Highly efficient C-H oxidative activation by a porous Mn III-porphyrin metal-organic framework under mild conditions

Article abstract of DOI:10.1002/chem.201302025

A simple strategy to rationally immobilize metalloporphyrin sites into porous mixed-metal-organic framework (M'MOF) materials by a metalloligand approach has been developed to mimic cytochrome P450 monooxygenases in a biological system. The synthesized porous M'MOF of [Zn₂(MnOH-TCPP)- (DPNI)]·0.5DMF·EtOH·5.5H₂O (CZJ-1; CZJ = Chemistry Department of Zhejiang University; TCPP = tetra-kis(4-carboxyphenyl) porphyrin); DPNI = N, N′-di(4-pyridyl)-1, 4, 5, 8-naph- thalenetetracarboxydiimide) has the type of doubly interpenetrated cubic aPo topology in which the basic Zn₂-(COO)₄ paddle-wheel clusters are bridged by metalloporphyrin to form two-dimensional sheets that are further bridged by the organic pillar linker DPNI to form a three-dimensional porous structure. The porosity of CZJ-1 has been established by both crystal-lographic studies and gas-sorption isotherms. CZJ-1 exhibits significantly high catalytic oxidation of cyclohexane with conversion of 94% to the mixture of cyclohexanone (K) and cyclohexanol (A) (so-called K-A oil) at room temperature. We also provided solid experimental evidence to verify the catalytic reaction that occurred in the pores of the M'MOF catalyst.

Full text of DOI:10.1002/chem.201302025

FULL PAPER
DOI: 10.1002/chem.201302025
III
À
Highly Efficient C H Oxidative Activation by a Porous Mn –Porphyrin
Metal–Organic Framework under Mild Conditions
Ming-Hua Xie,[a] Xiu-Li Yang,[a] Yabing He,[b] Jian Zhang,[c] Banglin Chen,*[b] and
Chuan-De Wu*[a]
Abstract: A simple strategy to rational-
ly immobilize metalloporphyrin sites
thalenetetracarboxydiimide) has the
type of doubly interpenetrated cubic a-
Po topology in which the basic Zn2-
porous structure. The porosity of CZJ-
1 has been established by both crystal-
lographic studies and gas-sorption iso-
therms. CZJ-1 exhibits significantly
high catalytic oxidation of cyclohexane
with conversion of 94% to the mixture
of cyclohexanone (K) and cyclohexanol
(A) (so-called K–A oil) at room tem-
perature. We also provided solid exper-
imental evidence to verify the catalytic
reaction that occurred in the pores of
the M’MOF catalyst.
into
framework (M’MOF) materials by a
metalloligand approach has been de-
porous
mixed-metal–organic
AHCTUNGERTG(NNUN COO)4 paddle-wheel clusters are
A
U
bridged by metalloporphyrin to form
two-dimensional sheets that are further
bridged by the organic pillar linker
veloped to mimic cytochrome P450
monooxygenases in a biological system.
