A new organic-inorganic hybrid based on dimeric [Mn2V22O64]10 - Polyoxoanion as catalyst for oxidation of sulfides

Article abstract of DOI:10.1016/j.inoche.2016.04.014

A new organic-inorganic hybrid compound constructed from [Mn₂V₂₂O₆₄]^{10 -} units, H₆[(C₆H₄NO₂Cu(H₂O)₄)]₂[Mn₂V₂₂O₆₄]·28H₂O 1, has been synthesized and characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction (XPRD) and TG. Compound 1 is composed of dimeric [Mn₂V₂₂O₆₄]^{10 -} polyoxoanions, metal-organo fragments [(C₆H₄NO₂Cu(H₂O)₄)]^{2 +} and lattice water molecules. Moreover, a three-dimensional supramolecular structure is formed in 1 by the extensive hydrogen bond interaction among the terminal oxygen atoms of [Mn₂V₂₂O₆₄]^{10 -} anions, the coordinated waters of Cu^{2 +} ions and crystal water molecules. Compound 1 exhibits remarkable catalytic activity for the heterogeneous oxidation of sulfides under mild condition.

Full text of DOI:10.1016/j.inoche.2016.04.014

A new organic-inorganic hybrid based on dimeric [Mn2V22O64]10 − poly-
oxoanion as catalyst for oxidation of sulfides
Ting-ting Wang, Ying Lu, Ding Liu, En-bo Wang
PII:
DOI:
Reference:
S1387-7003(16)30111-3
doi: 10.1016/j.inoche.2016.04.014
INOCHE 6290
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
9 March 2016
15 April 2016
17 April 2016
Please cite this article as: Ting-ting Wang, Ying Lu, Ding Liu, En-bo Wang,
A new organic-inorganic hybrid based on dimeric [Mn2V22O64]1
catalyst for oxidation of sulfides, Inorganic Chemistry Communications (2016), doi:
0.1016/j.inoche.2016.04.014
0 −
polyoxoanion as
1
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ACCEPTED MANUSCRIPT
1
0-
A new organic-inorganic hybrid based on dimeric [Mn V O ]
2
22 64
polyoxoanion as catalyst for oxidation of sulfides
Ting-ting Wang, Ying Lu,* Ding Liu, En-bo Wang*
Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of
Chemistry, Northeast Normal University, Renmin Street No. 5268, Changchun, Jilin
1
30024, PR China
*
Corresponding author. Tel: +86-431-85098787; Fax: +86-431-85098787.
E-mail: wangeb889@nenu.edu.cn; luy968@nenu.edu.cn
1

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Abstract
A new organic-inorganic hybrid compound constructed from [Mn V O ] units,
1
0-
2
22 64
H [(C H NO Cu(H O) ] [Mn V O ]·28H O 1, has been synthesized and
6
6
4
2
2
4 2
2
22 64
2
characterized by single-crystal X-ray diffraction, IR, powder X-ray diffraction (XPRD)
10-
and TG. Compound 1 is composed of dimeric [Mn V O ]
polyoxoanions,
2
22 64
2+
metal-organo fragments [(C H NO Cu(H O) ]
and lattice water molecules.
6
4
2
2
4
Moreover, a three-dimensional supramolecular structure is formed in 1 by the
extensive hydrogen bond interaction among the terminal oxygen atoms of
10-
2+
[
Mn V O ]
anions, the coordinated waters of Cu ions and crystal water
2
22 64
molecules. Compound 1 exhibits remarkable catalytic activity for the heterogeneous
oxidation of sulfides under mild condition.
Keywords: inorganic-organic hybrid; polyoxoanion; structure; heterogeneous
oxidation; desulfurization.
2

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The rapid progress of exploring organic-inorganic hybrid materials is driven by the
interest of their structural diversity and fascinating properties [1]. Most of these
hybrid solids are extended architectures, which are built from metal ions, metal
clusters or metal oxides and rigid or flexible multidentate ligands acting as organic
connectors. Polyoxometalates (POMs) are intriguing nanosized inorganic clusters that
have attracted much attention in the last several years due to the structural variety as
well as interesting and often unexpected properties in fields as diverse as catalysis,
medicine, and materials science [2]. Meanwhile, an important interest in the chemistry
of POMs is focused on the design and synthesis of novel organic-inorganic
POM-based hybrids with unusual structures and properties. The synthesis of new
POMs-based organic-inorganic hybrid materials have developed rapidly in recent
years [3]. However, compared with the extensive works on the construction of
organic-inorganic hybrid based on heteropolymolybdates and heteropolytungstates,
less research has been conducted in the field of heteropolyvanadates-based
organic-inorganic
hybrid.
During
the
design
and
synthesis
of
7
-
heteropolyvanadates-based organic-inorganic hybrid, the unusual [MnV O ]
1
3
38
polyoxoanion caught our attention, which was first isolated by Pope and co-workers
7
-
[
4]. [MnV O ] is a kind of functional POM, which shows catalytic oxidation
13 38
performance in some organic reactions, and its antibacterial/antitumor medical
activities have been studied. In 2005, Liu group has prepared an organic-inorganic
hybrid
compound
K (HABOB) [MnV O ]·9H O
(ABOB
=
3
4
13 38
2
7
-
N-amidino-4-morpholincarboxamidine) from the [MnV O ] anion [5]. And our
13
38
3

