2D Co-based coordination polymer with a histidine derivative as an efficient heterogeneous catalyst for the oxidation of cyclohexene

Article abstract of DOI:10.1039/c7ce00349h

The hydrothermal reaction of CoCl₂ and 4-((1-carboxy-2-(1H-imidazol-4-yl)ethylamino)methyl)benzoic acid (H₂L) generated a {Co₂(H₂O)}-based 2D coordination framework, {(Co(L)(H₂O))₂(H₂O)}_n (1). Heterogeneous catalytic experiments on the allylic oxidation of cyclohexene show that activated 1 exhibits high catalytic activity using tert-butylhydroperoxide (t-BuOOH) as the oxidant toward the formation of tert-butyl-2-cyclohexenyl-1-peroxide. The activation energy for the oxidation of cyclohexene with catalyst 1 was approximately calculated as 91.98 kJ mol^-1. This work demonstrates that a degree of creativity in the coordinatively unsaturated metal sites in CPs could significantly enhance their heterogeneous catalytic activity and selectivity.

Full text of DOI:10.1039/c7ce00349h

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2
D Co-based coordination polymer with histidine derivative as
an efficient heterogeneous catalyst for the oxidation of
cyclohexene
Received 00th January 20xx,
Accepted 00th January 20xx
a,*
a
a
a
b,*
DOI: 10.1039/x0xx00000x
Fan Yu, Xin Xiong, Kexing Huang, Yinliu Zhou, and Bao Li
www.rsc.org/
Abstract: Hydrothermal reaction of CoCl
2
and 4-((1-carboxy-2-(1H-imidazol-4-yl)ethylamino)methyl)benzoic acid (H
2
L)
generated a {Co (H O)}-based 2D coordination framework, {(Co(L)(H
2
2
2
O)) (H O)} (1). Heterogenous catalytic experiments
2
2
n
on allylic oxidation of cyclohexene show that activated 1 exhibits highly catalytic activity using tert-butylhydroperoxide (t-
BuOOH) as oxidant toward formation of tert-butyl-2-cyclohexenyl-1-peroxide. The activation energy for the oxidation of
-1
cylcohexene with 1 catalyst was approximately calculated as 91.98 kJ mol . This work demonstrates that creativity of
coordinatively unsaturated metal sites in CPs could significantly enhance heterogeneous catalytic activity and selectivity.
7
catalytic system.
Introduction
In the past decades, coordination polymers (CPs) have been
attracting great attention owing to their potential applications
Catalytic oxidation of cyclohexene into value-added
oxygenated derivatives is particularly important and
extensively investigated because its oxidation products are
useful intermediates in organic synthesis and the fragrance
in various scientific research fields. Recently, CPs based
heterogeneous catalysts have been also investigated due to its
8
catalytically active sites and accessible processing methods.
1
Though an amount of interesting and novel catalysts based on
CPs have been explored, the rational design of CPs based
heterogeneous catalysts with high catalytic performance
under mild reaction conditions, environmental benignity and
industry. The traditional catalytic procedures produce a large
number of environmental pollutants during the process of
oxidation. Therefore, the development of effectively green
processes for the catalytic oxidation of alkenes is becoming
9
2
easy operation procedures still remains a painful challenge.
urgently necessary. Many studies have revealed that
In the transitional metal complexes utilized as heterogeneous
0,11
transition metal complexes containing redox active transition
metals are important homogenous catalysts which could
1
catalysts, cobalt based CPs attract great attention.
