Inorganic-organic hybrid polyoxovanadates based on [V4O12]4-or [VO3]22-clusters: Controllable synthesis, crystal structures and catalytic properties in selective oxidation of sulfides

Article abstract of DOI:10.1039/d0dt03015e

By rationally controlling hydrothermal conditions, three new inorganic-organic hybrid polyoxovanadates (POVs) [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole) have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar structures including [V4O12]4- clusters; complex 3, however, was isolated as a structure by including the [VO3]22- cluster under a different synthetic condition compared with those of 1 and 2. Both complexes 1 and 2 display an interesting 3D supramolecular structure, and complex 3 shows a 2D two parallel networks supramolecular structure linked by a [Co2O2] unit due to the different coordination environments of the central metals. Three inorganic-organic hybrid POVs asheterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with high conversion and high selectivity (up to 99.5 for sulfoxides and 98.5% for sulfones respectively catalyzed by 1). Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant) abatement with high activity and selectivity towardthe corresponding sulfoxide. Moreover, complex 1 can be reused at least three times in sulfoxidationreactions without losing its activity.

Full text of DOI:10.1039/d0dt03015e

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DOI: 10.1039/D0DT03015E
Journal Name
Article
Inorganic-Organic Hybrid Polyoxovanadates Based on [V4O12]4- or
2-
[VO3]2 Clusters: Controllable Synthesis, Crystal Structures and
Catalytic Properties in Selective Oxidation of Sulfides
Received 00th January 20xx,
Accepted 00th January 20xx
Jikun Li,*a,b Chuanping Wei,a Daigaojie Guo,a Congcong Wang,a Yinfeng Han,a Guofang He,a
Jianping Zhang,a Xianqiang Huang,c and Changwen Hu*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
By rationally controlling of the hydrothermal conditions, three new inorganic-organic hybrid polyoxovanadates (POVs)
[Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) (1-vIM = 1-vinylimidazole)
have been synthesized and thoroughly characterized by single X-ray diffraction (SXRD), powder X-ray diffraction
(PXRD), infrared spectroscopy (FT-IR), and elemental analyses (EA). Interestingly, complexes 1 and 2 have similar
4-
2-
structures including [V4O12
] clusters, complex 3 however, was isolated as a structure including [VO3]2 cluster under a
different synthetic condition compared with that of 1 and 2. Both complexes 1 and 2 display an interesting 3D
supramolecular structure and complex 3 shows a 2D two parallel network supramolecular structure linked by a
[Co2O2] unit due to the different coordination environments of the central metals. Three inorganic-organic hybrid
POVs as heterogeneous catalysts are active in the selective oxidation of sulfides to produce sulfoxides or sulfones with
high conversion and high selectivity (up to 99.5% for sulfoxides and 98.5% for sulfones respectively catalyzed by 1).
Complex 1 is also used as catalyst in the oxidative CEES (2-chloroethyl ethyl sulfide, a sulfur mustard simulant)
abatement with high activity and selectivity toward corresponding sulfoxide. Moreover, complex 1 can be reused for at
least three times in sulfoxidation reactions without losing its activity.
polymeric [V2O7]4-, [V4O12]4- and [V6O18]6- etc, from [VO3]nn- chains to
[VxOy]n- networks.4 Compared with other properties, only a few
Introduction
research focused on catalysis of inorganic-organic hybrid POVs 5
.