The synthesized porous M’MOF of
[Zn2(MnOH–TCPP)-
DPNI to form
a three-dimensional
ACHTUNGTRENNUNG(DPNI)]·0.5DMF·EtOH·5.5H2O (CZJ-
Keywords: heterogeneous catalysis ·
metalloporphyrins · metal–organic
frameworks · oxidation · porous
materials
1; CZJ=Chemistry Department of
Zhejiang University; TCPP=tetra-
kis(4-carboxyphenyl)porphyrin);
DPNI=N,N’-di(4-pyridyl)-1,4,5,8-naph-
Introduction
manufacture of organic pharmaceutical compounds. Howev-
À
er, activation of C H bonds, particularly those within satu-
À
C H activation is a very important chemical process that
rated hydrocarbons, is very difficult given the fact that the
single bonds in hydrocarbons are very stable. Extensive
could revolutionize the chemical industry.[1] Because this
À
À
chemical process can readily transform a C H bond into a
study on C H activation did not start until the discovery of
C X bond (X=C, O, N, and so forth), the realization of an
a few organometallic catalysts back in the 1960s and 1970s,[2]
and now it is certainly one of the most active research areas
À
À
efficient C H activation process can allow us to fully utilize
in chemistry.[3] Controlled direct C H oxidative activation
À
a variety of low-cost hydrocarbons such as methane, ethane,
propane, hexane, and cyclohexane as raw materials for the
production of useful synthetic organic chemicals. Further-
more, direct C H activation can also shorten the multistep
organic syntheses that have been widely implemented in the
of cyclohexane can produce a mixture of cyclohexanone (K)
and cyclohexanol (A) (so-called K–A oil), which is a very
important chemical for the industrial production of Nylon-6
and Nylon-6,6.[4] Although a tremendous amount of research
endeavors have been pursued to target efficient catalysts for
the oxidation of cyclohexane, no significant breakthrough
has been made.[5,6]
À
[a] Dr. M.-H. Xie, X.-L. Yang, Prof. Dr. C.-D. Wu
Center for Chemistry of High-Performance
and Novel Materials, Department of Chemistry
Zhejiang University, Hangzhou, 310027 (P.R. China)
Fax : (+86)571-87951895
The potential of metal–organic frameworks (MOFs) for
this important C H activation was pioneered by Suslick
À
et al., who developed an MnIII–porphyrin MOF catalyst.[7] It
has been well known that synthetic metalloporphyrin molec-
ular compounds can mimic catalytic properties of cyto-
chrome P450;[8] this metalloporphyrinic MOF approach
should be very promising to target efficient heterogeneous
catalysts for hydrocarbon oxidation.[9] However, such a
promise has not been fulfilled partly because of the difficul-
ties a) to synthesize high-quality large crystals for single-
crystal structure characterization, b) to stabilize the frame-
works and sustain their pore structures, and c) to construct
pores with suitable pore sizes, catalytic metal sites, and elec-
tronic environments to induce their high catalytic activities.
This situation has been significantly improved recently,[10–12]
E-mail: cdwu@zju.edu.cn
[b] Dr. Y. He, Prof. Dr. B. Chen
Department of Chemistry
University of Texas at San Antonio
One UTSA Circle, San Antonio
TX 78249-0698 (USA)
Fax : (+1)210-458-7428
E-mail: Banglin.Chen@utsa.edu
[c] Prof. Dr. J. Zhang
Fujian Institute of Research on the Structure of Matter
Chinese Academy of Sciences
Fuzhou, 350002 (P.R. China)
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201302025.
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which is attributed to scientific advances in structural char-
acterization and our capability to master the synthesis of
such framework materials with predictable structures.[13] To
immobilize metalloporphyrin sites into the porous mixed-
metal–organic frameworks (M’MOFs) by making use
of two types of linkers,[14] we target a highly efficient hetero-
À
geneous M’MOF catalyst for direct C H oxidative activa-
tion. Herein we report the structure, porosity, and
catalytic oxidation property of [Zn2(MnOH–TCPP)-
ACHTUNGTRENNUNG(DPNI)]·0.5DMF·EtOH·5.5H2O (CZJ-1; CZJ=Chemistry
Department of Zhejiang University; TCPP=tetrakis(4-car-
boxyphenyl)porphyrin); DPNI=N,N’-di-(4-pyridyl)-1,4,5,8-
naphthalenetetracarboxydiimide; Scheme 1), which exhibits
Scheme 1. a) Zn
2ACHTUNGTRENNUNG(COO)4 SBU, b) Mn–TCPP metalloAHCTUNRTGEGUNlNN iACHTNGURTENgNUGN and, and c) DPNI
organic pillar linker.
significantly high efficiency in the catalytic oxidation of cy-
clohexane with conversion of 94% to a mixture of cyclohex-
anone and cyclohexanol at room temperature.
Figure 1. X-ray crystal structures of a) CZJ-1, b) CZJ-1ꢀ2styrene, and
c) CZJ-1-Ti viewed along the channels, respectively.
