Article

pubs.acs.org/IC

Co(II)-MOF: A Highly Ecient Organic Oxidation Catalyst with Open

Metal Sites
Jian-Cheng Wang, Feng-Wen Ding, Jian-Ping Ma, Qi-Kui Liu, Jun-Yan Cheng, and Yu-Bin Dong*
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for
Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong
Normal University, Jinan 250014, P. R. China
S Supporting Information
*

ABSTRACT: A porous Co(II)-MOF (1) was synthesized by the

combination of a bent imidazole-bridged ligand and p-phthalic acid
(PTA) with Co(OAc)2 under solvothermal conditions. This Co(II)MOF (1) is able to undergo a reversible MeOH substitution reaction
on the Co(II) center via a single-crystal-to-single-crystal process. The
desolvated Co(II)-MOF (2) with the open Co(II) sites is very stable
(up to 350 C). Furthermore, 2 is a highly active heterogeneous
catalyst for various organic substrates oxidation in the presence of tertbutyl hydroperoxide (TBHP) under milder conditions. The
importance of open Co(II) sites in 2 for the organic substrates
oxidation is directly evidenced by the single-crystal X-ray diraction.

INTRODUCTION
Organic oxidation, especially the inert CH bond of hydrocarbons, constitutes one of the most desirable but challenging
issues.1 For example, the oxidation of cyclohexane is the main
industrial way to a mixture of cyclohexanone (K) and
cyclohexanol (A), the important intermediates in the
production of Nylon-6 and Nylon-66, and also raw materials
for the production of adipic acid.2a,b The present commercial
process for cyclohexane oxidation is carried out at ca. 150 C
and 12 MPa pressure, aording 57% conversion to so-called
KA-oil.2c,d In addition to that, the oxidation of olens and
alcohols is also important, not only for fundamental study but
also for ne chemical production.3 Therefore, the development
of more ecient catalysts, especially ecient versatile catalysts,
for organic oxidation is highly demanded and important.
On the other hand, traditional oxidation catalysts based on
transition metal molecular complexes such as Co, Cu, Fe, and
Mn are usually homogeneous ones, which makes their cyclic
utilization almost impossible. For environmental and natural
resource issues, the construction of new types of heterogeneous
catalysts is highly valued.4 Fortunately, metalorganic frameworks (MOFs), as an emerging class of functional porous
materials, provide a new tunable platform to fabricate
heterogeneous catalysts.5 As we know, MOFs themselves are
inherent heterogeneous catalysts due to their inorganic
organic hybrid composition and polymeric nature. Furthermore, the construction of MOF-type heterogeneous catalysts is
convenient, and they can be easily prepared via assembly or a
postsynthetic approach. However, catalysis based on MOFs is
far less explored as compared to the huge amount of known
MOF structures. Among various MOFs, the MOFs with open
2015 American Chemical Society

metal sites are more appreciated. They are widely accepted to

be the important candidates for applications such as catalysis,6
adsorption/separation,7 storage,8 and sensing.9
In this contribution, we report the synthesis of a Co(II)MOF (1) that can undergo a reversible MeOH binding at the
Co(II) atom in a single-crystal-to-single-crystal (SC-SC)
fashion. The desolvated Co(II)-MOF (2), which contains the
coordinatively unsaturated Co(II) sites, is porous and robust.
Furthermore, it is a high-eciency recyclable versatile
heterogeneous catalyst for cyclohexane, olens, and alcohols
oxidations under milder conditions.

EXPERIMENTAL SECTION

Materials and Measurements. All the chemicals were obtained

from commercial sources and used without further purication.
Intermediate A (Scheme 1) for ligand L was prepared according to the
literature method.10 Infrared (IR) spectra were obtained in the 400
4000 cm1 range using a Bruker ALPHA FT-IR Spectrometer.
Elemental analyses were performed on a PerkinElmer model 2400
analyzer. 1H NMR data were collected on an AM-300 and Varian
Advance 600 spectrometer. Chemical shifts are reported in relative
to TMS. All crystal data were obtained by Agilent SuperNova X-ray
single crystal diractometer. GC-MS analysis data were performed on
a J&K S011525300 gas chromatographic (Agilent 6890GC5973MS). The separation data were obtained by Agilent 1260 Innity
HPLC system equipped with an Agilent C18 reverse phase column
(150 4.6 mm, 5 m). Thermogravimetric analyses were carried out
on a TA Instrument Q5 simultaneous TGA under owing nitrogen at
a heating rate of 10 C/min. XRPD patterns was obtained on D8
Received: August 23, 2015
Published: October 26, 2015
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Scheme 1. Synthesis of L