Co(II)
3
,4 atoms could adopt varied coordination geometries such as
selectively oxidize cyclohexene to the specific oxydates.
octahedral,
tetrahedral,
square-pyramidal,
trigonal-
However, the performance of these catalysts is still limited,
and the recovery of the catalysts from the reaction systems is
very difficult since the oxidation reactions are usually
performed in the liquid phase. Based on the environmental
and economic considerations, heterogeneous catalysts are
bipyramidal and square-planar, which makes it easy to bear
1
2,13
unsaturated coordination sites with catalytic activity.
all the above considerations in mind, we selected histidine
derivatives, 4-((1-carboxy-2-(1H-imidazol-4-
yl)ethylamino)methyl)benzoic acid (H L), acted as the organic
With
5
,6
2
desired to improve the effect. Currently, it is still very hard
for the synthesis of effectively green heterogeneous catalysts
since the troublesome synthesis process and unclear catalytic
mechanism of heterogeneous catalysts. Therefore, to probe
the effective catalysts and explain the detailed catalytic
mechanism becomes the main challenge in a heterogeneous
linker to produce the cobalt based CPs. The amino acid
derivative was produced via adorning auxiliary coordinative
group as benzoate on the amino acid scaffold. Through the
published research results related with the amino acid
derivatives, this kind of ligands reserves the classical N-O
chelate coordinate mode and possesses large bulk effect,
which could be easy to result in CPs with remnant coordinative
1
4
sites and much more stabilization. In consistent with our
assumption, a 2D cobalt(II) based CP, {(Co(L)(H O)) (H O)} ),
2
2
2
n
(1
had been successfully constructed by the utilization of the
designed derivative. Single-crystal X-ray diffraction studies
reveal that water molecules were finally coordinated on the
cobalt ion, which could be easily activated via heat.
Subsequently, particular attention is given to investigate the
effect of activated cobalt based heterogeneous catalyst in the
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allylic oxidation of cyclohexene using tert-butylhydroperoxide coordinated aqua molecule inter-links two adjacent cobalt
t-BuOOH) as oxidant and selectively catalyzes the oxidation atoms to form the dinuclear unit. The Co-N and -O bond
(
reaction toward formation of tert-butyl-2-cyclohexenyl-1- distances range from 2.088(4) to 2.350(3) Å, in accordance
peroxide. Furthermore, we presented a probable mechanism with the Co(II) state. Each L ligand utilizes its part of amino acid
to illustrate the high catalytic activation and selectivity for the to chelate one cobalt ion, which was further connected by the
1
catalytic oxidation. In order to compare the catalytic activity benzoate part of other derivative to form the 1D chain. The
, an isomorphic Mn-based CP, {(Mn(L)(H O)) (H O)} ), staggered 1D chains was cross-linked by coordinated aqua
of
1
2
2
2
n
(2
had been also constructed and utilized as the catalyst in the molecules to construct the 2D layer structure.
oxidation of cyclohexene under the same experiment Electronic spectra of 1
condition. Catalytic results reveal much lower effect compared
Electronic spectra of phase-pure micro-crystal samples of
1
are
is consistent
with an octahedral environment of divalent cobalt. One
with 1.
also measured. The pink color of compound
1
Table 1. Crystal data of 1 and 2
absorption band centered at 226 nm could be assigned to n →
* transitions caused by ligand-centered electronic transitions;
1
2
π
the other at 512 nm might be ascribed to [ T (F)
Chemical formula
Formula Mass
C
28
H
32Co
746.46
2
N
6
O
11
C
28
H
32Mn
742.41
2
N
6
O
11
4
4
→
T (P)]
1g
1
g
transitions, in accord with the typical hexa-coordinated
octahedral coordination environment of high spin Co(II)
species.
Crystal system
Monoclinic
22.089(13)
6.142(4)
13.906(9)
125.968(9)
1527.0(16)
C2
Monoclinic
22.4588(11)
6.1786(4)
14.1282(7)
127.551(4)
1554.29(15)
C2
a/Å
b/Å
c/Å
β/°
Unit cell volume/Å
Space group
Z
3
2
2
No. of reflections measured
No. of independent reflections
5487
2954
1275
1275
Final R
Final wR(F ) values (I > 2σ(I))
Final R values (all data)
1
v2alues (I > 2σ(I))
0.0606
0.1639
0.0715
0.1796
0.0624
0.1769
0.0640
0.1806
1
2
Final wR(F ) values (all data)
Results and discussion
Synthesis of 1
The complex
1
and
2
was synthesized by hydrothermal
and were further
reaction at 90
℃
. The compositions of
1
2
deduced from single crystal X-ray diffraction, elemental
analyses, and IR spectrum. Crystal data are listed in Table 1.