Results and Discussion
of the activated sample was different from the freshly as-
synthesized sample, thus indicating that some structural
phase transformations might occur during the desolvation
process. We have successfully characterized the structure of
the desolvated framework CZJ-1-a by single-crystal X-ray
diffraction analysis. As expected, CZJ-1-a retains the identi-
cal framework connectivity to the as-synthesized CZJ-1 and
thus the same doubly interpenetrated cubic a-Po topology,
and the framework shrinks by 18% in terms of unit-cell
volume. It is interesting that the original PXRD pattern of
CZJ-1 can be regenerated when a desolvated sample of
CZJ-1-a was exposed to DMF vapor at 808C for 24 h (see
Figure S7 in the Supporting information). These results sug-
gest that CZJ-1 is flexible.[13j,k] The porous nature of CZJ-1
was further confirmed by the CO2 sorption isotherm. The
evacuated CZJ-1 at 908C for 6 h under high vacuum takes
up 47 cm3 gÀ1 of CO2 at 273 K and 1 atm, which is about half
that of the reported M’MOF ZnMn-RPM activated by su-
percritical CO2 activation of a surface area of 1000 m2 gÀ1.[11]
We examined CZJ-1 as a potential catalyst for the catalyt-
ic epoxidation of styrene. The catalytic epoxidation was car-
ried out using iodosylbenzene (PhIO) as the oxidant at
room temperature. As shown in Table 1, CZJ-1 exhibits
high catalytic activity in which styrene can be almost fully
Compound CZJ-1 was synthesized by heating a mixture of
MnOH H4TCPP, DPNI, and zinc nitrate in a mixed solvent
À
of DMF, EtOH, and nitric acid at 808C for two days. The
structure, composition, and phase purity were characterized
by single-crystal and powder X-ray diffraction (PXRD), as
well as elemental and thermogravimetric analysis (TGA).
The single-crystal X-ray diffraction study revealed that
CZJ-1 has the doubly interpenetrated cubic a-Po topology,
which has been well established in traditional porous
MOFs.[13i,14,15] The basic Zn
2ACHTNUTRGENNG(U COO)4 paddlewheel clusters as
the secondary building units (SBUs) are bridged by Mn–
TCPP to form two-dimensional sheets, which are further
bridged by the organic pillar linker DPNI to form a three-
dimensional porous structure. As shown in Figure 1a, CZJ-1
has pores of about 6.1ꢁ7.8 ꢂ2, taking into account the van
der Waals radii, viewed along the channels in which the
metal sites have been uniformly immobilized on the pore
surfaces. PLATON calculations indicate that CZJ-1 has an
accessible pore volume of 51.9%.[16]
TGA shows that CZJ-1 loses solvent molecules between
25 and 1508C (11.5%), and the desolvated framework can
be thermally stable up to 3608C. After the as-synthesized
CZJ-1 was heated at 908C under vacuum for 6 h, the PXRD
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Table 1. Selective oxidation of olefins catalyzed by CZJ-1.[a]
stable during the catalytic reaction. The catalytic
property of CZJ-1 was further compared with the
analogous homogeneous catalyst Mn–tetraphenyl-
porphyrin (Mn–TPP) under identical conditions. As
shown in Figure S26 of the Supporting Information,
heterogeneous CZJ-1 is apparently superior to ho-
mogeneous Mn–TPP: CZJ-1 not only exhibits sys-
tematically high catalytic activity but also signifi-
cantly high catalytic stability. Compound CZJ-1 ba-
sically keeps the similar catalytic activities even
after the sixth run, whereas Mn–TPP loses its cata-
lytic activities after the second run.
We are aware that an ideal heterogeneous cata-
lyst should have accessible catalytic sites and pores
by substrate molecules to facilitate substrate trans-
formation. We therefore examined the accessibility
of the open channels to substrate molecules of styr-
ene, cyclohexene, and cyclohexane by 1H NMR
spectroscopy. Compound CZJ-1 takes up 2.5 mole-
Entry
Substrate
Catalyst
Conv.
[%][b]
Select.