Scheme 2. Synthesis of 1 and 2

Synthesis of 2 ([Co3L(PTA)2.5(OAc)]solvent). 1 was allowed to

stand at ambient temperature for ca. 15 min to generate 2
quantitatively. IR (KBr pellet cm1): 3425(s), 1613(s), 1506 (m),
1384 (vs), 1149(w), 1017(vw), 1016(w), 918(w), 823(m), 750(v),
544(m). Elemental analysis(%): calcd for C49H35Co3N4O12: C 56.12,
H 3.36, N 5.34; found: C 56.52, H 3.46, N 5.33.
Synthesis of 1 ([Co3L(CH3OH) (PTA)2.5(OAc)]solvent). 2 was
soaked in MeOH at ambient temperature for 24 h to aord 1
quantitatively. IR (KBr pellet cm1): 3425(s), 1614(s), 1569(s), 1505
(m), 1384 (vs), 1129(w), 1072(vw), 1017(w), 824(m), 750(v),
527(m).
Typical Catalytic Procedure for Cyclohexane. A mixture of
cyclohexane (10 mL), TBHP (0.31 mmol, 30.8 L) and C5H6Cl (0.10
mmol, 10.16 L, as internal reference) was stirred at ambient
temperature for 5 min, and then 2 (2%) was added inside. The mixture
was stirred at 60 C for 22 h (monitored by GC) to aord the
corresponding KA oil. The conversions and products were determined
by GC-MS. 2 was recovered by centrifugation and ltration, and then
directly reused in the next run under the same reaction conditions.
Typical Catalytic Procedure for Styrene and Its Derivatives.
2 (2%) was added to a MeCN solution (10 mL) of the substrate (1.0
mmol) and TBHP (2.0 mmol), and the mixture was stirred at 60 C
(monitored by GC) to aord the corresponding products. The
conversions and products were determined by GC-MS. 2 was
recovered by centrifugation and ltration, and then directly reused
in the next run under the same reaction conditions.
Typical Catalytic Procedure for Benzyl Alcohol and Its
Derivatives. 2 (2%) was added to a CH3CN (10 mL) solution of
alcohol substrates (1 mmol) and TBHP (2 mmol), the mixture was
stirred under aerobic conditions. The conversions and products were
determined by GC.
X-ray Structure Determination.11 All single-crystal X-ray
intensity data were measured at 100 K on a Agilent SuperNova
CCD-based diractometer (Cu K radiation, = 1.54184 ). After
determination of crystal quality and initial tetragonal unit cell
parameters, a hemi sphere of frame data was collected. The raw data
frames were integrated with CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02082013 CrysAlis171. NET)
(compiled Aug 2 2013, 16:46:58). Empirical absorption correction
using spherical harmonics, implemented in SCALE3 ABSPACK

Advance X-ray powder diractometer with Cu K radiation ( =

1.5405 ).
Synthesis of L. Synthesis of B. A mixture of A (10.58 mmol, 4.00
g) and NaH (11.64 mmol, 0.28 g) in THF (50 mL) was stirred at 80
C, and then CH3CH2I (11.64 mmol, 2.63 g) was added in the
reaction system. The mixture was further stirred at 80 C to aord
crude product. B was obtained as a yellow crystalline solids (2.89 g,
68%) after purication by chromatography on silica gel using
CH3COOEt as the eluent. IR(KBr pellet cm1): 3442 (m),
2981(m), 1916(vw), 1637(m), 1500(vs), 1471(s), 1387(s), 1067(s),
1009(vs), 948(s), 838(vs), 818(s), 660(m), 561(m). 1H NMR (400
MHz, CDCl3, 25 C, TMS, ppm): = 8.31 (s, 1H, -C3HN2), 7.63
7.65(d, J = 8.0 Hz, 2H, -C6H4), 7.327.39(m, 4H, -C6H4), 7.21
7.23(d, J = 8.0 Hz, 2H, -C6H4), 3.933.98 (q, J = 10.0 Hz, 2H,
CH2), 1.311.34 (t, J = 9.0 Hz, 3H, CH3). Elemental
Analysis(%): calcd for C17H14N2Br2: C 50.28, H 3.47, N 6.90, Br
39.35; found: C 50.45, H 3.49, N 6.92, Br 39.54.
Synthesis of L. A mixture of B (5.00 mmol, 2.03g), pyridine-4boronic acid (12.00 mmol, 1.48g), K2CO3 (40.00 mmol, 5.53 g),
tetrakis(triphenylphosphine)palladium (0.50 mmol, 0.57 g) in a mixed
solvent system (EtOH: H2O: toluene =3:2:3) was stirred at reux for
48 h. Ligand L was obtained as yellow crystalline solids (1.70 g, 84.2%)
after chromatography purication. IR (KBr pellet cm1): 3423(ms),
3032(vw), 2969(vw), 2360(vw), 1595 (vs), 1496 (m), 1397(m),
1189(w), 1109(w), 992(w), 950(w), 857(w), 815(vs), 766(vw),
736(vw), 658(w), 543(w), 515(w). 1H NMR (300 MHz, CDCl3, 25
C, TMS, ppm): = 8.758.77 (d, J = 6.0 Hz, 2H, -C6H4N), 8.63
8.75 (d, J = 6.0 Hz, 2H, -C6H4N), 7.817.83 (d, J = 6.0 Hz, 2H,
-C6H4), 7.75 (s, 1H, -C3HN2), 7.627.66 (m, 4H, -C6H4N), 7.51
7.58 (m, 6H, -C6H4), 3.923.99 (q, 2H, CH2), 1.291.40 (t, 3H,
CH3). Elemental Analysis(%): calcd for C27H22N4: C 80.57, H 5.51,
N 13.92; found: C 80.64, H 5.49, N 13.67.
Synthesis of 1 ([Co3L(CH3OH)0.5(H2O)0.5(PTA)2.5(OAc)]solvent). A
mixture of L (4.06 mg, 0.01 mmol), p-phthalic acid (PTA) (1.66 mg,
0.01 mmol), Co(OAc)2 (0.01 mmol, 2.13 mg) and MeOH (2 mL) was
sealed in a glass tube and then heated at 120 C for 72 h. After the
mixture was allowed to cool to room temperature (50 h), red-purple
crystals of 1 were isolated. Yield, 78%. IR (KBr pellet cm1): 3424(s),
2360(w), 1613(s), 1568(s), 1504 (m), 1384 (vs), 1072(vw),
1016(vw), 824(m), 750(v), 524(m).
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Table 1. Crystal Data and Structural Renement Parameters for 1, 2, and 1a
formula
fw
/
crystal system
space group
T/K
a ()
b ()
c ()
(deg)
(deg)
(deg)
V (3)
Z
cak/gcm3
/mm1
F (000)
GOF
data/restraints/parameters
R1 [I > 2(I)]
wR2 [all data]
a