The broad bands in the 3579-3534, 3449-3331 and 3103-2883
-1
cm region are assigned to the O-H, N-H and C-H stretching
vibrations, respectively. The IR spectra also show characteristic
absorption bands mainly attributed to the asymmetric (νas: ca.
−
1
−1
1
600 cm ) and symmetric (νs: ca. 1385 cm ) stretching
vibrations of the carboxylate groups. No band in the region
−
1
1
690–1730 cm , indicates complete deprotonation of the
carboxylate groups, and is consistent with the result of the X-
ray diffraction analysis.
Crystal structure of 1 and 2
Single crystal X-ray diffraction results indicate that complexes
1
and
asymmetric units. Herein, the detailed structural description of
complex as the example had been presented. Compound
crystallizes in the monoclinic space group C2. The asymmetric
unit of
2 are isostructural with similar cell parameters and
1
1
1
contains one histidine derivatives, one cobalt ion and Figure 1. a) the asymmetric unit of 1, hydrogen atoms were omitted for clarity; b) the
two coordinated water molecules, shown in Figure 1. The perspective view of double-layered 2D structure of 1 along b-axis direction; c) the
perspective view of double-layered 2D structure of 1 along c-axis direction.
central cobalt ion adapts highly-distorted octahedral
configuration and is coordinated by two carboxylate oxygen
Catalytic properties of 1 and 2
atoms from benzoate and amino acid, two aqua molecules and
two N atoms from imidazole ring and amino N atom. One
2
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mmol, based on cobalt). TON = 435 , TON(turnover number) = moles converted/mol of
As a test reaction for catalytic activity, the liquid-phase
-
1
active Co site. TOF = 0.138 h .
oxidation of cyclohexene in the presence of
1 and 2 was also
examined using tert-butyl hydroperoxide as oxidant. Normally,
cyclohexene oxide acted as the main product of the reaction of
catalytic epoxidation was detected with the cobalt-based CPs
as catalyzer. However, the different and interesting catalytic
To confirm the heterogeneous nature of the catalytic
reaction,
after reaching approximately 65% conversion (which took
about h for 1) at 60 °C. It is clear from Figure 2 that no
further catalytic conversion was observed, indicating that
cobalt ions (if any) leaching from are not responsible for the
1 was removed from the hot solution by filtration
3
result was exhibited when
1 utilized as catalytic agent in the
oxidations of cyclohexene. In contrast to other reports about
the lesser extent of catalytic effect with respect to the Co-
based CPs, the catalytic data demonstrates that oxidation of
1
observed activity. The filtrate was also analyzed by atomic
absorption spectroscopy (AAS), which indicated that no free
cobalt(II) ions in the filtrate were detected due to the
concentration of cobalt(II) ions beyond the lower detection
cyclohexene in the presence of
1
is fast, and several turnovers
(Figure 2), whereas the
are possible in the presence of
1
reaction occurring in the absence of catalyst under the same
conditions is almost negligible (ca. 1% conversion after 6 h).
The reaction was first tested on the oxidation reaction using t-
limit of the AAS instrument. The results indicated that
1
behaves as a truly heterogeneous catalyst. More importantly,
the catalyst could be easily retrieved and reused. The results of
oxidation with the recycled catalyst in five times exhibit the
similar efficiency, which indicated reusable and efficiently
BuOOH as oxidant at 60 °C, giving the maximum substrate
conversion of 82.56% after 6 h. The main reaction product is
tert-butyl-2-cyclohexenyl-1-peroxide ( named as P1), followed
by the by-product, 2-cyclohexen-1-one ( named as P2) and
cyclohexene oxide ( named as P3), which were further
validated by combined gas chromatographic and mass
catalytic activity of 1, even with little higher catalytic result of
the second time that might be caused by the error in
operation.