As a class of multinuclear complexes, polyoxometalates (POMs)
have some excellent physicochemical properties, such as the
ability to accept electrons and protons reversibly, variability in
cluster structures or size and high chemical stability, which
have broad their application prospects in the fields of catalysis,
materials, biology and energy, etc.1 Polyoxovanadates (POVs)
is a unique branch of POMs due to their diverse structures,
multiple valence states and variable coordination
configurations. All these properties make POVs a preferred
building block for the design and assembly of POVs-based
inorganic-organic hybrid materials.2 Many factors, such as
initial reactants along with their stoichiometry ratios, pH value,
temperature and solvents etc, can influence the ultimate
structures of inorganic-organic hybrid POVs.3 As for POVS, the
structure of [VxOy]n- ranges from monomeric [VO4]3- unit to
It is worth mentioning that the introduction of transition-metal
species into the POVs systems usually led to heterogenous catalysts
in various organic reactions with excellent performence. Up to now,
some inorganic-organic hybrid POVs, such as M(HAep)2(VO3)4
(M
= Co, Ni, Cu; Aep =
1-(2-aminoethl)piperazine),6
[{CoNi(H2O)2(Bpe)2}(V4O12)]·4H2O·Bpe,7
[{Ag(Bpy)}4(V4O12)]·2H2O, [{Ag(Dpa)}4(V4O12)]·4H2O and {Ag4(2-
Pzc)2}(V2O6) (Bpy = 4,4'-bipyridine; Dpa = 1,2-bis(4-pyridyl)-
ethane;
Pzc
=
pyrazinecarboxylate),8
[Ag(Bbi)]{Ag(Bbi)}4{Ag3(V4O12)2}]·2H2O (Bbi
=
1,4-bis(N-
imidazolyl)butane),9
Mn(Bpy)(V4O11)(Bpy),10
=
resorcin[4]arene),11
[Co2L0.5V4O12]·3DMF·5H2O
(L
[Co(bib)]{V2O6} and [Ni(en)(bib)]{V2O6}·2H2O (bib = 1,4-bis(1H-
imidazoly-1-yl)benzene), en = ethylenediamine)12 etc., have
been used in the catalytic field of the oxidation of sulfides, the
cyanosilylation of aldehydes with trimethylsilyl cyanide, the
decomposition of methylene blue, splitting of water,
degradation of pollutants, and the cycloaddition of CO2 with
epoxides.
As important high value added products, sulfoxides and
sulfones are commonly used as chiral auxiliaries,13 oxo-transfer
reagents14 and versatile building blocks for the construction of
chemical and biological molecules.15 The desirable route to
obtain sulfoxides and sulfones is the selective oxidation of
a. College of Chemistry and Chemical Engineering, Taishan University, Tai’an,
271021, Shandong, P. R. China.
b. Key Laboratory of Cluster Science Ministry of Education, Beijing Key Laboratory of
Photoelectronic/Electrophotonic, School of Chemistry, Beijing Institute of
Technology, Beijing, 100081 P.R. China.
c. Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell
Technology, School of Chemistry & Chemical Engineering, Liaocheng University,
Liaocheng, 252059, Shandong, P. R. China.
E-mail address: lijk0212@163.com, cwhu@bit.edu.cn.
Electronic Supplementary Information (ESI) available: characterization data, copies
of IR and PXRD spectra and single crystal data. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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sulfides using environmental economical oxidant to replace organic hybrid POVs and their catalytic properties in oxidation
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the traditional stoichiometric oxidants.16-19 Nevertheless, only of sulfides and alcohols, epoxidation ofDoOleI:f1i0n.10a3n9d/DC0hDaTn03-L0a15mE
a few procedures are suitable for switchable synthesis of reaction were also studied. To further investigate the
sulfoxides or sulfones via the oxidation reaction of sulfides controlling synthetic method and advance our research in the
with the same oxidant.20-23 The vanadium peroxides are field of oxidative catalytic activity of POVs based catalysts,30
effective oxidants either stoichiometric or catalytic using H2O2 herein, we synthesized three new inorganic-organic hybrid
as the terminal environmentally friendly oxidant in many POVs complexes [Ni2(1-vIM)7H2O][V4O12]·H2O (1), [Cu2(1-
oxidative transformations including sulfoxidation process. vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) by selecting 1-
Therefore, exploring new synthetic methods for more stable, vinylimidazole (1-vIM) as the N-donor ligand to assemble with
highly active and selective catalysts based on vanadium ammonium metavanadate and different metal ions under
clusters in sulfoxidation transformation is essential.
Imidazoles, in general, are important in biomolecules,24 and characterized by SXRD, PXRD, FT-IR and EA. In order to
pharmaceutical applications25 etc. The substituent at the compare
the catalytic activity, complex [Co4(1-
hydrothermal conditions. Complexes 1-3 have been thoroughly
heteroatom blocks up the possibility for tautomerism type of vIM)14][V4O12]2·6H2O (4) was also synthesized according to our
the original imidazole and the non-coordinated nitrogen atom previous work.31 Further, the catalytic activity of complexes 1-
remains a site of high tendency to coordinate to metal 4 as heterogeneous catalysts were probed in the selective
centers.26 In our previous works, 1-methylimidazole,27 1- oxidatition of sulfides using H2O2 as oxidant. By optimizing the
ethylimidazole,28 1-propylimidazole and 1-isopropylimidazole29 reaction conditions, we can obtain sulfoxides or sulfones with
have been used as N-donor ligands to synthesize inorganic- high conversion and selectivity respectively.