C49.50H38Co3N4O13
1073.63
1.54184
Triclinic
P1
100.00(10)
11.5791(4)
15.2623(6)
19.2483(9)
70.394(4)
76.587(3)
82.732(3)
3112.6(2)
2
1.146
6.639
1096
1.046
11720/7/636
0.0552
0.1453

C49H35Co3N4O12
1048.60
1.54184
Triclinic
P1
100.00(10)
11.6664(6)
14.9859(8)
19.4221(11)
75.584(5)
75.343(5)
87.679(4)
3180.8(3)
2
1.095
0.823
1068
1.038
11323/0/618
0.0396
0.1049

C50H39Co3N4O13
1080.64
1.54184
Triclinic
P1
100.00(10)
11.5784(7)
15.3081(12)
19.2580(11)
70.388(6)
76.659(5)
83.048(6)
3125.0(4)
2
1.148
6.615
1104
0.945
11117/0/636
0.0706
0.1768

R1 = F0| |Fc/|F0|, wR2 = {[w(F02 Fc2)2]/[w(F02)2]}1/2.

a large solvent-accessible volume of 1098.7 3 (35.3% of a total

unit cell volume of 3112.6(2) 3). The crystallographically
unidentied MeOH molecules (conrmed by 1H NMR
spectrum, Supporting Information) are located inside.
Interestingly, compound 1 can undergo a reversible MeOH
substitution at ambient temperature in which the single-crystal
nature is maintained (Scheme 2). As shown in Figure 2, when 1
was allowed to stand at room temperature for a while (15
min), 2 was generated; meanwhile, the crystal changed color
from pink to purple. Single-crystal X-ray diraction revealed
that 2 possesses the same structural motif as 1 (Table 1). Upon
closer observation of the structure, the coordinated MeOH/
H2O molecule was detached from the Co(2) center. As
indicated in Figure 2, the six-coordinated sphere of {Co(2)O5N} in 1 changed to a coordinatively unsaturated vecoordinated {Co(2)O4N} in 2 while no coordination mode
change for the other three types of Co(II) centers is observed
during the transformation process. Compared to 1, the solvent
accessible void volume in 2 eectively increased (1307.2 3,
41.1% of the total unit cell volume 3180.8(3) 3) after removal
of the coordinating MeOH molecules. In addition, 1 can be
readily regenerated (1) without losing its single crystallinity
when 2 was soaked in MeOH for 24 h (Table 1). The
simulated and measured XRPD patterns are well consistent
with each other, indicating this reversible solvent substitution
triggered SC-SC transformation is clean (Supporting Information). It is noteworthy that the encapsulated MeOH guest
molecules in 2 can be completely removed at ca. 150 C
(monitored by thermogravimetric analysis (TGA), Supporting
Information) and the empty framework with open Co(II) sites
is stable up to ca. 350 C based on TGA and XRPD
measurements (Supporting Information). Such a highly
thermally stable MOF with open metal sites could be used as
the heterogeneous catalyst for the organic reactions carried out
at higher temperature.
The permanent porosity of compound 2 was determined by
measuring nitrogen-gas (N2) adsorption at 77 K. It exhibits