To further investigate the quick catalytic reaction, the
chemical kinetics including the rate constant and activity
energy was determined. The rate constant (k) for these
reactions, which was utilized to calculate the activation energy,
was determined at different temperatures (30, 40, 50 and 60
spectrometric product analysis.
selectivity toward the formation of tert-butyl-2-cyclohexenyl-
-peroxide (ca. 72%), which is relative higher than the
1 has an exceptionally high
1
homogeneous catalysis with cobalt(II)-based CPs when alkyl
hydroperoxides are utilized as the oxidant. A further increase
of reaction time to 12 h did not bring about higher conversion
and more excellent selectivity. In terms of the crystal structure,
the open Co(II) sites on the surfaces should be responsible for
the excellent catalytic activity since no accessible void in the
unit cell could be observed. In addition, the steric
configuration along with the designed derivative and
°C), as shown in Figure 2. The conversion in the presence of
increased with the reaction temperature from 30 to 60
1
°
C,
along with the increasing of rate constant ( listed in Table 2 ).
The increasing trend of rate constant (k) for the conversion of
cyclohexene indicates that the oxidation of cyclohexene was
an energy-activated process. According to the Arrhenius
−
1
equation, the plot of ln k versus T gave an activation energy
1
mol . The energy of activation for the
corresponding spacial conformation of
1
might play important
−
(
Ea) in units of kJ
·
roles in resulting different main product compared to other
6
similar Co-based catalysts.
a
oxidation of cylcohexene in the presence of
1
was finally
approximately calculated as 91.98 kJ mol , which are well
validated that as catalyst plays an important role in
-1
1
decreasing the energy of activation and promote the
corresponding reaction quickly.
Figure 3. (left) Allylic oxidation of cyclohexene with 2 as catalyst (square) and filtration
of 2 (star) at 60 ℃ ; (right) Cyclic experiments utilized the same catalyst at 60 ℃ . Reaction
conditions: cyclohexene (10 mmol), t-BuOOH (18.5 mmol), 1,2,4-trichlorobenzene (1.5
mmol; as internal standard), 1 (0.0135 mmol, based on manganese).
Figure 2. (1): Conversion versus time curves for cyclohexene oxidation with 1 as
Comparably, substituted
1
catalyst with catalyst
2, much
catalyst at 30 ℃ ( black ), 40 ℃ ( red ), 50 ℃ ( blue ) and 60 ℃ ( green ); (2): Fitness of the
conversion of cyclohexene at different temperature; (3)Allylic oxidation of cyclohexene lower catalytic productivity had been presented at 60
°C,
with 1 as catalyst (square) and filtration of 1 (star) at 60 ℃ ;(4) Cyclic experiments giving the maximum substrate conversion of 52.36% with the
utilized the same catalyst at 50 ℃ . Reaction conditions: cyclohexene (10 mmol), t-
selectivity toward the formation of tert-butyl-2-cyclohexenyl-
BuOOH (18.5 mmol), 1,2,4-trichlorobenzene (1.5 mmol; as internal standard), 1 (0.0135
1
-peroxide (ca. 75%) after 8 h, shown in Figure 3. No free
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Mn(II) ions in the filtrate were detected due to the would convert to trivalent one, and then recovery. The
concentration of Mn(II) ions beyond the lower detection limit transition between Co(II) and Co(III) species seems easily
of the AAS instrument, which was also verified by the filtration compared to Mn catalyst due to the electronic configurations
experiment. The results indicated that
heterogeneous catalyst. However, the catalytic effect of
obviously not good as , which might be ascribed to the
2 behaves as a truly of spin state of different metal ions, which might be
1
5
2
is responsible for the difference of catalytic results.
1
natural advantage of cobalt ions compared to manganese ions.