Scheme 1. The controlling synthesis of complexes 1-3. All hydrogen atoms are omitted for clarity.
react with metal(II) chlorides (NiCl2·6H2O, CuCl2·2H2O and
CoCl2·6H2O) and 1-vIM under hydrothermal conditions (Scheme
1). As expected, similar structures of inorganic-organic hybrid
POVs based on [V4O12]4- unit were obtained under the same
reaction conditions except the metal(II) ions for complexes 1, 2
and 4 (Complex [Co4(1-vIM)14][V4O12]2·6H2O (4) was reported in
our previous work31). Different from complexes 1 and 2, the
Results and discussion
Syntheses
To further explore the control toward the formation of the
various architectures of inorganic-organic hybrid POVs with
potential applications, we chose NH4VO3 as vanadium source to
crystal quality of complex 4 is poor. When we try to improve the
2 | J. Name., 2012, 00, 1-3
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crystal quality of 4 and adjust the synthetic conditions with 2(a)); then, the [V(1)O4] tetrahedron provides one of its terminal
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reducing both CoCl2·6H2O and 1-vIM to half amounts, a new O atoms O(2) to coordinate with [Ni(1-DvIOMI:)120(H.102O39)/2D]20+DsTu0b30u1n5iEt
complex
3
based on [VO3]22- unit was isolated successfully.
connecting the adjacent 1D chain to a 2D network parallel to the
[110] plane (Figure 2(b)); at last, the [V(2)O4] tetrahedron uses
one of its terminal O atoms to connect with [Ni(1-vIM)4]2+
subunit linking the 2D network to a 3D supramolecular
Structural analysis of complex [Ni2(1-vIM)7H2O][V4O12]·H2O (1)
According to the coordination environment of the central
nickel atoms, the molecular formula of 1 should be written as
[Ni0.5(1-vIM)2]3[Ni0.5(1-vIM)H2O][V4O12]·H2O. As shown in Figure
1, the SXRD analysis reveals that 1 consists of four Ni2+ cations
(the atom occupancy rate of all Ni atoms in the crystal data is
0.5), one [V4O12]4- anion cluster, and seven 1-vIM ligands. All
four Ni atoms in 1 are six-coordination in an octahedral
geometry. The coordination atoms of Ni(1), Ni(3) and Ni(4)
include two O atoms come from two [VO4] tetrahedron and four
N atoms from four 1-vIM ligands around the central nickel atom.
The six-coordinated Ni(2) center is ligated by two O atoms come
from two [VO4] tetrahedron, four N atoms from four 1-vIM
ligands and two O atoms from two water molecules. All V atoms
in [V4O12]4- anion cluster possess a distorted [VO4] tetrahedral
geometry. Among them, the coordination atoms of V(1) include
two bridging O atoms from two adjacent [VO4] tetrahedrons and
structure (Figure 2(c))
.
two bridging
O atoms from [Ni(1)N4O2] and [Ni(2)N2O4]
octahedrons, respectively. The coordination environments of
V(2) and V(3) are same and achieved by two bridging O atoms
from two adjacent [VO4] tetrahedrons, one bridging O atoms
from [Ni(3)N4O2] for V(2) and [Ni(4)N4O2] for V(3) octahedrons
and a terminal O atom. The coordination environment of V(4)
however, includes two bridging O atoms from two adjacent [VO4]
tetrahedrons and two terminal O atoms.
Figure 2. (a) The 1D chain structure in 1. (b) The 2D network in 1. (c) The 3D
supramolecular structure of 1. Color code: [NiN4O2] octahedron, sky blue. All
hydrogen and carbon atoms are omitted for clarity and nitrogen atoms in (c)
are also omitted.
Figure 1. The crystal structure of complex 1. All hydrogen atoms are omitted
for
clarity.
Complex
1
displays an interesting 3D supramolecular
structure. Such an intriguing structure can be described in the
following steps: first, four adjacent [VO4] tetrahedrons are
connected by the corner-sharing O atoms to form [V4O12]4-
clusters and the alternate [V(1)O4] and [V(3)O4] tetrahedrons of
each [V4O12]4- cluster are linked by two [Ni(1-vIM)4]2+ subunits,
giving rise to a 1D chain structure along the [110] plane (Figure
Figure 3. The crystal structure of complex 2. All hydrogen atoms are omitted
for
clarity.