scaling algorithm. Analysis of the data showed negligible crystal decay

during data collection. The structure was solved by a combination of
direct methods and dierence Fourier syntheses, and rened by fullmatrix least-squares against F2, using the SHELXTL software package.
The species in this region were too severely disordered to be modeled,
and were treated with SQUEEZE/PLATON. These species include
some CH3OH and H2O molecules. The contribution of the disordered
species was removed from the structure factor calculations. The
tabulated F(000), MW and density reect known cell contents only.
Eventually, all non-hydrogen atoms of the framework were rened
with anisotropic displacement parameters. Hydrogen atoms were
placed in geometrically idealized positions and included as standard
riding atoms.

RESULTS AND DISCUSSION

Crystal Structures and SC-SC Transformation. Compound 1 was simply synthesized as red-purple crystalline solids
by the combination of L, p-phthalic acid (PTA) coligand, and
Co(OAc)2 in MeOH under solvothermal conditions (120 C)
in good yield (Scheme 2). The single-crystal diraction
revealed that 1 crystallized in the triclinic space group P1
(Table 1). There are four crystallographically independent
Co(II) centers in 1. They all adopt distorted octahedral
coordination spheres, including {Co(1)O6}, {Co(2)O5N},
{Co(3)O4N2}, and {Co(4)O6}. As shown in Figure 1, six
PTA coligands act as the bridges to link two Co(1) and one
Co(2) atoms to generate the trinuclear {(Co(1)2Co(2)} core,
while four PTA coligands and two coordinating OAc anions to
bind two Co(3) and one Co(4) atoms into the {Co(3)2Co(4)}
core. Notably, a coordinating MeOH/H2O (1:1) solvent
molecule is attached to the Co(2) center with a Co(2)
O(13) bond length of 2.130(3) . In the solid state, two sets of
trinuclear Co3 clusters are further linked alternatively by L and
PTA into a 3D framework. An inspection of Figure 1 reveals
that the overall array of 1 contains a 3D intersecting channel
system and wide open windows, with an approximate eective
cross section of ca. 12 8 (down a), 10 8 (down b), 13 8
(down c), and 10 8 2 (down [1 0 1]), which is reected in
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Figure 1. (ab) Two sets of trinuclear Co3 cluster cores and the coordination spheres of Co(1), Co(2), Co(3), and Co(4) found in 1. (cf)
Channels opening along the crystallographic a, b, c, and [1 0 1] directions in 1.

Figure 2. Reversible MeOH substitution-triggered single-crystal-to-single-crystal transformation. The corresponding single-crystal pictures are given
in the inset.

classic type I isotherms characterized by a sharp uptake under

low relative pressures in the range P/P0 = 105102 (Figure
3), a signature feature of microporous materials. The lack of
hysteresis indicates that the adsorption and desorption
mechanisms are similar and that the adsorption is reversible.
The BrunauerEmmettTeller (BET) surface areas were
found to be 595 m2 g1 for 2 (Supporting Information). The

pore-size distributions of 2 were calculated by nonlocal density

functional theory (NLDFT). Compound 2 shows a narrow
pore width (5.5 , Supporting Information), which is slightly
smaller than the theoretical values predicted from their crystal
structures.
Catalytic Properties of 2. Compound 2 with open Co(II)
sites was used to test the catalytic activity for the solvent-free
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Table 3. Summary of the Reported Cyclohexane Oxidation

Reactions Using MOFs as the Heterogeneous Catalysts
Catalyst
PIZA-3
Cu3(OH)(-pz)32+
Mn-TMPyPrho-ZMOF
NH4[Cu3(OH)(4carboxypyrazolato)3]
ZnMn-RPM
MIL-101 family
MOF-253

Figure 3. N2 adsorption isotherms for compound 2 at 77 K. Red and

black circles represent adsorption and desorption branches,
respectively.