[%][b]
1
2
3
4
5
6
7
8
9
styrene
styrene
styrene
cyclohexene
styrene
styrene
styrene
styrene
styrene
CZJ-1
CZJ-1
CZJ-1
CZJ-1
MnCl2
DPNI
>99
98
94
99
27
5
64
80
78
98
98[c]
95[d]
>99
80
97
94
94
67
À
MnOH H4TCPP
MnOH H4TCPP and DPNI
MnOH H4TCPP, DPNI, and Zn
À
À
N
[a] Olefin (0.1 mmol), PhIO (0.15 mmol for styrene, 0.20 mmol for cyclohexene), cata-
lyst (0.005 mmol; 5 mol%), and acetonitrile (1.5 mL) sealed in a Teflon-lined screw-
cap vial were stirred at room temperature for 6 h. [b] Conversion [%] and selectivity
[%] were determined by GC-MS using an SE-54 column. [c] The second cycle. [d] The
sixth cycle.
oxidized into the epoxide product with 98% selectivity after
6 h (Table 1, entry 1). These excellent heterogeneous cata-
lysts should not only have high catalytic activity and selec-
tivity, but should also be highly stable and thus be easily re-
cycled for long-term usage. Compound CZJ-1 can be simply
recovered by filtration, which was subsequently reused in
successive runs. Even after the sixth recycle, the recovered
CZJ-1 (Table 1, entry 3) still exhibits a very high conversion
of 94% and selectivity of 95%, thus indicating that CZJ-1 is
indeed a superior heterogeneous catalyst for styrene epoxi-
dation at room temperature. A study of the turnover num-
bers (TONs) indicated that the catalyst CZJ-1 can be utiliz-
ed in much lower amounts and still be highly stable after
14068 turnovers without affecting its high catalytic activity.
We further examined the catalytic activity for the epoxida-
tion of cyclohexene at room temperature. Again, CZJ-1
(Table 1, entry 4) exhibits much higher catalytic activity
(99%) and selectivity (99%).
cules of styrene, 4.0 molecules of cyclohexene, and 2.0 mole-
cules of cyclohexane per formula unit, respectively. Such dif-
ferent sorption capacities of CZJ-1 for these substrates
might be attributed to their different molecular geometries
and sizes (Figure S9 in the Supporting Information). Styrene
is longer than cyclohexene and cyclohexane, but is a flatter
molecule with a thickness of about 3.4 ꢂ. The double bond
within cyclohexene makes it thinner (3.4–3.8 ꢂ) than cyclo-
hexane (3.8 ꢂ), so the packing of cyclohexene can be more
efficiently realized than that of cyclohexane within CZJ-1,
which enables CZJ-1 to take up more cyclohexene mole-
cules than cyclohexane.
The single-crystal X-ray structure study on the styrene-in-
cluded crystal CZJ-1ꢀ2styrene clearly indicated that styrene
molecules do locate inside the pore channels of the CZJ-1
framework (Figure 1b), which provided the fundamental
basis for the examined heterogeneous catalytic reaction to
take place inside the pores.[17] The unit-cell parameters of
CZJ-1ꢀ2styrene can be transferred to a=22.041, b=16.530,
c=16.713 ꢂ; a=89.947, b=116.282, and g=93.3318. Com-
pared with the unit-cell parameters of CZJ-1, the unit-cell
lengths were not significantly affected during the single-crys-
tal-to-single-crystal transformation. However, large varia-
tions were observed in the a, b, and g angles. Due to the
fact that the a and g angles are significantly deviated from
The recycle usage of CZJ-1 basically establishes its heter-
ogeneous nature, and the active catalytic sites should be the
MnIII–porphyrin moieties within the pores in CZJ-1. To fur-
ther confirm this claim, we compared the catalytic activities
of CZJ-1 with their molecular components of MnCl2, DPNI,
À
and MnOH H4TCPP, and their mechanically combined mix-
tures under identical reaction conditions. MnCl2 and DPNI
show very low catalytic activity with conversions of 27
(Table 1, entry 5) and 5% (Table 1, entry 6), respectively.