ACCEPTED MANUSCRIPT
previous work has reported a series of organic-inorganic compounds constructed of
7-
[
MnV O ] anion and rare earth metal-organic coordination units with 1D and 3D
13
38
infinitely extended structures [6].
For achieving POMs-based organic-inorganic hybrid with catalytic performance,
7
-
we chose [MnV O ] as starting material and sccessfully synthesized a new
1
3
38
organic-inorganic hybrid, H [(C H NO Cu(H O) ] [MnV O ] ·28H O 1, by the
6
6
4
2
2
4 2
11 32 2
2
7
-
2+
aqueous solution reaction of [MnV O ] , Cu ion and isonicotinic acid at 45 °C for
1
3
38
4
h [7]. Pope and his co-workers firstly reported the crystal structure of
10-
vanadomanganate (IV) salts K Mn V O ·20H O in 1988. The [Mn V O ]
1
0
2
22 64
2
2
22 64
polyanion consists of a centrosymmetric arrangement of two MnV moieties linked
11
by two linear unsupported V-O-V bridges [8]. However, no organic-inorganic hybrid
10-
based on [Mn V O ]
polyoxoanion has been reported until now. To our
2
22 64
knowledge, 1 represents a rare example of organic-inorganic hybrid based on
10-
[
Mn V O ] polyoxoanion.
2 22 64
Compound 1 has been characterized in the solid state by elemental analyses, IR
Fig. S1), TG (Fig. S2), PXRD (Fig. S8) and single-crystal X-ray diffraction analysis
9]. Moreover, 1 was used as catalyst for the oxidation of sulfides containing
(
[
dibenzothiophene (DBT), benzothiophene (BT) and 4,6-dimethyldibenzothiophene
4,6-DMDBT) with tert-butyl hydroperoxide (TBHP) as the oxidant, what’s more the
(
main factors affecting the process including temperature, and O/S (TBHP/DBT)
molar ratio were also investigated in detail.
The X-ray diffraction analysis reveals that the structure of compound 1 consists of
4

ACCEPTED MANUSCRIPT
10-
dimeric
[Mn V O ]
polyoxoanions,
metal-organo
fragments
2
22 64
2
+
10-
[
(C H NO Cu(H O) ] and lattice water molecules (Fig. 1). The [Mn V O ]
6 4 2 2 4 2 22 64
5
-
anion comprises two [MnV O ] clusters of edge-shared VO octahedra linked by
11
32
6
fusion at two vertices. The V-O bond lengths range from 1.585 to 2.416 Å. The Mn-O
bond lengths are 1.879-1.915 Å, and the O-Mn-O angles are in the range of
8
6.73(16)-174.47(16)°, which are in close agreement with those described in the
literature [4]. A three-dimensional supramolecular structure is formed in 1 by the
extensive hydrogen bond interaction among the terminal oxygen atoms of
10-
2+
[
Mn V O ]
anions, the coordinated waters of Cu ions and crystal water
2
22 64
molecules (Fig. 2).
<
<
Fig. 1 Here>
Fig. 2 Here>
In the IR spectrum of compound 1 (Fig. S1), the peaks at 964, 831, 710, and 538
-1
cm are attributed to v (V=O) and v (V-O-V). The other peaks at 2097, 1907, 1579,
-1
1
390, 1246 cm can be assigned to isonicotinic acid molecules. The TGA curve of
compound 1 (Fig. S2) exhibits three continuous weight loss stages in the temperature
range 27-380°C, corresponding to the loss of lattice waters, coordinated water
molecules and isonicotinic acid molecules. The whole weight loss is 23.9%,
agreement with the theoretical weight loss value (calcd. 23.5%).
Due to more stringent environment regulations, wide interest in the area of deep
desulfurization of fuel oils increased quickly. Yet, hydrodesulfurization (HDS) is
difficult to reduce sulfur-containing heterocyclic compounds to an ultra-low level [11].
5

