TCPP)Cl (1.9 1.9
1.9 nm3) units, which PMOF-
interconnect with each other to form square-like pores (1.9
1.9 nm2) intercrossing in three orthogonal directions.
Therefore, Ir-PMOF- (Hf) can be regarded as a multi-channel
-




1(Hf) shows typical type-I isotherm, indicative of micro-
porosity. A N2 uptake of 535 cm3 g-1 is obtained, and the
Brunauer-Emmet-Teller (BET) surface area is calculated as
1758 m2 g-1. According to Density Functional Theory (DFT) pore

1
platform for heterogeneous catalysis with self-supporting
parallel nanoreactors and transportation channels, where
catalytic Ir-porphyrin sites are confined in CSs with open
windows for convenient reactant/product feeding and release.
The powder X-ray diffraction (PXRD) patterns of bulk
samples closely match with the simulated one from single-
crystal data, indicative of satisfactory phase purity (Figure S1).
distribution plot of Ir-PMOF-1(Hf), the pore diameter of the
sample is approximately 1.6 nm (Figure S8), which
approximates to the single-crystal analysis (1.9 nm). As
calculated by PLATON analysis, the effective solvent accessible
void in the crystal lattice is 78.4% of the cell volume.
The superiority of Ir-PMOF-1(Hf) in Si-H insertion reaction
has been examined by the model reaction of ethyl 2-
diazoacetate (EDA) and phenylsilane (PhSiH3). In the presence
As the crystal structure of Ir-PMOF-1(Hf) shows, the atomic
ratio of Hf : Ir : Cl is 4 : 1 : 1, which is further confirmed by
energy-dispersive X-ray spectroscopy (EDS) and X-ray
photoelectron spectroscopy (XPS) analyses (Figures S2-3;
Tables S3-4). Two intense peaks around 65.1 and 62.2 eV
appear in the XPS spectrum, which are assignable to Ir 4f5/2
and Ir 4f7/2, respectively.26
of 0.8 mol [M]% of the metal catalysts, including Ir-PMOF-1(Hf),
Ir(TPP)(CO)Cl (TPP = 5,10,15,20-tetraphenylporphyrin) and
Rh2(OAc)4, the reactions of a 1:5 molar ratio mixture of EDA
and PhSiH3 in DCM after 3 min produce the Si-H insertion
product of ethyl 2-(phenylsilyl)acetate (2a) in 93, 86 and 83%
yields, respectively (Table 1, entries 1-3). In each reaction, EDA
was completely consumed. In addition to the Si-H insertion
products, the self-coupling reaction products of EDA, i.e.
diethyl fumarate and maleate account for all initial EDA. The
similar reaction catalyzed by Cu(OTf)2 is found ineffective, and
2a is formed in only 41% yield after 48 h (entry 4). When
decreasing the molar percent of [Ir] to 0.04%, the reaction in
The thermal gravimetric (TG) curve of the desolvated Ir-
PMOF-
340 C, where the framework starts to decompose (Figure S4).
The variable temperature PXRD experiments disclose that the
framework porosity can sustain heating up to 220 C (Figure
S5). Ir-PMOF- (Hf) exhibits excellent chemical stability. After
1(Hf) crystallites displays no obvious weight loss up to


1
immersing the fresh crystals in a wide range of solvents, such
as dicholoromethane (DCM), ethyl acetate (EA), diethyl ether
(Et2O), acetonitrile (MeCN), tetrahydrofuran (THF), methanol
(MeOH) and water for 3-5 days, the PXRD patterns of the
the presence of Ir-PMOF-1(Hf) still achieves 76% yield,
although a much longer reaction time of 12 h is required (entry
5). Based on these catalytic results, the turnover frequency
(TOF) and the turnover number (TON) of Ir-PMOF-1(Hf) can be
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Table 1. Catalytic Si-H Insertion.a
View Article Online
DOI: 10.1039/C6SC03288E
Entry Catalyst
Time
Product
Yield(%)
93
1
Ir-PMOF-1(Hf)
3 min 2a
2
3
Ir(TPP)(CO)Cl
Rh2(OAc)4
Cu(OTf)2
Ir-PMOF-1(Hf)
Ir-PMOF-1(Hf)
3 min 2a
3 min 2a
86
83
41
76
82
4
48 h
12 h
2a
2a
Figure 3. Chemoselective Si-H insertion heterogeneously
catalysed by Ir-PMOF-1(Hf) framework. Numbers show molar
ratio.
5b
6
6 min 2b
7 min 2c
5 min 2d
20 min 2e
metalloporphyrin complexes,9 Cu(I/II)5 and Ag(I)7 salts, under
whose catalysis the secondary and tertiary silanes display prior
activity to primary silanes.