¯
908, the space group of CZJ-1ꢀ2styrene is triclinic P1 as op-
posed to monoclinic C2/m for CZJ-1, and the unit-cell pa-
rameters were correspondingly reduced to the reported
ones. When a sample of CZJ-1ꢀ2styrene was exposed to
the DMF vapor at 808C for 24 h, the sharp PXRD peaks of
CZJ-1ꢀ2styrene were almost identical to that of CZJ-1,
which once again confirmed the flexible and reversible
framework of CZJ-1 (see Figure S8 in the Supporting Infor-
mation). We also intentionally interrupted the catalytic oxi-
dation of styrene after 2 h and collected the solid CZJ-1 cat-
alyst to study the chemical species inside the pores. GC-MS
analysis of the desorbed species from this solid catalyst indi-
cates that the collected solid catalyst CZJ-1 does encapsu-
À
MnOH H4TCPP and its mechanical mixtures with DPNI
and/or Zn(NO3)2 do show quite moderate catalytic activity
G
that can transform 64–80% of the styrene into the styrene
epoxide (Table 1, entries 7–9) but still are not as efficient as
heterogeneous CZJ-1 (>99% conversion).
No trace product was detected when the filtrate from a
mixture of PhIO and solid CZJ-1 in acetonitrile was used in-
stead of CZJ-1 as the catalyst, which proved that the present
catalyst platform is heterogeneous in nature. The PXRD
pattern of the recovered solid after catalysis is identical to
the as-synthesized sample, thus indicating that CZJ-1 is
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B. Chen, C.-D. Wu et al.
late both reactant styrene and product 1,2-epoxyethylben-
zene molecules of about 1.6 and 0.9 moles per CZJ-1. More-
over, we further designed an experiment to evaluate the ac-
cessibility of the porphyrinic metal sites inside the pores of
CZJ-1. The crystals of CZJ-1 were suspended in toluene
tions. As shown in molecular homogeneous catalysts
{[FeIV(O)
A
R
and
{[FeIV(O)
ACHTNUGETRNNU(G Bn-tpen)]-
AHCTUNGTRENNUNG
l)ethylenediamine) for the catalytic oxidation of hydrocar-
bons, oxidation of cyclohexane is the most difficult among
the different substrates Ph3CH, cumene, PhEt, PhMe, 2,3-di-
methylbutane (2,3-DMB), and cyclohexane because of the
with TiACHTUNGTRENNUNG(OEt)4 for three days. Structural analysis on a newly
formed crystal of CZJ-1-Ti showed that the Ti species are
combined with the hydroxyl group on porphyrin MnIII cati-
ons (Figure 1c). These solid experimental results suggest
that CZJ-1 firstly adsorbed styrene molecules inside the
pore space to react with the catalytic metal sites, and further
transformed into the product 1,2-epoxyethylbenzene mole-
cules, which are then released from the pores of the catalyst
solid into the reaction solution during the catalytic oxidation
of styrene by the microporous CZJ-1 catalyst.
As demonstrated above, the catalytic reactions take place
inside the pore space; the inclusion of the substrate reac-
tants is essential for the catalytic chemical transformations.
It is thus expected that such microporous M’MOF heteroge-
neous catalyst will exhibit size-selective catalytic activities.
Indeed, CZJ-1 does not exhibit any catalytic activity toward
the oxidation of 1,1,2,2-tetraphenylethene, because 1,1,2,2-
tetraphenylethene is too bulky (about 8.2ꢁ12.7 ꢂ2) to have
access into the pores of CZJ-1. On the contrary, the homo-
geneous molecular catalyst Mn–TPP can catalyze oxidation
of 1,1,2,2-tetraphenylethene in 18.1% conversion.
The success of CZJ-1 as a stable heterogeneous catalyst
for the highly efficient and selective oxidation of styrene
and cyclohexene motivated us to examine this powerful
M’MOF catalyst on a much more challenging oxidation re-
action: oxidation of cyclohexane. Strikingly, CZJ-1 exhibits
extremely high catalytic activity for the oxidation of cyclo-
hexane even at room temperature with the conversion up to
94% and about 100% selectivity toward K–A oil
(Scheme 2). Even after recycling six times, the recovered
À
much stronger C H bond dissociation energy (DCÀH) of
about 99.3 kcalmolÀ1 in cyclohexane.[18] Previous efforts di-
rected at metalloporphyrin-containing mixed-metal–organic
À
frameworks for C H oxidation activation have been mainly
focused on those unsaturated hydrocarbons such as styrene
À
and ethylbenzene. Oxidative activation of the C H in unsa-
turated hydrocarbons is much easier than the one in saturat-
ed hydrocarbons.[10] Hence, the highly efficient and selective
oxidation of cyclohexane catalyzed by CZJ-1 is remarkable.
