Synthesis of a pair of homochiral manganese-based coordination polymers as stable catalyst for the selective oxidation of cis-cyclooctene

Article abstract of DOI:10.1016/j.inoche.2018.03.009

A pair of homochiral manganese-based coordination polymers [Mn(H₂O)₂(bpy)(L-DBTA)] (L-1) and [Mn(H₂O)₂(bpy)(D-DBTA)](D-1): Syntheses, crystal structures and catalytic properties for the selective oxidation of cis-cyclooctene. The homochiral manganese-based 3D supermolecule framework exhibits high catalytic activity (38.85% conversion based on cis-cyclooctene and 76.13% selectivity for epoxycyclooctane) and stability for selective oxidation of cis-cyclooctene in the absence of solvent using TBHP as radical initiator and oxygen (in the air) as oxidant at 80 °C.

Full text of DOI:10.1016/j.inoche.2018.03.009

Accepted Manuscript
Synthesis of a pair of homochiral manganese-based coordination
polymers as stable catalyst for the selective oxidation of cis-
cyclooctene
Guangju Zhang, Yang Shi, Ying Wei, Qingguo Zhang, Yanping
Zhang, Kedi Cai, Siqi Xiu
PII:
DOI:
Reference:
S1387-7003(18)30083-2
doi:10.1016/j.inoche.2018.03.009
INOCHE 6913
To appear in:
Inorganic Chemistry Communications
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Revised date:
Accepted date:
26 January 2018
24 February 2018
9 March 2018
Please cite this article as: Guangju Zhang, Yang Shi, Ying Wei, Qingguo Zhang, Yanping
Zhang, Kedi Cai, Siqi Xiu , Synthesis of a pair of homochiral manganese-based
coordination polymers as stable catalyst for the selective oxidation of cis-cyclooctene. The
address for the corresponding author was captured as affiliation for all authors. Please
check if appropriate. Inoche(2017), doi:10.1016/j.inoche.2018.03.009
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ACCEPTED MANUSCRIPT
Synthesis of a pair of homochiral Manganese-based coordination polymers as stable
catalyst for the selective oxidation of cis-cyclooctene
Guangju Zhang,* Yang Shi, Ying Wei,* Qingguo Zhang,* Yanping Zhang, Kedi Cai, Siqi Xiu
College of Chemistry, Chemical Engineering, Bohai University, Jinzhou 121013, Liaoning Province, China
Keywords: coordination polymers; selective oxidation; catalysis
A pair of homochiral manganese-based coordination polymers
catalytic activity (38.85% conversion based on cis-cyclooctene
[Mn(H2O)2(bpy)(L-DBTA)] (L-1) and [Mn(H2O)2(bpy)(D- and 76.13% selectivity for epoxycyclooctane) and stability for
DBTA)](D-1): Syntheses, crystal structures and catalytic properties selective oxidation of cis-cyclooctene in the absence of solvent
for the selective oxidation of cis-cyclooctene. The homochiral using TBHP as radical initiator and oxygen (in the air) as
manganese-based 3D supermolecule framework exhibits high
oxidant at 80 ℃.
compounds [20-22]. The chemical transformations including
(ep)oxidation are interesting since epoxides are key starting
materials for a wide variety of products in organic chemistry.
For many years, coordination polymers/MOFs are demonstrated
to be one of the most promising catalysts for the oxidation of a
variety of substrates such as alkanes, olefins, alcohols, sulfides, and
aromatic amines [23-26]. The most studied reaction catalysed by
coordination polymers is probably the epoxidation of ole fins [27].
A significant advantage of many of these complexes is that they
can be prepared from inexpensive metal sources, e.g [28].
Although coordination polymers/MOFs could be used as catalysts
with high catalytic activity in various reactions [29]. (such as,
cyanosilylation, hydrogenation, polymerization, oxidation, and
isomerization), the search and design of highly-effective catalysts
with high yields and selectivities are a challenging task for
oxidation reactions, especially hydrocarbon oxidations, using tert-
butyl hydroperoxide (TBHP) as radical initiator and oxygen (in the
air) as oxidant [30-32].
Chirality is a widespread phenomenon in nature, playing a very
important role in many areas of society and science [1]. Therefore,
lots of scientists focus on the topic of preparation of chiral
materials [2]. In the past few years, chiral metal−organic
frameworks (MOFs) or coordination polymers (CPs) are of great
interest, because of their intriguing potential applications in optical
resolution, enantioselective synthesis, asymmetric catalysis, and so
on [3]. In general, homochiral coordination polymers can be
obtained by three routes [4]. The first is using a chiral organic
bridging ligand to link the metal centers in the framework [5]. The
second is using a chiral molecule as an auxiliary ligand that does
not bridge the metal centers but forces chirality by coordinating to
the metal center [6]. The third is spontaneous resolution upon
crystallization without any chiral sources [7]. Recent research has
proved that the usage of chiral species as reactant precursors
represent the more straightforward and effective approach toward
homochiral solids for it is much easier to control the chirality of the
aimed products [8].
Here we report
a pair of homochiral manganese-based
Chiral catalysis acts as the core issues of chemistry and play
significant roles in current chemical industry, as well as pharmacy
and biomimetic chemistry [9-12]. To date, solid catalysts have
been almost exclusively inorganic materials. Due to its crucial role
in many chemical processes, heterogeneous catalysis is one of the
key elements of our industrialized society, and thus has direct
impact on the global economy. It is reported that approximately
nine-out of-ten chemical processes utilize heterogeneous catalysts
[13,14]. However, the design of more active and selective
heterogeneous catalysts leading to more environmental friendly
processes is still a priority and a challenge [15].
coordination polymers, namely [Mn(H2O)2(bpy)(L-DBTA)] (L-1)
and [Mn(H2O)2(bpy)(D-DBTA)] (D-1) from manganese salt with
L-DBTA=(-)-dibenzoyl-L-tartaric acid, D-DBTA=(+)-dibenzoyl-
D-tartaric acid, and bpy (4,4'-Bipyridine). Both compound L-1 and
D-1 exhibit a 3D supermolecule framework and the further
selective catalytic oxidation of cis-cyclooctene experiments
indicated that these manganese-based coordination polymers
possess excellent catalytic ability for the selective oxidation of cis-
cyclooctene.
Oxidation is an important pathway to large-scale production of
chemicals. However, poor efficiency is the common weakness [16].
Recently, the important concept of “green chemistry” has been
associated with this type of catalytic reactions, which involves the
use of molecular oxygen directly from air [17]. Among various
oxidants, molecular oxygen is a cheap, clean and readily available
oxidant, making it ideal for hydrocarbon oxidation from both
economic and environmental perspectives [18-20]. Furthermore,
oxidation is an important method for the synthesis of chemical
intermediates in the manufacture of hightonnage commodities,
high-value fine chemicals, agrochemicals, and pharmaceuticals
[13,14]. Selective oxidation of hydrocarbons is of great interest in
synthetic organic chemistry and chemical industry for the
conversion of petroleum-based feedstocks to more valuable
chemicals such as diols, epoxides, alcohols and carbonyl
Scheme 1. Schematic representation of the synthesis of L-1 and D-1
assembled from manganese salt with mixed ligands bpy and L-DBTA and
D-DBTA.
1