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respectively connecting the adjacent 1D zigzag chains to a 2D
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network parallel to the bc plane (Figure D4O(bI:)1)0; .1a0t3l9a/sDt0,DtTh0r3o0u1g5hE
another direction of the [V4O12]4- pseudo plane, the [V(1)O4] and
[V(4)O4] connects with [Cu(1-vIM)4]2+ subunits linking the above
2D network to a 3D supramolecular structure (Figure 4(c))
.
Figure 5. The crystal structure of complex 3. All hydrogen atoms are omitted
for clarity.
Structural analysis of complex [Co(1-vIM)H2O][VO3]2 (3)
The structure analyses show that complexes [Co4(1-
31
vIM)14][V4O12]2·6H2O (4) (Supporting Information Figure S11
and [Ni0.5(1-vIM)2]3[Ni0.5(1-vIM)H2O][V4O12]·H2O (1)
)
are
isostructural and crystallize in the triclinic space group P-1,
with very similar cell parameters. Yet, the crystal quality of 4 is
poor. When we try to improve its crystal quality by adjusting the
2-
synthetic conditions, a new complex 3 based on [VO3]2 unit
was obtained.
As shown in Figure 5, the structural formula of 3 is [Co(1-
vIM)H2O][VO3]2, in which there are two crystallographically
independent vanadium atoms with tetrahedral coordination
environments. [VO4] tetrahedrons in 3 are linked to each other
Figure 4. (a) The 1D zigzag chain structure in 2. (b) The 2D network in 2. (c)
The 3D supramolecular structure of 2. Color code: [CuN4O2] octahedron, light
green. All hydrogen and carbon atoms are omitted for clarity and nitrogen
atoms in (c) are also omitted.
n-
through two of their vertex. This joint, gives rise to [VO3]n
chains along the crystallographic b-axis (Figure 6(a)). The [V(1)O4]
and [V(2)O4] tetrahedrons using their other two vertex
coordinate to [Co(1-vIM)H2O]2- subunits respectively, joining the
Structural analysis of complex [Cu2(1-vIM)8][V4O12]·H2O (2)
According to the coordination environment of the central
copper atoms, the molecular formula of 2 should be written as
[Cu0.5(1-vIM)2]4[V4O12]·H2O. Although complexes 1 and 2 have
the same [V4O12]4- anion cluster, the coordination environments
of [VO4] tetrahedrons are very different. In 1, the [V(1)O4]
n-
adjacent [VO3]n chains together and forming a 2D network
parallel to bc plane (Figure 6(b)). Interestingly, a [Co2O2] square
plane structure unit (Figure S1) is formed via a bridging O(2)
atom derived from the [V(1)O4] tetrahedron coordinating to two
[Co(1-vIM)H2O]2- simultaneously. Through the [Co2O2] unit
another 2D network parallel to the previous network is formed
tetrahedron coordinate to
[Ni(1-vIM)4]2+ and [Ni(1-
vIM)2(H2O)2]2+ subunits respectively, and the [V(4)O4]
tetrahedron is free. As shown in Figure 3, in 2 however, each
[VO4] tetrahedron in [V4O12]4- cluster coordinate to one [Cu(1-
vIM)4]2+ subunit respectively. The alternate [V(1)O4] and [V(3)O4]
tetrahedrons of each [V4O12]4- cluster coordinate to two [Cu(1-
vIM)4]2+ subunits, giving rise to a 1D zigzag chain structure along
the crystallographic c-axis (Figure 4(a)); there are two directions
of the [V4O12]4- pseudo planes in the 1D zigzag chain structure
and through one direction of the [V4O12]4- pseudo plane, the
[V(1)O4] and [V(4)O4] coordinates to [Cu(1-vIM)4]2+ subunits
n-
by joining the [VO3]n chains together (Figure 6(c)). This
structure is relatively rare in the reported hybrid POVs
complexes.
The selected bond lengths and angles are listed in Table S2.