According to the assumed mechanism, the divalent catalyst
Table 2. Conversion and Kinetic Parameters at Optimum Molar Ratio of the Allylic Oxidation of Cyclohexene with 1 as Catalyst
OOBuꢀt
O
Catalyst 1
tꢀBuOOH
+
+
O
-
1
-1
-1
Temp. (℃ )
Total Con. (wt %)
P1 Con. (wt %)
P2 Con. ( wt %)
16.93
P3 Con. ( wt %)
15.85
k ( L mol
s
)
E
a
( kJ mol
)
-
-
-
-
6
3
4
5
6
0
0
0
0
10.58
33.51
55.58
82.56
67.22
62.8
3.36×10
1.73×10
3.60×10
9.94×10
5
17.59
19.61
91.98
5
5
73.94
71.93
14.50
11.56
15.23
12.84
tꢀBuOH
+
tꢀBuO
tꢀBuOOH
+
OOBu-t
+
Co(II)ꢀCP
tꢀBuOOH
HOꢀCo(III)ꢀCP
OH
tꢀBuOO
+
+
Co(II)ꢀCP
H O
2
Scheme 1. The proposed reaction mechanism of 1-catalyzed allylic oxidation of cyclohexene
cyclohexenyl radical to result in tert-butyl-2-cyclohexenyl-1-
1
0b
Oxidation Mechanism with 1 Catalyst.
peroxide.
In addition, the O-O bond of tert-butyl-2-
cyclohexenyl-1-peroxide is not stable and thermally
decomposes to give the byproduct 2-cyclohexen-1-one.
With the consideration of tert-butyl-2-cyclohexenyl-1-peroxide
as the main product and previous mechanistic studies of cobalt
catalysis, a reaction pathway that freely diffusing peroxy
radicals are generated by reductive cleavage of tert-butyl
hydroperoxo coordinated onto cobalt(III) centers in CP had
been set up.
Conclusions
In summary, we have succeeded in preparing a catalyst based
In the initiation step, t-BuOOH ligands preferentially utilize an on cobalt coordination complex containing histidine derivative
oxygen atom to coordinate onto the unoccupied coordination through self-assembly under hydrothermal reaction
6
.
a,9f
site of Lewis acid Co(II) ions in the assemble of
1
Electrons conditions, which exhibits high catalytic effect for oxidizing
transfer from the Co(II) centers to the peroxy bond of t- cyclohexene to give allylic products under mild condition. The
BuOOH, causing the breakdown of weak O−O bonds, and bring Co-based catalyst undergoes no metal leaching, and could be
out of tert-butoxy radicals (t-BuO
the one hand, the resulting HO-Co(III) species might release research work highlights the potential of developing CPs as
·
) and HO-Co(III) species. On easily recovered from the catalytic reaction system. This
1
0e
the
·
OH radical via fission of the Co−O bond, which would highly stable, molecularly tunable, recyclable and reusable
heterogeneous catalysts for alkene oxidation, which would
further react with t-BuOOH molecule to produce t-BuOO
·
radical. The HO-Co(III) species could recover the initial catalyst lead to commercial exploitation of Co-based CPs with the
which could repeat the catalytic again. On the other hand, the highly catalytic activity toward formation of oxygenated
resulting t-BuO·
radical quickly draw a hydrogen ion from cyclohexene derivatives.
cyclohexene to yield 3-cyclohexenyl radical and t-BuOH. Then,
the excess t-BuOO· radical continuously combine with 3-
4
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temperature under the same conditions as above description.
And the catalytic results were fitted by NONLIN software by
utilizing Arrhenius equation.
Experimental Section
Materials and Methods. All reagents and solvents were
purchased from commercial sources. The ligand was
1
synthesized according the reference.
4a
FT-IR spectra were
−
1
measured in the 4000−400 cm range on a Mattson Alpha-
Centauri spectrometer. Elemental analysis (C, H, N) was
performed on a VarioEL III Elemental Analyzer. The catalytic
products were measured by GC equipment with a capillary (30
m long × 0.25 mm i.d., WondaCAP 17) and FID detector (GC-
Acknowledgements
We gratefully acknowledge the National Natural Science
Foundation of China ( nos. 51403079 and nos. 21471062 ) and
Jianghan university for generous financial support.