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Oxidative desulfurization (ODS) is regarded as a promising strategy to remove the
refractory aromatic thiophenes [12]. In recent years, owing to their fast reversible
multielectron transformation activity, POMs have been extensively investigated as
catalysts in a variety of oxidation reactions, including epoxidation and desulfurization
[
13]. Thus, the oxidations of sulfides were chosen as test reactions to assess the
catalytic activity of compound 1. Oxidations of dibenzothiophene (DBT),
benzothiophene (BT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in the
presence of 1 were performed in CH Cl medium at 60 °C using tert-butyl
2
2
hydroperoxide (TBHP) as the oxidant respectively (Scheme S1). We investigated the
main factors affecting the process including the experiment temperature, O/S
(TBHP/DBT) molar ratio and effect of the amount of catalyst in detail. The effect of
the amount of TBHP on the oxidation desulfurization of DBT under various
TBHP/sulfur (O/S) molar ratios at 60 °C catalyzed by 1 was shown in Table 1. The
removal of sulfide could reach 99.6% when the equivalent of TBHP is 4, further
increasing the O/S ratio to 6 and 8 the sulfurization efficiency and the removal of
DBT didn’t change too much. So in view of the cost of the oxidant and the
productivity, O/S molar ratio at 4 was the appropriate condition (entry 3).
<
Table 1 Here>
The effect of temperature on the desulfurization of DBT catalyzed by 1 was
investigated (Fig. 3). The removal of substrate increased significantly with the
reaction temperature changed from 50 °C to 60 °C. It can be found that DBT was
almost eliminated completely at 60 °C after 100 min. Moreover, when the temperature
6

ACCEPTED MANUSCRIPT
dropped to 55 or 50 °C, the removal of DBT was not so perfect as the 60 °C, which
can only reach 83% and 75%, respectively. In view of the desulfurization effect,
6
0 °C was better than the others and too high temperature will contribute to the
consumption of energy, so the reaction temperature of 60 °C was recommended.
Fig. 3 Here>
<
The effect of the amount of catalyst on the desulfurization of DBT catalyzed by 1
was shown in Table 2. When the amount of catalyst was increased from 3 mg to 5 mg,
the the removal of DBT increased from 92.3% to 99.6% in 100 min. As expected, the
more amount of catalyst brings more active sites, which contributes to the conversion
completed earlier. By considering the removal of the sulfide had reach the deep
dusulfurization level and the cost of the catalyst in the desulfurization system, the
appropriate amount of catalyst 5 mg was chosen.
The experimental data demonstrate that 1 shows fairly good catalytic activity for
the oxidations of the three sulfurcontaining substrates in Table 3. The maximum
substrate conversions were 98.8% achieved after 150 min for BT, 99.6% after 100
min for DBT and 99.1% after 170 min for 4,6-DMDBT (Fig. S3). Moreover, the three
substrates were finally oxidized into the corresponding sulfones with 100% selectivity
as verified by GC-MS (Fig. S4) and FT-IR (Fig. S5) measurements. The results of the
experiments performed in the presence of POM precursor [NH ] [MnV O ]·18H O
4
7
13 38
2
or raw material isonicotinic acid are presented in Table 3. From the experimental
results we can see that the isonicotinic acid didn’t accelarate the conversion too much.
The sulfide removal of DBT was only 46.2%, which was almost equal as that in the
7

ACCEPTED MANUSCRIPT
blank experiment (45.8%). When [NH ] [MnV O ]·18H O acting as catalyst, the
4
7
13 38
2
sulfide removal of DBT was 75.9%, which is superior to that in the blank experiment
(45.8%) but inferior to that with compound 1 as catalyst (99.6%).
Catalyst 1 can be almost completely recovered from the reaction vessel after a
catalytic test run by simple centrifugal separation. The recovered catalyst was reused
in successive four runs with only slightly decreased substrate conversion (Fig. S6).
The catalyst was characterized by IR and PXRD (Fig. S7-8) after being recycled 4
times. From the IR and PXRD we find that the catalyst didn’t change after the
oxidative desulfurization experiment. So the desulfurization rate of the catalyst
decreased from 99.6% to 90.4% after four recycles may be caused by the loss of
catalyst during the catalyst seperation process.
<
<
Table 2 Here>
Table 3 Here>
In summary, a new organic-inorganic hybrid compound constructed from
10-
[
Mn V O ] units has been synthesized and characterized by single-crystal X-ray
2 22 64
diffraction, IR, XPRD and TG. Moreover, compound 1 was used for the oxidation of
sulfur compounds such as dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene
(4,6-DMDBT) and benzothiophene (BT) with TBHP as an oxidant under mild
condition and showed high activity. 1 is not only stable, but also can be used as
heterogenous catalyst in the oxidation of sulfides with recycling for 4 times. This
work demonstrates that it is a feasible way to construct crystalline materials with
catalytic performance employing catalytic active POMs.
8