AuMIL-53(Cr) and
AuMIL-101(Cr)
AuPdMIL-101

cyclohexane oxidation. Compound 2 was activated by heating

at 70 C (2 h) for removal of encapsulated MeOH guest before
the oxidation reaction (Supporting Information). Table 2

CZJ-1
(MnIII-TCPP)]
Zr-PCN-221(Fe)

Table 2. Solvent-Free Cyclohexane Oxidation Catalyzed by 2

NHPI/Fe(BTC)
CoII-MOF (2), this work
a

Solvent/Oxidant
CH3CN/PhIO
CH3CN/
HNO3/H2O2
cyclohexane/
TBHP
cyclohexane/
TBHP
CH2Cl2/ArINTs
CH3CN/
TBHP-O2
cyclohexane/
1.0 MPa O2
cyclohexane/
1.2 MPa O2
cyclohexane/
1.5 MPa O2
CH3CN/PhIO
CH2Cl2/PhIO
cyclohexane/
TBHP
cyclohexane/
6 bar O2
cyclohexane/
TBHP

Condition

Yieldref

r.t./2 h
r.t./6 h

47.812
2.732.213

65 C/24 h

91.514

70 C/24 h

415

r.t./24 h
70 C/8 h

2016
3817

160 C/8 h

60.818

130 C/8 h

31.319

160 C/4 h

50.820

r.t./22 h
r.t./6 h
65 C/11 h

9421
20.622
92.323

160 C/24 h

5.724

60 C/22 h

88

Overall CH conversion.

Selectivity (%)

Entry

Conversion (%)a

1
2
3
4
5

85
87
88
87
83

34
30
28
29
33

66
70
72
71
67

TMPyPrho-ZMOF,14 CZJ-1,21 and Zr-PCN-221(Fe)23 performed better than Co(II)-MOF (2). On the other hand, some
reported results did not provide solid evidence for the catalyst
reusability or the reused MOF-catalysts that display a stable
catalytic activity. Therefore, 2 herein could be a benecial
complement for the MOFs to heterogeneous cyclohexane
oxidation catalysts.
In order to gain insight into the heterogeneous nature of 2, a
leaching test was carried out. As indicated in Figure 4, no
further reaction took place without 2 after initiation of the
oxidation reaction at 14 h. This nding indicates that no
leaching of the catalytically active sites occurs and that 2
exhibits a typical heterogeneous catalyst nature. As a
heterogeneous catalyst, 2 can be reused. After each catalytic
cycle, 2 could be easily recovered by centrifugation and
ltration, and then directly reused in the next run under the
same reaction conditions. As shown in Table 2, KA oil was still
obtained in an ideal yield (83%) after ve catalytic cycles.
Actually, the catalytic activity of 2 only gradually dropped and
the conversion of cyclohexane was still above 70% at run 10
within 22 h. As indicated in Figure 4, after ve consecutive
catalytic runs, 2 was demonstrated to be highly crystalline from
XRPD patterns. In addition, the 1H NMR performed on the
reaction ltrate, which was obtained by hot ltration during
reaction, indicated that no proton resonances related to L were
detected, which further conrmed 2 as a heterogeneous catalyst
is stable under reaction conditions. Typical XPS data of 2
before and after the oxidation reaction were shown in Figure 4.
The Co 2p core lines of the samples are split into Co 2p3/2
(781.1 eV) and Co 2p1/2 (796.8 eV) main peaks accompanied
by satellite bands at 785.8 and 802.3 eV, respectively.
Prominent Co 2p3/2 satellite bands are indicative of a highspin Co(II) state.26 No dierence was observed before and after
the catalytic reactions, further implying 2 is stable during the
reaction processes. Furthermore, SEM images (Figure 5)
revealed that the morphology of the Co(II)-framework is

Conversion is determined by GC-MS.

shows that 2 exhibits a high catalytic activity for cyclohexane

oxidation. The treatment of cyclohexane with TBHP in the
presence of 2 at 60 C for 22 h aorded the KA oil in 8388%
yields (Table 2, entries 15 and Supporting Information). No
dierence in yield was observed after 22 h of monitoring by
GC. Additionally, this 2-catalyzed oxidation is clean, and almost
no other oxidation products were detected. This is dierent
from the most reported MOFs-catalyzed cyclohexane oxidation
results (Table 3):1224 the cyclohexanol is the preferable
product (70%), and a relatively smaller amount of cyclohexanone (30%) is produced (Table 2). High selectivity of
cyclohexanol species, however, was observed on a series of
metal-containing molecular sieves.25
It is worth pointing out that the oxidation reaction described
herein needs no additional organic solvents except the reaction
substrates. Thus, as this oxidation is easy to manipulate and
avoids the use of toxic and volatile solvents, it could be
considered as a clean catalytic organic synthesis approach. In
addition, the coordinating solvent molecules play a key role in
this cyclohexane oxidation. For example, 1 catalyzed the
cyclohexane oxidation with MeOH/H2O to result in a very low
conversion (24 h, <19%) at 60 C, which suggests that the
open Co(II) atoms indeed are the key active catalytic sites for
this cyclohexane oxidation.
So far, a series of examples of MOFs-catalyzed cyclohexane
oxidation were reported. As indicated in Table 3, the overall KA
oil conversions in most cases are low, and only Mn10869

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Figure 4. Left: leaching test for catalytic oxidation based on 2. Middle: XRPD pattern of 2 and its XRPD patterns after each catalytic cycle. Right:
XPS spectra of 2 before and after the oxidation reaction.

retained, which demonstrated that 2 is durable for the catalytic

oxidation reactions.

