Two kinds of cobalt–based coordination polymers with excellent catalytic ability for the selective oxidation of cis-cyclooctene

Article abstract of DOI:10.1016/j.inoche.2017.10.001

Two kinds of cobalt–based coordination polymers {[Co(dsd)(H₂O)₄]·4,4′-bpy}(1) and {[Co(dsd)(H₂O)₄]·H₂O} (2) with the chain structure possess excellent catalytic ability for the selective oxidation of

Full text of DOI:10.1016/j.inoche.2017.10.001

Accepted Manuscript
Two kinds of cobalt–based coordination polymers with excellent
catalytic ability for the selective oxidation of cis-cyclooctene
Guangju Zhang, Yang Shi, Ying Wei, Qingguo Zhang, Kedi Cai
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DOI:
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doi:10.1016/j.inoche.2017.10.001
INOCHE 6789
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29 September 2017
1 October 2017
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ACCEPTED MANUSCRIPT
Two kinds of cobalt–based coordination polymers with excellent catalytic ability for
the selective oxidation of cis-cyclooctene
Guangju Zhang,*Yang Shi, Ying Wei, *Qingguo Zhang,* Kedi Cai
College of Chemistry, Chemical Engineering, Bohai University, Jinzhou 121013, Liaoning Province, China
Keywords: coordination polymers; selective oxidation; catalysis
Two
kinds
of
cobalt–based
coordination
polymers with the chain structure possess excellent catalytic ability for the
{[Co(dsd)(H2O)4]·4,4'-bpy}(1) and {[Co(dsd)(H2O)4]·H2O)} (2)
selective oxidation of cis-cyclooctene.
The search for functional materials has emerged with a
considerable importance over the last two decades, with
remarkable efforts towards the design and synthesis of novel
hybrid organic-inorganic compounds being performed
worldwide. Coordination polymers are a notable family of
hybrid materials showing infinite extended networks which
usually involve two main components: inorganic nodes (metal
ions or clusters) and organic linkers interconnected by
coordinative bonds to afford a network arrangement with
specific topology[1]. Such organic–inorganic hybrid compounds
can combine the unique characteristics of the components and
exhibit novel structural features, as well as new properties
arising from the synergistic interplay of the two components[2].
Of particular interest are those showing potential applications in
the fields of fuel gas storage[3,4], catalysis[5-7], magnetism[8-
10], separation and proton conduction[11,12], etc.
chemicals, agrochemicals and pharmaceuticals[18,19]. Alkene
selective oxidation has attracted much attention because of the
related products of epoxides are valuable and resourceful
commercial intermediates. For many years, coordination
polymers have been used as catalysts for a wide variety of
organic reactions. The most studied reaction catalysed by
coordination polymers is probably the epoxidation of
olefins[20]. Although coordination polymers/MOFs could be
used as catalysts with high catalytic activity in various
reactions[21] (such as, cyanosilylation, hydrogenation,
polymerization, oxidation, and isomerization), the studies on
their application in hydrocarbon selective oxidation reactions
(using t-BuOOH as oxidant) is still a huge challenge.
Here we report the synthesis of two cobalt-based coordination
polymers,
namely
{[Co(dsd)(H2O)4]·4,4'-bpy}(1)
and
{[Co(dsd)(H2O)4]·H2O)} (2) from cobalt salt with 4,4'-
Diamino-2,2'-stilbenedisulfonic acid (dsd) and 4,4'-Bipyridine
(4,4'-bpy). Both compound 1 and compound 2 exhibit a 3D
supermolecule framework and the further selective catalytic
oxidation of cis-cyclooctene experiments indicated that these
cobalt-based coordination polymers possess excellent catalytic
ability for the selective oxidation of cis-cyclooctene.
Based on the similarity to metal–organic frameworks (MOFs),
a logical application of coordination polymers could also be as
solid catalysts, which are similar to heterogeneous catalysts and
also allowed for easier post-reaction separation and recyclability
than homogeneous catalysts[13]. However, despite the elevated
metal content of coordination polymers, their use in catalysis is
largely hampered by the relatively low stability to thermal
treatments, chemical agents, and moisture, due to the presence
of the organic component. Furthermore, the activity and
selectivity of a catalytic reaction can be tuned by varying the
size, composition and morphology of inorganic-solid
catalysts[14].
In some coordination polymers, empty sites on the inorganic
secondary building units can be generated through the simple
removal of small neutral ligands from the metal coordination
environment of the “unactivated” material (mostly H2O, when
operating under hydrothermal synthetic conditions). The
preactivation of the material is expected to create open metal
sites potentially available for promoting catalysis while keeping
the framework crystalline texture intact. In addition, the
heterogeneous nature of a coordination polymer can be very
useful to separate the catalyst from the products of interest;
recover it after simple filtration procedures; and finally,
regenerate it for successive catalytic runs[15].
Figure 1 (a) Ball-stick view of the symmetric unit of 1. (b) view of the
1D N–Co–N chain running along the c axis. (d) Stick and polyhedral
view of the 3D framework.
Compound 1 crystallizes in the Orthorhombic with space
group Pbcn. The symmetrical unit contains one [Co(dsd)(H2O)4]
unit and one solvent 4,4'-bpy molecule for compound 1. As
shown in Figure 1a, Co atom is six-coordinated in an octahedral
coordination geometry, coordinated by two nitrogen atoms from
one dsd ligand and four oxygen atoms from four coordinate
water molecules. Each Co atom is bridged by two amidogen N
atoms to form a CoO4N2 unit. These Co units feature a 1D
Catalysis is a core issue of chemistry and plays a significant
role in current chemical industry, as well as environmental and
energy problems[16,17]. Furthermore, oxidation is an important
method for the synthesis of chemical intermediates in the
manufacture of high-tonnage commodities, high-value fine
1