It is speculated that the catalytically active species are
those in situ formed porphyrin–MnV =O, as is well establish-
ed in their homogeneous Mn–porphyrin catalysts. The con-
fined Mn–porphyrin sites within the CZJ-1 framework not
only prevent m-oxo dimerization, which is commonly ob-
served in homogeneous molecular catalysts, but might also
collaboratively work together to enhance their catalytic ac-
tivity, given the fact that the neighboring Mn–porphyrin
sites are quite close and flexible with Mn···Mn distances of
about 13.9 ꢂ. The pores of 6.1ꢁ7.8 ꢂ2 in this flexible
M’MOF CZJ-1 can readily encapsulate the substrate cyclo-
hexane while possibly excluding the larger molecules of cy-
clohexanone and cyclohexanol, thus facilitating the product
release and their chemical transformations. The specific
electronic environments around the catalytic MnIII catalytic
sites that have been tuned by both porphyrin moieties and
the secondary organic linker DPNI might play important
roles as well.
Conclusion
The power to rationally immobilize different metal sites, to
tune the pore structures by different combinations of metal-
loligands and organic linkers, and to subtly change the steric
and electronic environments around the metal catalytic sites
by systematically modifying the metalloligands, has high-
lighted the M’MOF approach to be a very promising strat-
Scheme 2. Selective oxidation of cyclohexane catalyzed by CZJ-1.
CZJ-1 can still display quite high catalytic activity with a
conversion of 79%. The turnover number can reach up to
2668 without any deactivated signal. The molecular compo-
À
egy to develop porous heterogeneous C H oxidative activa-
tion catalysts. This work is expected to initiate more exten-
sive research endeavors on this very important topic in the
near future.
À
nents MnOH H4TCPP and Mn–TPP, however, can only
lead to much lower conversions of 40 and 47%, respectively.
Moreover, the conversion of cyclohexane cannot be signifi-
cantly improved when additional DPNI and/or ZnACTHNUTRGNEUNG(NO3)2
À
were added to the reaction mixture (48% for MnOH
Experimental Section
À
H4TCPP and DPNI; and 52% for MnOH H4TCPP, DPNI,
Materials and methods: All of the chemicals were obtained from com-
mercial sources and were used without further purification. MnOH–
TCPP and DPNI were synthesized according to the literature.[19,20] Ele-
mental analysis was performed using a ThermoFinnigan Flash EA 1112
element analyzer. IR spectrum (KBr pellet) was taken using an
AVATAR-370 Nicolet spectrometer in the 4000–400 cmÀ1 region. TGA
and Zn
(NO3)2). Furthermore, these molecular homogeneous
catalysts immediately lose catalytic activity after the first
run.
These results show that CZJ-1 is a superior heterogeneous
catalyst for the oxidation of cyclohexane under mild condi-
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C H Oxidative Activation
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was carried out using an SDT Q600 compositional analysis instrument
compared with the authentic samples analyzed under the same condi-
tions.
from 30 to 8008C under N2 atmosphere at a heating rate of 108CminÀ1
.
PXRD was recorded using a Rigaku D/MAX 2550/PC for CuKa radiation
(l=1.5406 ꢂ). H NMR spectra were recorded on a 500 MHz spectrome-
ter in CDCl3, and the chemical shifts were reported relative to the inter-
nal standard TMS (d=0 ppm).