On the other hand, the oxidant of TBHP is essential for this

cyclohexane oxidation. The control experiment showed that no
oxidation products such as cyclohexanone and cyclohexanol
were detected based on GC-MS analysis when the experiment
was conducted in the absence of TBHP (Supporting
Information). Notably, the catalysis base on 2 might occur
on the external surface. In order to prove it, larger sized
substrate 1,2,3,4-tetrahydronaphthalene, which cannot be
uploaded into the pores of 2, was subjected to the conditions
of the above reaction. The corresponding oxidation product
was obtained in good yield (64.1%), which supported that the
catalytic reactions herein are a surface catalytic process
(Supporting Information).27
Interestingly, as a heterogeneous oxidation catalyst, 2 is
versatile. It can also be used to eectively catalyze the oxidation
of the styrene, substituted styrenes,28 and phenyl-substituted
alcohols29 with dierent para-substituents under milder
conditions (CH3CN, 60 C).
As shown in Table 4, the catalytic oxidation of styrene by 2
almost quantitatively yielded the styrene, and the selectivity is
mainly toward epoxide (61%). Notably, the conversion is still
above 90% even after 6 catalytic cycles (Supporting

Figure 5. Photographs and SEM images of as-synthesized (left) and

recovered 2 after catalytic ve-cycle (right).

Table 4. Catalytic Oxidation of Olens by 2a

a
b

Substrate (1 mmol), solvent (10 mL), oxidant (2 equiv), catalyst/substrate/oxidant = 2/100/200, 338 K, 2224 h under aerobic conditions.
Conversion is determined by GC. cSelectivity is determined by GC.
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Table 5. Catalytic Oxidation of Alcohols Catalyzed by 2a

a
b

Substrate (1 mmol), solvent (10 mL), oxidant (2 equiv), catalyst/substrate/oxidant = 2/100/200, 60 C, 1620 h under aerobic conditions.
Conversion is determined by GC. cSelectivity is determined by GC.

Table 6. Catalytic Oxidation of sec-Alcohols Catalyzed by 2a

Substrate (1 mmol), solvent (10 mL), oxidant (2 equiv), catalyst/substrate/oxidant =2:100:200 under aerobic conditions. bConversion is
determined by GC.

Information). In order to explore the eect of substituents on

this oxidation reaction, dierent types of olens were used as
substrates under the reaction conditions. When 4-chlorostyrene
with an electron withdrawing group of chloride at the paraposition is used, similar conversion as that for styrene, but
slightly lower selectivity to the epoxide product, was observed.
On the other hand, when an electron donating group,
methoxyl, was used as a substituent on styrene at the paraposition (4-methoxylstyrene), the selectivity is mainly toward
aldehyde, although the conversion is equivalent to that of
styrene. In addition, a tiny amount of ketone products are
detected (48%) during the reactions (Table 4).
For oxidation of primary alcohols, 2 still exhibits a high
catalytic activity for benzyl alcohol oxidation (conversion above
80% after 3 cycles, Supporting Information). Table 5 shows
that the conversions of benzyl alcohol and benzyl alcohols with

electron-withdrawing groups are high (8898%) and that the

reaction is selective toward aldehyde products. The highest
conversion was obtained (98%) when 4-methoxybenzyl alcohol
was used as the substrate, but the selectivity is mainly toward
carboxylic acid, which might be attributed to the strong
electronic eect of the electron donating methoxyl group.
This is dierent from the case for primary alcohols: only
ketone products are detected during oxidation of secondary
alcohols based on GC analysis. As shown in Table 6, the
conversion of 1-phenylethanol is high (above 90% after 3
cycles, Supporting Information). Again, the conversion of 1-(4methoxyphenyl)ethanol with an electron donating group (entry
3) is much higher than that of 1-(4-bromophenyl)ethanol
(entry 2), which clearly resulted from the inactivation eect of
bromide at the para-position.
10871