ACCEPTED MANUSCRIPT
Acknowledgments
This work was financially supported by the Science and Technology Development
Project Foundation of Jilin Province (No. 20130101006JC), and the Open Project
Program of the Key Laboratory of Polyoxometalate Science of Ministry of Education
(No. 130014555).
Appendix A. Supplementary material
CCDC 1446402 contains the supplementary crystallographic data for 1. The data can
be obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associated with this article
can be found, in the online version.
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3
4
13 38
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2

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7–
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13
38
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1
[
4
7
13 38
2
mL distilled water, then isonicotinic acid (0.25 g, 2 mmol) was added, the
mixture was heated at 40 °C for 0.5 h. And Cu(NO ) ·3H O (0.24 g, 1.0 mmol)
3
2
2
were added in succession. Then the mixture was heated at 45 °C for 4 h, after
this time the mixture was cooled to room temperature and filtered. The filtrate
was kept for two weeks at ambient conditions, then red brown crystals of 1 were
isolated. Calcd for 1: C, 18.34; H, 4.52; N, 4.28; Mn, 1.86; V, 22.48 and Cu, 9.43
(%). Found: C, 18.57; H, 4.32; N, 4.13; Mn, 1.67; V, 22.16 and Cu, 9.05 (%). IR
−
1
(
cm ): 20917 (m), 1907 (w), 1579 (m), 1390 (m), 1246 (w), 964 (s), 831 (s),
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7
[
[
1
0-
and three manganese(IV) ions: unusual structural features of Mn V O
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2
22 64
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3
-
Mn V O H , J . Am. Chem. Soc. 111 (1989) 586–591.
3
12 40
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the SADABS program [10b]. The structure was solved by direct methods and
2
refined by full-matrix least squares on F using the SHELXTL program package
1
3

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[
10c]. Crystallographic data for compound 1: C H Cu Mn N O V , F =
12
86
2
2
2
104 22
w
3
1
1
280.47, Triclinic, Space group P-1 with a = 11.537(2) Å, b = 12.407(3) Å, c =
3
8.856(3) Å, α= 98.50(3)°, β = 96.61(3)°, γ = 112.11(3)°, V = 2429.8(9) Å , Z =
, F(000) = 1618, GOF = 1.060, R = 0.0537, and wR = 0.1638 [I ≥ 2 σ (I)].
1
2
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4

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1
5

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5-
Fig. 1 View of the local connections [MnV O ] units and organic ligands.
11
32
Fig. 2 The three-dimensional supramolecular structure formed by 1.
1
6

ACCEPTED MANUSCRIPT
Fig. 3 The effect of temperature on the desulfurization of DBT catalyzed by 1.
1
7

ACCEPTED MANUSCRIPT
a
Table 1. Effect of O/S on the Removal of DBT .
Entry
TBHP[eq] Substrate
Product
t [min]
Removal
%]
[
1
2
3
4
5
2
3
4
6
8
100
100
100
100
100
58.1
82.1
99.6
99.8
99.8
a
Conditions: a mixture of catalyst (5 mg, 0.0015 mmol), sulfide (15 mg, 0.08
mmol), in CH Cl (2 mL) was stirred at 60 °C.
2
2
a
Table 2 The effect of the amount of catalyst on the Removal of DBT in the oxidative
desulfurization experiment.
Removal
Entry catalyst[mg] Substrate
Product
t [min]
[
%]
1
2
3
3
4
5
100
92.3
97.8
99.6
100
100
a
Conditions: sulfide (15 mg, 0.08 mmol), and TBHP (0.32 mmol, 4 equiv.) in
CH Cl (2 mL) was stirred at 60 °C.
2
2
1
8

ACCEPTED MANUSCRIPT
a
Table 3 Oxidation of sulfide to sulfone with TBHP catalyzed by catalyst 1
Removal,
Entry
Substrate Product Catalyst t [min]
[%]
1
2
3
4
5
6
7
8
1
none
1
150
150
170
170
100
100
100
100
98.8
20.4
98.8
10.9
99.6
45.8
75.9
46.2
none
1
none
MnV13
C H NO
6
5
2
a
Conditions: a mixture of catalyst (0.0015 mmol), sulfide (0.08 mmol), and TBHP
0.32 mmol) in CH Cl (2 mL) was stirred at 60 °C.
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Graphical Abstract
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Synopsis
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A new organic-inorganic hybrid compound constructed from [Mn V O ] units,
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22 64
H [(C H NO Cu(H O) ] [Mn V O ]·28H O, has been synthesized and it exhibits
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6
4
2
2
4 2
2
22 64
2
remarkable catalytic activity for the heterogeneous oxidation of sulfides under mild
condition.
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Highlights
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. A rare example of organic-inorganic hybrid based on [Mn V O ] polyoxoanion
2 22 64
has been synthesized.
. The hybrid exhibits high activity in the oxidation of sulfide.
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