7
8
9
Ir-PMOF-1(Hf)
Ir-PMOF-1(Hf)
Ir-PMOF-1(Hf)
33
73
51
28
91
84
To further evaluate the chemoselectivity of Ir-PMOF-1(Hf)
towards primary silanes, a competition experiment has been
carried out, employing a 0.9 : 1.35 : 2.7 molar ratio mixture of
PhSiH3, Ph2SiH2 and Ph3SiH as the Si-H sources, and thus the
amounts of the primary, secondary and tertiary Si-H bonds are
equal (Figure S10).7 One equivalent of EDA reacts with this
mixture to give rise to Si-H products 2a-c in the molar ratio of
10 Ir-PMOF-1(Hf)
11 Ir-PMOF-1(Hf)
12 Ir-PMOF-1(Hf)
1 h
2f
3 min 2g
3 min 2h
1 : 0.7 : 0.3 in the presence of Ir-PMOF-
BDA reacts with this mixture to produce 2d-f in the molar ratio
of 1 0.7 0.3. For comparison, the similar reactions induced
by Ir(TPP)(CO)Cl and Rh2(OAc)4 generates 2a-c in the ratios of
1 : 1 : 0.4 and 1 : 1.5 : 1.2, respectively. Competition
experiments between two of the three silanes under the
1(Hf). In a similar way,
aReaction conditions: 0.8 mol [M]% of the catalyst. The yields
are based on the conversions of diazoacetates to the Si-H
insertion products. In each reaction, EDA has been
completely consumed. bCatalyst amount: 0.04 mol [Ir]%.
：
：
estimated up to 2325 h-1 and 1900, respectively.
catalysis of Ir-PMOF-
1
(Hf) have also been carried out, the
2c are 1 : 0.7 and 1 : 0.2,
molar ratios of 2a 2b and 2a
:
:
Ir-PMOF-
secondary silane. The reaction of EDA and diphenylsilane
(Ph2SiH2) in the presence of 0.8 mol [Ir]% of Ir-PMOF- (Hf)
1(Hf) is also efficient in inducing the reaction of
respectively. Considering that the Si-H insertion products 2a-c
do not undergo further Si-H insertion in the presence of Ir-
1
PMOF-1(Hf), we have also carried out a similar competition
experiment but employed a 1 : 1 : 1 molar ratio mixture of
PhSiH3, Ph2SiH2 and Ph3SiH instead. The catalytic result
leads to the formation of ethyl 2-(diphenylsilyl)acetate (2b) in
82% yield (entry 6). For comparison, the Si-H insertion reaction
of the tertiary silane such as triphenylsilane (Ph3SiH) is sluggish,
discovered that 2a, 2b and 2c were formed in the molar ratio
and the product, ethyl 2-(triphenylsilyl)acetate
(2c), is
of 1 : 0.5 : 0.1 (Figure 3).
The inverted chemoselectivity for the carbenoid insertion
into primary Si-H bonds induced by Ir-PMOF-1(Hf) may be
generated in only 33% yield (entry 7). Changing the diazo
compound to benzyl 2-diazoacetate (BDA), the reactions with
PhSiH3, Ph2SiH2 and Ph3SiH give the Si-H insertion products 2d-
ascribed to the following two reasons. On one hand, the active
sites are located on the axial positions of the metalloporphyrin
motifs which enclose a confined nanospace, imposing more
steric effect toward bulky reactants than free metal catalysts
such as dirhodium(II) tetracarboxylates. As a result, the
sterically unfavored tertiary silanes display poor
chemoselectivity in case of the heterogeneous catalyst Ir-
f
in the yields of 73, 51 and 28%, respectively, and the reaction
time has been lengthened from 5 min to 1 h (entries 8-10).
Besides phenylsilane, other primary silanes like n-butylsilane
(BuSiH3) can also react with both of EDA and BDA in the
presence of Ir-PMOF-1(Hf) to generate Si-H insertion products
2g and 2h in high yields (entries 11 and 12). After the above
catalytic reactions, the PXRD patterns of the recycled catalyst
samples remain almost intact, confirming that the porous
framework of Ir-PMOF-
process (Figure S9).
PMOF-
homogeneous catalyst Ir(TPP)(CO)Cl. On the other hand, the
porosity of Ir-PMOF- (Hf) brings additional size selectivity and
1(Hf) compared to the similar metalloporphyrin-based
1(Hf) can well tolerate the catalytic
1
channel diffusion difference to enforce the confinement effect;
therefore, the least bulky primary silane and its corresponding
Si-H insertion product can be transported through the multi-
Comparison among the above catalytic activities of
differently substituted silanes obviously discloses a reactivity
order of primary > secondary > tertiary silanes (entries 1, 6-10).
channels of the self-supported catalytic Ir-PMOF-1(Hf) easily
This reactivity order induced by Ir-PMOF-1(Hf) is strikingly
than those of secondary and tertiary analogues. The overall
result might explain the high chemoselectivity and reactivity
different from the known order of Si-H insertion
homogeneously catalyzed by dirhodium(II) tetracarboxylates,4
4 | J. Name., 2012, 00, 1-3
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This work was supported by the 973 Program (2012CVBie8w21Ar7ti0cl1e)O,ntlhinee
DOI: 10.1039/C6SC03288E
NSFC Projects (21373278, 91222201), the STP Project of Guangzhou
(15020016), the NSF of Guangdong Province (S2013030013474), the
RFDP of Higher Education of China (20120171130006) and the
Fundamental Research Funds for the Central Universities.