2
014C, Shimadzu, Japan). All UV/vis spectra were tested by a
Cary TU-1900 double beam UV−vis spectrophotometer.
Synthesis of {(Co(L)(H O)) (H O)} ). A mixture of CoCl
L ( 8.8mg, 0.02mmol) were added to a
O ( 4 mL ) .The mixture solution was sealed in a
Notes and references
2
2
2
n
(
1
2 2
·6H O
1
(a) K. Brown, S. Zolezzi, P. Aguirre, D. Venegas-Yazigi, V. Paredes-
Garcia, R. Baggio, M. A. Novak and E. Spodine, Dalton Transactions,
(
9.5mg, 0.04mmol), H
2
solution of H
2
2
009, 1422-1427; (b) P. Aguirre, K. Brown, D. Venegas-Yazigi, V.
Teflon-lined steel autoclave and the pH adjusted to about 7
o
with 2mol/L NaOH, then heat at 90 C for 3 days. After it was
Paredes-Garcia and E. Spodine, in Macromolecular Symposia, eds. J.
Costamagna, F. M. Rabagliati and B. L. Rivas, Editon edn., 2011, vol.
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cooled to room temperature and filtration, pink block crystals
of
1
in a yield of 50.4% (based on L) were obtained. Anal. Calcd
11: C, 45.05; H, 4.32; N, 11.26. Found: C, 44.69;
2 6
for C28H32Co N O
−
1
H, 3.98; N, 11.62. IR ( KBr pellet, cm ): 3377, 3231, 2924, 1606,
532, 1397, 1311, 1081, 995.
Synthesis of {(Mn(L)(H O))
method to 1, excepted for the metal salt as MnCl
11: C, 45.54; H, 4.37; N, 11.38. Found: C,
1
(H
2
O)}
n
(
2). Similar synthesis
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2
2
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2
. Anal. Calcd
2 6
for C28H32Mn N O
−
1
45.03; H, 3.88; N, 11.93. IR ( KBr pellet, cm ): 3372, 3230,
924, 1606, 1531, 1396, 1310, 1082, 994.
2
2
X-Ray Structural Determination. X-ray diffraction data of
0.2 0.1 0.1 mm ) and ( 0.2 0.2 0.1 mm ) were
collected on Bruker diffractometer using Mo-K = 0.71073
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1
(
×
×
2
×
×
α (λ
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3
2
015, 145, 589-595; (b) H. Noh, Y. Cui, A. W. Peters, D. R. Pahls, M.
2
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squares procedure based on F values. The hydrogen atom
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allowed to ride on the parent atoms. CCDC-1533551 (
1) and
CCDC-1533552 (2) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre.
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Catalytic Oxidation of Cyclohexene. 1 or
2 was added to a
solution of cyclohexene (10 mmol), t-BuOOH (18.5 mmol, 70%
in water ), 1,2,4-trichlorobenzene (1.5 mmol; as internal
standard), catalyst (0.0135 mmol, based on metal ions) at
3
1.
room temperature.The reaction mixture was stirred at 60 °C.
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0
.25 mm Acrodisc nylon filter. Then, the sample was identified
8
by GC MS and quantified by GC. For investigations on metal
−
leaching from the catalyst, the hot reaction mixture was
filtered at the reaction temperature after 3 h. To investigate
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2
6
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2
D Co-based coordination polymer with histidine derivative as
an efficient heterogeneous catalyst for the oxidation of
cyclohexene
By utilizing the histidine derivatives acted as the organic linker, a 2D cobalt based
coordination polymer had been constructed. The activated cobalt based heterogeneous
catalyst shows highly catalytic activity in the allylic oxidation of cyclohexene and
selectively
catalyzes
the
oxidation
reaction
toward
formation
of
tert-butyl-2-cyclohexenyl-1-peroxide.