A typical procedure for oxidation of cyclohexane: A mixture of catalyst
CZJ-1 (0.005 mmol), cyclohexane (0.1 mmol), and PhIO (0.2 mmol) in
CH3CN (1.0 mL) was sealed in a small Teflon-lined screw-cap vial and
stirred at room temperature for 20 h. The identities of the products were
determined by analyzing aliquots of the bulk solution using GC-MS and
compared with the authentic samples analyzed under the same condi-
tions, whereas the conversion and selectivity were obtained by GC analy-
sis with an FID using a capillary SE-54 column.
1
Synthesis of [Zn
2ACHTUNGTRENNUNG(Mn–TCPP)ACHTNUGTRENNUNG
À
A
mixture of MnOH H4TCPP (44 mg, 0.05 mmol), ZnCAHTUNGTRENNNUG
(44.5 mg, 0.15 mmol), DPNI (42 mg, 0.1 mmol), and 1.0m nitric acid
(150 mL, 0.15 mmol) in a mixed solvent of DMF (3 mL) and EtOH
(7 mL) was sealed in a screw-cap vial and heated at 808C for two days.
Brownish crystals of CZJ-1 were filtered, washed with DMF, EtOH, and
diethyl ether, and dried in the air. Yield: 75%. IR (KBr pellet): n˜ =1719
(s), 1677 (s), 1654 (w), 1607 (m), 1560 (m), 1514 (w), 1483 (w), 1384 (s),
1345 (s), 1249 (s), 1205(s), 1147 (w), 1011 (s), 870 (w), 805 (m), 779 (m),
716 (m), 669 (m), 643 (w), 532 (w), 493 cmÀ1 (w); elemental analysis
calcd (%) for CZJ-1: H 3.62, C 57.67, N 7.57; found: H 3.56, C 58.02, N
7.63. Crystals of CZJ-1 were easily broken into fragments during solvent
evaporation. We thus carefully activated the ethanol-exchanged crystals
of CZJ-1 under vacuum at À208C for 24 h to prevent crystal cracking
and to generate the solvent-free CZJ-1-a. Compound CZJ-1ꢀ2styrene
was accordingly prepared by immersing the solvent-free CZJ-1-a crystals
in styrene at À208C for 12 h. Compound CZJ-1-Ti was prepared by sus-
Study of the TONs for epoxidation of styrene by CZJ-1: Styrene
(100 mmol), PhIO (150 mmol), and CZJ-1 (0.005 mmol) in acetonitrile
(50 mL) were reacted at room temperature. The aliquots were regularly
taken out for GC analysis to determine the conversion of styrene and
TONs (TON is defined as the mole ratio of the substrate converted to
the catalyst).
Study of the TONs for oxidation of cyclohexane by CZJ-1: Cyclohexane
(50 mmol), PhIO (100 mmol), and CZJ-1 (0.0025 mmol) in acetonitrile
(50 mL) were sealed in a Teflon-lined screw-cap vial and reacted at room
temperature. The aliquots were regularly taken out for GC analysis to
determine the conversion of cyclohexane and TONs.
pending the crystals of CZJ-1 in a solution of Ti
À208C for 3 d.
ACHTUNGRTEN(NGNU OEt)4 in toluene at
Single-crystal X-ray data collections and structure determinations: The
determinations of the unit cells and data collections for the crystals of
compounds CZJ-1, CZJ-1-a, CZJ-1ꢀ2styrene, and CZJ-1-Ti in sealed ca-
pillaries were performed using an Oxford Xcalibur Gemini Ultra diffrac-
tometer with an Atlas detector. The data were collected using graphite-
monochromated-enhanced ultra Cu radiation (l=1.54178 ꢂ) at 293 K.
The data sets were corrected by empirical absorption correction by using
spherical harmonics, implemented in the SCALE3 ABSPACK scaling al-
gorithm.[21] The structures of all compounds were solved by direct meth-
ods and refined by full-matrix least-squares methods with the SHELX-97
program package.[22] The solvent molecules in compounds CZJ-1 and
CZJ-1-Ti are highly disordered; the SQUEEZE subroutine of the
PLATON software suite was used to remove the scattering from the
highly disordered guest molecules.[16] The resulting new files were used to
further refine the structures. The H atoms on C atoms were generated
geometrically.
Acknowledgements
This work was financially supported by the NSF of China (grant no.