Notes and references
1
(a) G. Férey, Chem. Soc. Rev., 2008, 37, 191; (b)T. Devic and
C. Serre, Chem. Soc. Rev., 2014, 43, 6097; (c) Z. Fang, B.
Bueken, D. E. De Vos and R. A. Fischer, Angew. Chem. Int.
Ed., 2015, 54, 7234; (d) A. Schneemann, V. Bon, I.
Schwedler, I. Senkovska, S. Kaskel and R. A. Fischer, Chem.
Soc. Rev., 2014, 43, 6062; (e) H. Furukawa, K. E. Cordova, M.
O'Keeffe and O. M. Yaghi, Science, 2013, 341, 1230444; (f)
S. Horike, S. Shimomura and S. Kitagawa, Nat. Chem., 2009,
Figure 4. Recycling experiments
towards primary silanes in the Ir-PMOF-
heterogeneous Si-H insertion reactions.
1(Hf)-catalyzed
1
, 695; (g) J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.-Y.
Su, Chem. Soc. Rev., 2014, 43, 6011; (h) J. Gascon, A.
Corma, F. Kapteijn, F. X. Llabr s i Xamena, ACS Catal., 2014,
, 361.
é
Moreover, the crystalline catalysts can be easily isolated by
centrifugation, and reused at least ten times for Si-H insertion
of PhSiH3 with EDA (Figure 4; Table S5). During the ten reaction
runs, the yields of 2a were in the range of 74-92%. From the 1st
to 6th run, it took less than 15 min to finish the reaction,
whereas the 7th, 8th and 9th run needed 26, 55 and 90 min,
respectively, to complete. The reduced activity from 7th run
might be due to the reactants and products stucked in the
4
2
(a) S. Kitagawa and R. Matsuda, Coordin. Chem. Rev., 2007,
251, 2490; (b) R. A. Fischer and C. Wöll, Angew. Chem. Int.
Ed., 2008, 47, 8164. (c) S. M. Cohen, Chem. Rev., 2012, 112
970.
,
3
4
M. O'Keeffe, M. A. Peskov, S. J. Ramsden and O. M. Yaghi,
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pores of the Ir-PMOF-1(Hf) framework. In order to remove the
adsorbed organic compounds in the interior and exterior
surfaces during the catalytic reactions, the recycled Ir-PMOF-
1
(Hf) catalyst should be washed with DCM (3  8 mL) before
the successive runs. The PXRD patterns of the recycled catalyst
after the 1st, 3rd, 5th and 10th runs show comparable diffraction
profile with the as-synthesized sample (Figure S11).
5
(a) L. A. Dakin, S. E. Schaus, E. N. Jacobsen and J. S. Panek,
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,
8496.
6
7
R. Vicente, J. Gonɀále
ɀ
, L. Riesgo, J. Gonɀále
ɀ and L. A.
Lópe
ɀ, Angew. Chem. Int. Ed., 2012, 51, 8063.
Conclusions
M. J. Iglesias, M. C. Nicasio, A. Caballero, P. J. Pérez, Dalton
Trans., 2013, 42, 1191.
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In summary, we have successfully imparted outstanding
carbenoid transfer catalysis of homogeneous Ir-porphyrin to a
porous, robust and stable Ir-PMOF-1(Hf), underlying a new
8
9
field of heterogeneous MOF catalysis via introducing rarely
explored noble metal-porphyrins (e.g. Ir, Ru and Rh).
Engineering of confined and catalytic CSs in an MOF, in
collaboration with its open porosity, presents multi-channel
crystalline nanoreactors for selective Si-H insertion, offering
higher efficiency than the corresponding homogeneous
catalysts with excellent TOF and TON. An inverted reactivity
and selectivity order of Si-H insertion reaction, i.e. primary >
secondary > tertiary, which is unattainable by conventional
metal catalysts, is achieved, and the self-supported catalyst is
easy to recycle and separate. These results demonstrate the
versatility of MOF catalysis that can not only incorporate
excellent features of homogeneous catalysts, but also endow
metal catalysis with uniqueness in heterogeneous conditions
to accomplish catalytic process unachievable by homogeneous
catalysts.
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