ACCEPTED MANUSCRIPT
ladder along the c axis interconnected via dsd ligands (as
further extension of reaction time, when the reaction to 24 h,
cis-cyclooctene conversion rate is 25.79%, the selectivity of
poxycyclooctan is 79.63%, thus, cis-cyclooctene conversion rate
and selectivity of poxycyclooctan are increasing over time. At
the same time, the selectivity of 1,2-cyclooctanediol fell from
11.41% to 6.67%, the same cycloocten-2-one also fell from
14.05% to 12.95%. When the compound 2 as catalyst 2, the
conversion rate of selective catalytic oxidation of cis-
cyclooctene and different oxidation products change with time
as shown in Figure 3b and Table 2. When using the catalyst 2
and the reaction time is 12 h, the substrate cis-cyclooctene rate
is 12.61%, the main product is poxycyclooctane and selectivity
of 64.94%. Along with the further extension of reaction time,
when the reaction to 24 h cis-cyclooctene conversion rate is
24.76%, the selectivity of poxycyclooctan is 71.40%, thus, cis-
cyclooctene conversion rate and selectivity of poxycyclooctan
are increasing over time. At the same time, the selectivity of
1,2-cyclooctanediol fell from 20.52% to 17.41%, the same
cycloocten-2-one also fell from 14.22% to 10.41%.
illustrated in Figure 1b). The adjacent chains are further
aggregated into a three-dimension (3D) network through the
hydrogen bonds between the 4,4'-bpy and sulfonic acid groups
oxygen atoms. As shown in Figure 1c, the neighboring chains in
one row are parallel. The 4,4'-bpy ligands are filled in the free
space of structure by extensive hydrogen bonding interactions to
maintain the stability of the framework.
Compound 2 crystallizes in the Monoclinic with space group
C2/c. The symmetric unit contains one [Co(dsd)(H2O)4] unit
and one solvent water molecule for compound 2. As shown in
Figure 2a, Co atom is six-coordinated in an octahedral
coordination geometry, coordinated by two nitrogen atoms from
one dsd ligand, four oxygen atoms from four coordinate water
molecules. Each Co atom is bridged by one dsd ligand to form a
wave-like chain running along the c axis (Figure 2b). The
adjacent chains are inter-linked by intermolecular hydrogen
bonding interactions to afford a 3D architecture (Figure 2c). The
lattice water molecules are filled in the free space of structure
by extensive hydrogen bonding interactions to maintain the
stability of the framework.
Figure 2 (a) Ball-stick view of the symmetric unit of 2. (b) view of the
1D N–Co–N chain running along the c axis. (d) Stick and polyhedral
view of the 3D framework.
Considering that cobalt plays an important role in current
petrochemical and plastic industries, as both a hetero and
homogeneous catalyst[22-25]. In the following experiments, the
catalytic performance of compound 1 and 2 for the selective
oxidation of cis-cyclooctene is further studied. In 50 ml three
neck flask with a reflux condensation device, successively
added 10 ml cis-cyclooctene, 0.020 g catalyst and 0.5 ml tertiary
butyl-hydrogen peroxide, magnetic stirring, 80 ℃ constant
temperature oil bath. After the samples of 4, 8, 12, 16, 20 and
24 h were cooled to room temperature, the filter was analyzed
by the gas chromatograph(GC). Finally, the products of the
catalytic reaction were poxycyclooctane, 1,2-cyclooctanediol
and cycloocten-2-one.
Figure
3 The relationship between the conversion of cis-
cyclooctene/selectivity of different products and reaction time with
compound 1 (a) and 2 (b) as catalyst, respectively. The relationship
between the conversion of cis-cyclooctene/selectivity of
different products and recycling times with compound 1 (c) and
2 (d) as catalyst, respectively.
Table 1. Effect of variety of reaction time on selective oxidation of cis-
cyclooctene using compound 1 as catalyst 1.
Product Selectivity (%)
Reaction
time (h)
Conversion
(%)
ΣselC8§
0
0
0
0
0
0
4
8
12
16
20
24
70.23 14.48
72.73 14.22
74.21 14.05
76.44 13.78
77.63 13.33
79.63 12.95
15.27
12.88
11.41
9.34
8.22
6.67
5.08
99.98
99.83
99.67
99.56
99.38
99.25
10.16
14.21
19.58
22.37
25.79
Scheme 1 The equation of cis-cyclooctene epoxidation.
Reaction conditions: compound 1 (20 mg), cis-cyclooctene (10 mL),
TBHP (0.5 mL), 80 ºC, 24 h, atmospheric pressure.
When the compound 1 as catalyst 1, the conversion rate of
selective catalytic oxidation of cis-cyclooctene and different
oxidation products change with time as shown in Figure 3a and
Table 1. From the picture we can see very intuitively, when
using the catalyst 1 and the reaction time is 12 h, the substrate
cis-cyclooctene conversion rate is 14.21%, the main product is
poxycyclooctane and selectivity of 74.21%. Along with the
§Total selectivity to C8 partial oxidation products.
Table 2. Effect of variety of reaction time on selective oxidation of cis-
cyclooctene using compound 2 as catalyst 2.
Product Selectivity (%)
2

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Appendix A. Supplementary material
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3

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Graphical Abstract
Cobalt-based coordination polymers possess
excellent catalytic ability for the selective
oxidation of cis-cyclooctene.
Highlights
> Two cobalt-based coordination polymers
exhibit a 3D supermolecule framework.
> Catalytic ability for the selective oxidation of
cis-cyclooctene.
4