ACCEPTED MANUSCRIPT
Single-crystal X-ray diffraction analyses reveal that compounds
On the basis of the manganese plays an important role in alkenes
catalysis, as a heterogeneous catalyst [35-37]. We used L-1 as a
catalyst to study the catalytic performance of the selective
oxidation of cis-cyclooctene. First, 10 mL of cis-cyclooctene and
0.020 g of L-1 were placed in a 50 mL three-necked flask with a
reflux condensation device and magnetic stirring was continued.
Then 0.5 mL t-butyl hydroperoxide (TBHP) as an initiator was
added dropwise to the three-necked flask, and finally the above
L-1 and D-1 are isostructural and their crystal system, space group,
unit cell dimensions, related bond distances, and bond angles are
only slightly different (Scheme 1), hence only the structure of L-1
will be discussed in detail. L-1 crystallizes in the chiral
orthorhombic system with space group P212121, and the flack
parameter of 0.022(10) further indicates that the absolute
configuration is correct. As illustrated in Fig. 1a, the asymmetric
unit of L-1 contains one crystallographically independent Mn atom, mixed solution was stirred at 80 °C for 24 h. After the samples of 4,
one L-DBTA ligand, one bpy ligand, and two coordinated water
molecules. The Mn1 centre displays a distorted octahedral
[MnN2O4] geometry, being coordinated by two oxygen atoms from
two L-DBTA ligands, two coordinated water molecules, and two
nitrogen atoms from two bpy ligands. In L-1, the bpy bridges Mn
atoms into a 1D nonlinear chain, and the whole L-DBTA acts as
bidentate ligand to extend adjacent chains into 2D wavelike layer
via its two monodentate carboxylate groups (Fig. 1b). There is a
window in 2D layer with dimension of 11.5 ×7.9 Å based on the
Zn•••Zn distances (Fig 1c). The 2D layers are extended to 3D
supramolecular framework with hydrogen bondings between
carboxylate oxygen atoms of the L-DBTA and coordinated water
molecules (Scheme 1).
8, 12, 16, 20, and 24 h were cooled to room temperature, the filter
was analyzed by the gas chromatograph(GC), the products of the
selective oxidation of cis-cyclooctene were poxycyclooctane, 1,2-
cyclooctanediol, and cycloocten-2-one.
As shown in Table 1 and Fig. 3a, the detailed conversion of cis-
cyclooctene and selectivity of oxidation products demonstrate the
catalytic performance of L-1 for the selective oxidation of cis-
cyclooctene, which reveals that the percentage of conversion and
the selectivity reach 26.42% and 61.87% after 12 h, respectively.
After 24 h reaction, high conversion efficiency of 38.85% and high
selectivity up to 76.13% are achieved simultaneously. With time
going on, both the conversion of cis-cyclooctene and the selectivity
of epoxycyclooctane are increased. At the same time, the
selectivity of cycloocten-2-one decreases from 23.62% to 13.10%.
Similarly, the selectivity of 1,2-cyclooctanediol decreases from
14.16% to 10.02%.
Fig. 1 The asymmetric units of L-1 and D-1 (a). The 2D interdigitated
architecture along the c axes (b) and (c). Hydrogen atoms and lattice water
molecules are omitted for clarity.
Fig. 3 The process of cis-cyclooctene epoxidation. (a) The relationship
between the conversion of cis-cyclooctene/selectivity of different products
and reaction time with compound L-1 as catalyst. (b) The relationship
between the conversion of cis-cyclooctene/selectivity of different products
and recycling times with compound L-1 as catalyst.
To confirm the enantiomeric nature of L-1 and D-1, the circular
dichroism (CD) spectra were measured in KBr pellets [33,34]. As
shown in Fig. 2, the CD spectra of L-1 and D-1 in the solid state
show that Cotton effects are in the wavelength range of 200-500
nm. Further close observation reveals that the CD spectra are
mirror images of one another, which conclusively demonstrates
that L-1 and D-1 are enantiomers. This phenomena indicated that
the chiral information was transferred from chiral DBTA ligand to
the metal centre and finally to the whole framework.
Table 1. Effect of variety of reaction time on selective oxidation of cis-
cyclooctene using compound L-1 as catalyst.
Product Selectivity (%)
Reaction
time (h)
Conversion
(%)
ΣselC8§
0
0
0
0
0
0
46.63 36.61
54.39 29.78
61.87 23.62
67.41 19.49
72.68 15.16
76.13 13.10
16.75
15.73
14.16
12.63
11.53
10.02
20.07
23.38
26.42
30.63
34.65
38.85
4
8
12
16
20
24
99.99
99.87
99.65
99.53
99.37
99.25
Reaction conditions: compound L-1 (20 mg), cis-cyclooctene (10 mL),
TBHP (0.5 mL), 80 ºC, 24 h, atmospheric pressure.
§Total selectivity to C8 partial oxidation products.
Whether the catalyst can be recycled reliably is an important
indicator to evaluate the stability of the catalyst. We used the cis-
cyclooctene epoxidation reaction system as a model to conduct a
Fig. 2. Solid state CD spectra of L-1(red) and D-1(black) in KBr pellets.
2