DOI: 10.1021/acs.inorgchem.5b01938
Inorg. Chem. 2015, 54, 1086510872

Article

Inorganic Chemistry

2015, 44, 19221947. (f) Zhu, Q.-L.; Qiang, X. Chem. Soc. Rev. 2014,
43, 54685512.
(6) (a) Wang, K.; Feng, D.; Liu, T.-F.; Su, J.; Yuan, S.; Chen, Y.-P.;
Bosch, M.; Zou, X.; Zhou, H.-C. J. Am. Chem. Soc. 2014, 136, 13983
13986.
(7) (a) Wiers, B. M.; Foo, M.-L.; Balsara, N. P.; Long, J. R. J. Am.
Chem. Soc. 2011, 133, 1452214525. (b) Zhou, W.; Wu, H.; Yildirim,
T. J. Am. Chem. Soc. 2008, 130, 1526815269. (c) Vilhelmsen, L. B.;
Walton, K. S.; Sholl, D. S. J. Am. Chem. Soc. 2012, 134, 1280712816.
(8) Xiang, S.; Zhou, W.; Gallegos, J. M.; Liu, Y.; Chen, B. J. Am.
Chem. Soc. 2009, 131, 1241512419.
(9) Shustova, N. B.; Cozzolino, A. F.; Reineke, S.; Baldo, M.; Dinca,
M. J. Am. Chem. Soc. 2013, 135, 1332613329.
(10) Powell, A. B.; Ueda, Y. S. M.; Bielawski, C. W.; Cowley, A. H. J.
Am. Chem. Soc. 2011, 133, 52185220.
(11) (a) CrysAlisPro, Version 1.171.36.32 (release 02-08-2013
CrysAlis171.NET); Agilent Technologies (compiled Aug 2
2013,16:46:58). (b) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; University of Utrecht: Utrecht, The Netherlands, 1998.
(12) Suslick, K. S.; Bhyrappa, P.; Chou, J. H.; Kosal, M. E.; Nakagaki,
S.; Smithenry, D. W.; Wilson, S. R. Acc. Chem. Res. 2005, 38, 283.
(13) Di Nicola, C.; Karabach, Y. Y.; Kirillov, A. M.; Monari, M.;
Pandolfo, L.; Pettinari, C.; Pombeiro, A. J. L. Inorg. Chem. 2007, 46,
221230.
(14) Alkordi, M. H.; Liu, Y. l.; Larsen, R. W.; Eubank, J. F.; Eddaoudi,
M. J. Am. Chem. Soc. 2008, 130, 1263912641.
(15) Quartapelle Procopio, E.; Linares, F.; Montoro, C.; Colombo,
V.; Maspero, A.; Barea, E.; Navarro, J. A. R. Angew. Chem., Int. Ed.
2010, 49, 73087311.
(16) Farha, O. K.; Shultz, A. M.; Sarjeant, A. A.; Nguyen, S. T.;
Hupp, J. T. J. Am. Chem. Soc. 2011, 133, 56525655.
(17) Maksimchuk, N. V.; Kovalenko, K. A.; Fedin, V. P.; Kholdeeva,
O. A. Chem. Commun. 2012, 48, 68126814.
(18) Long, J. L.; Wang, L. M.; Gao, X. F.; Bai, C. H.; Jiang, H. F.; Li,
Y. W. Chem. Commun. 2012, 48, 1210912111.
(19) Sun, Z. G.; Li, G.; Liu, L. P.; Liu, H. O. Catal. Commun. 2012,
27, 200205.
(20) Long, J. L.; Liu, H. L.; Wu, S. J.; Liao, S. J.; Li, Y. W. ACS Catal.
2013, 3, 647654.
(21) Xie, M.-H.; Yang, X.-L.; He, Y. B.; Zhang, J.; Chen, B. L.; Wu,
C.-D. Chem. - Eur. J. 2013, 19, 1431614321.
(22) Zou, C.; Zhang, T. F.; Xie, M.-H.; Yan, L. J.; Kong, G.-Q.; Yang,
X.-L.; Ma, A.; Wu, C.-D. Inorg. Chem. 2013, 52, 36203626.
(23) Feng, D. W.; Jiang, H.-L.; Chen, Y.-P.; Gu, Z.-Y.; Wei, Z. W.;
Zhou, H.-C. Inorg. Chem. 2013, 52, 1266112667.
(24) Mikami, Y.; Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H.
ChemCatChem 2013, 5, 19641970.
(25) Tian, P.; Liu, Z.; Wu, Z.; Xu, L.; He, Y. Catal. Today 2004, 93
95, 735742.
(26) Ma, R.; Liang, J.; Takada, K.; Sasaki, T. J. Am. Chem. Soc. 2011,
133, 613620.
(27) Zhang, X.-M.; Zhao, C.-W.; Ma, J.-P.; Yu, Y.; Liu, Q.-K.; Dong,
Y.-B. Chem. Commun. 2015, 51, 839842.
(28) (a) Zhang, J.; Biradar, A. V.; Pramanik, S.; Emge, T. J.; Asefa, T.;
Li, J. Chem. Commun. 2012, 48, 65416543. (b) Xie, M.-H.; Yang, X.L.; Wu, C.-D. Chem. Commun. 2011, 47, 55215523. (c) Lee, D. H.;
Kim, S.; Hyun, M. Y.; Hong, J.-Y.; Huh, S.; Kim, C.; Lee, S. J. Chem.
Commun. 2012, 48, 55125514.
(29) (a) Qi, Y.; Luan, Y.; Yu, J.; Peng, X.; Wang, G. Chem. - Eur. J.
2015, 21, 15891597. (b) Zhou, Y.-X.; Chen, Y.-Z.; Cao, L.; Lu, J.;
Jiang, H.-L. Chem. Commun. 2015, 51, 82928295.