21073158), Zhejiang Provincial Natural Science Foundation of China
(grant no. Z4100038), the Fundamental Research Funds for the Central
Universities (grant no. 2013FZA3006), and the Welch Foundation AX-
1730 (B.C.).
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sis with
column.
a flame-ionization detector (FID) using a capillary SE-54
A typical procedure to study the chemical species adsorbed inside the
pores of CZJ-1 during oxidation of styrene: Compound CZJ-1
(0.015 mmol), styrene (0.6 mmol), and PhIO (0.3 mmol) in CH3CN
(1.5 mL) reacted at room temperature for 2 h. The solid was recovered
by filtration, quickly washed with acetonitrile three times, digested by
dilute aqueous ammonia solution, and then extracted by diethyl ether.
The aliquots of the bulk solution was subjected to GC-MS analysis, and
Chem. Eur. J. 2013, 00, 0 – 0
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B. Chen, C.-D. Wu et al.
Zhang, L. Zhang, L. Wojtas, P. Nugent, M. Eddaoudi, M. J. Zawor-
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ic, space group C2/m; a=21.453(5), b=16.258(5), c=15.921(5) ꢂ;
b=130.17(4)8; V=4243(2) ꢂ3; Z=2; m=2.296 mmÀ1; R1=0.1279,
wR(F2)=0.2546,
and
S=1.072.
CZJ-1ꢀ2styrene:
¯
C88H52MnN8O12Zn2; Mr =1599.06; triclinic, space group P1; a=
13.372(3), b=14.164(3), c=16.713(3) ꢂ; a=69.626(16)8, b=
68.786(17)8, g=73.544(17)8; V=2721.1(9) ꢂ3; Z=1; m=1.843 mmÀ1
;
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R1=0.1339,
wR(F2)=0.2799,
and
S=1.013.
CZJ-1-Ti:
C72H37.5MnN8O14.5Ti0.5Zn2; Mr =1456.23; monoclinic, space group
C2/m; a=22.136(4), b=16.647(4), c=16.551(3) ꢂ; b=114.63(2)8;
V=5543.9(19) ꢂ3; Z=2; m=2.071 mmÀ1
;
R1=0.0997, wR(F2)=
0.2220, and S=1.060. CCDC-923792 (CZJ-1), -882569 (CZJ-1-a),
-882227 (CZJ-1ꢀ2styrene), and -923793 (CZJ-1-Ti) contain the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
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[14] H. Chung, P. M. Barron, R. W. Novotny, H.-T. Son, C. Hu, W. Choe,
Cryst. Growth Des. 2009, 9, 3327.
[15] CZJ-1: C72H37MnN8O13Zn2; Mr =1407.78; monoclinic, space group
C2/m, a=22.058(7), b=16.907(2), c=16.240(4) ꢂ; b=121.36(4)8;
V=5172(2) ꢂ3; Z=2; m=1.895 mmÀ1; R1=0.0882, wR(F2)=0.1757,
and S=0.891. CZJ-1-a: C72H36MnN8O12Zn2; Mr =1390.77; monoclin-
[22] G. M. Sheldrick, Program for Structure Refinement; University of
Gçttingen, Germany, 1997.
Received: May 27, 2013
Published online: && &&, 0000
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À
C H Oxidative Activation
FULL PAPER
Copycatalyst: To mimic the cyto-
chrome P450 oxidation catalyst, a
Metalloporphyrins
manganese–porphyrin metalloACTHUNTGRENNUGliACHTUTNGRENNUGgand
M.-H. Xie, X.-L. Yang, Y. He,
J. Zhang, B. Chen,*
C.-D. Wu* ..................... &&&& — &&&&
has been incorporated into a 3D
porous mixed-metal–organic frame-
work as the highly efficient heteroge-
neous catalyst for alkene epoxidation
and cyclohexane oxidation at room
temperature (see figure).
À
Highly Efficient C H Oxidative Acti-
vation by a Porous MnIII–Porphyrin
Metal–Organic Framework under Mild
Conditions
Chem. Eur. J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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&
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These are not the final page numbers!