ACCEPTED MANUSCRIPT
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no significant changes are observed in the conversion rate of cis-
cyclooctene and the selectivity of reaction products for each cycle
until 24 h under the same reaction conditions for 5 cycles. The
result shows that the catalyst has great recycling performance. In
order to further confirm the L-1 acts as the catalyst for this reaction,
we carried out the blank control experiment (the reaction without
catalyst) and the filtrate test (When the reaction was carried out for
24 h, the solid catalyst in the reaction liquid was removed by hot
filtration to obtain a clear reaction solution. The clear solution was
allowed to react under the same reaction conditions for 24 h. Then,
the cis-cyclooctene conversion rate and the selectivity of reaction
products was tested). The final result of the blank control
experiment is that the cis-cyclooctene conversion rate and the
selectivity of reaction products are zero. This reaction proves that
the absence of the catalyst reaction is not carried out.
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cyclooctene and the selectivity of reaction products are also still
zero, which demonstrate that the filtrate does not participate in the
catalytic reaction. All above-mentioned catalytic experiments show
that L-1 indeed acts as a heterogeneous catalyst in the present
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In conclusion,
a
pair of homochiral manganese-based
coordination polymers (L-1 and D-1) with 3D supramolecular
network has been constructed by the L/D-DBTA ligands and
manganese salt. The catalytic experiment indicates that these
manganese-based coordination polymers, directly used as a
heterogeneous catalyst without any supports, possess excellent
catalytic ability for the selective oxidation of cis-cyclooctene.
Recyclability experiments shows that L-1 is highly reusable and
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Acknowledgments
This work was financially supported by the National Nature Science
Foundation of China under Grant: NSFC No. 21373002 and 21503020;
Supported by Program for Liaoning Excellent Talents in University, No.
LJQ2013116 and The doctoral fund of Liaoning Province of China (No.
201601347). The Natural Science Foundation of Liaoning Province of
China (No.20170540021), the Project of Education Department of Liaoning
Province of China (No.LF2017004, LQ2017014), and the Liaoning
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ACCEPTED MANUSCRIPT
Graphical abstract
A pair of homochiral manganese-based coordination polymers possess excellent catalytic ability for the
selective oxidation of cis-cyclooctene.
4

ACCEPTED MANUSCRIPT
Highlights
> A pair of homochiral Manganese-based coordination polymers exhibit 3D supermolecule framework.
> Catalytic ability for the selective oxidation of cis-cyclooctene.
5