CONCLUSION
In summary, we report a novel 3D Co(II)-MOF (1) which can
reversible bind MeOH at the Co(II) atom without loss of its
single crystallinity. The desolvated Co(II)-MOF (2) with open
Co(II) sites is very robust and can be stable up to 350 C.
More importantly, it is a highly active recyclable solid catalyst
for oxidation of various organic substrates. The results indicate
that the open metal sites play a central role for the MOFcatalytic oxidation.

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.inorgchem.5b01938.
Additional characterization for 1, 1, and 2, experimental
details for organic oxidation and GC-MS analysis, and
ORTEP gures and tables of interatomic distances and
bond angles for 1, 1, and 2 (PDF)
X-ray crystallographic data for CCDC 1405798 (CIF)
X-ray crystallographic data for CCDC 1405799 (CIF)
X-ray crystallographic data for CCDC 1405800 (CIF)

AUTHOR INFORMATION

Corresponding Author

*E-mail: yubindong@sdnu.edu.cn.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We are grateful for nancial support from NSFC (Grant Nos.
21475078, 21271120, and 21201112), 973 Program (Grant
Nos. 2012CB821705 and 2013CB933800), and the Taishan
scholars construction project.

REFERENCES

(1) (a) Bromberg, S. E.; Yang, H.; Asplund, M. C.; Lian, T.;
McNamara, B. K.; Kotz, K. T.; Yeston, J. S.; Wilkens, M.; Frei, H.;
Bergamn, R. G.; Harris, C. B. Science 1997, 278, 260263. (b) Hwang,
K.-C.; Sagadevan, A. Science 2014, 346, 14951497.
(2) (a) Ulrich, H. Raw materials for Industrial Polymers; Hanser
Publishers: Munich, Germany, 1998. (b) Musser, M. T. Cyclohexanol
and Cyclohexanone. Ullmanns Encyclopedia of Industrial Chemistry;
Wiley-VCH Verlag: Weinheim, 2007. (c) Cavani, F.; Alini, S. In
Sustainable Industrial Processes; Cavani, F., Centi, G., Perathoner, S.,
Triro, F., Eds.; Wiley-VCH: 2009; p 367. (d) Hattori, H.; Ide, Y.;
Ogo, S.; Inumaru, K.; Sadakane, M.; Sano, T. ACS Catal. 2012, 2,
19101915. (e) Wang, C. H.; Chen, L. F.; Qi, Z. W. Catal. Sci.
Technol. 2013, 3, 11231128.
(3) Xia, Q. H.; Ge, H. Q.; Ye, C. P.; Liu, Z. M.; Su, K. X. Chem. Rev.
2005, 105, 16031662.
(4) (a) Thomas, J. M.; Raja, R.; Sankar, C.; Bell, R. G. Acc. Chem. Res.
2001, 34, 191. (b) Breynaert, E.; Hermans, I.; Lambie, B.; Maes, G.;
Peeters, J.; Maes, A.; Jacobs, P. Angew. Chem., Int. Ed. 2006, 45, 7584.
(c) Zhao, R.; Ji, D.; Lv, G.; Qian, G.; Yan, L.; Wang, X.; Suo, J. Chem.
Commun. 2004, 904. (d) Liu, Y.; Tsunoyama, H.; Akita, T.; Xie, S.;
Tsukuda, T. ACS Catal. 2011, 1, 2.
(5) (a) Corma, A.; Garca, H.; Llabres i Xamena, F. X. Chem. Rev.
2010, 110, 46064655. (b) Yoon, M.; Srirambalaji, R.; Kim, K. Chem.
Rev. 2012, 112, 11961231. (c) Zhao, M.; Ou, S.; Wu, C.-D. Acc.
Chem. Res. 2014, 47, 11991207. (d) Liu, J.; Chen, L.; Cui, H.; Zhang,
J.; Zhang, L.; Su, C.-Y. Chem. Soc. Rev. 2014, 43, 60116061.
(e) Dhakshinamoorthy, A.; Asiri, A. M.; Garcia, H. Chem. Soc. Rev.
10872

DOI: 10.1021/acs.inorgchem.5b01938
Inorg. Chem. 2015, 54, 1086510872