The bond lengths of V-O, V=O and angles of V-O-V in [V4O12]4-
clusters of 1, 2 and [VO3]22- cluster of 3 are approximative with
the similar structures reported previously.32-34 The bond valence
sum (BVS) calculations show that the oxidation states of all
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vanadium atoms are +V (Table S1), which are in good agreement of POVs. Especially, the 400-1000 cm-1 region is worthy of
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with the charge balance of complexes 1-3.
careful determination, where M-Ot (terDmOiIn: a10l.1o0x3y9g/De0nDTa0t3o0m15sE)
and M-Ob (bridging oxygen atoms) can be found. The V=Ot
stretching vibrations appear at 930, 925 and 916 cm-1 for 1, 2
and 3 respectively. The absorption bands at 797, 655 and 594
cm-1 for 1, 788, 654 and 600 cm-1 for 2 and 877 cm-1 788 cm-1
and 640 cm-1 for 3 can be attributed to the bridging V-O-V or
M-O-V stretching vibrations.35 The apparent stretch absorption
bands from 1650 cm-1 to 1510 cm-1 are assigned to C=C and
C=N (1-vIM ligand).36 Moreover, the absorption bands of
coordinated and free water molecules in complexes 1-3 can be
positioned at around 3300–3500 cm-1.37
Scheme 2. Conversion of methyl phenyl sulfide to sulfoxide and sulfone
catalyzed by M-POVs.
Table 1. Conversion of methyl phenyl sulfide to sulfoxide with different
catalysts or without catalyst.a
Catalysts
Conv.(%) Sele.(%)b Reaction system
No
12.6
>99
100
90.5
100
-
[VO(1-vIM)4]2V4O
·
12 6H2Oc
homogeneous
heterogeneous
heterogeneous
heterogeneous
heterogeneous
heterogeneous
d
Ni(1-vIM)4Cl2
28.2
98.6
98.8
91.5
98.2
1
2
3
4
98.7
96.5
98.5
96.8
amethyl phenyl sulfide (0.25 mmol, 1 equiv.), catalyst (8.75 μmol, 3.5 mol%),
30% aq H2O2 (0.3 mmol, 1.2 equiv.), 45 °C, ethanol (1 mL), 4 h. bSelectivity to
methyl phenyl sulfoxide. The byproduct is sulfone determined by GC-MS. cV
content equivalent to 1. dNi content equivalent to 1.
Catalytic Activities of Hybrid POVs in Sulfoxidation Reaction
The methyl phenyl sulfide was selected as a model substrate in
sulfoxidation reaction to evaluate the catalytic activities of
complexes 1-4 (Scheme 2). All catalysts were activated with
two equivalent H2O2 (mole ratio) by stirring them in ethanol at
45 °C for 20 min before using. After the activation process,
they were separated from ethanol and dried at ambient
conditions for use. After much experimentation on optimizing
solvent, amounts of catalyst and oxidant, temperature and the
reaction time, the high conversion of sulfide and selectivity
toward corresponding sulfoxide were reached under optimized
conditions. As shown in Table 1, complexes 1-4 all can
efficiently catalyze the oxidation of methyl phenyl sulfide to
methyl phenyl sulfoxide with the conversion of 91.5%-98.8%
and selectivity of 96.5%-98.7%. Among them, complexes 1, 2
and 4 showed higher activity than complex 3 under optimized
conditions. Given the similar coordination environments of
Ni2+, Cu2+ and Co2+ in complexes 1-4, the different catalytic
performance may be ascribed to the different vanadate units
in complex 3 ([VO3]22-) compared with complexes 1, 2 and 4
Figure 6. (a) The 1D [VO3]nn-chain structure in 3. (b) The 2D network in 3. (c)
Two parallel networks of 3. Color code: [CoNO5] octahedron, gold. All
hydrogen and carbon atoms are omitted for clarity.
PXRD and FT-IR spectra
The simulated and experimental PXRD patterns of three hybrid
POVs complexes 1-3 are shown in Figures S6-S8. The
diffraction peak positions of the experimental PXRD patterns
of 1-3 are in good agreement with the simulated patterns from
single crystal analysis, which indicate that the phase purity of
bulk powders is satisfactory.
As shown in Figures S2-S4, the FT-IR spectra for complexes
1-3 can afford some valuable information for the investigation
(
[V4O12]4-).
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Due to the similar catalytic activity of complexes 1, 2 and 4 reaction and can be reutilized at least 3 runs withVrieewmAartiincleinOgnliintes
and the higher yield, complex 1 was selected as the catalyst for activity and selectivity (methyl phenyl sulDfidOeI: 1c0o.1n0v3e9r/sDi0oDnT0o3f0t1h5eE
further investigation in sulfoxidation reactions. To probe the third run remained above 96%, Figure 8). The IR spectrum
role of each active center of complex 1 in the selective (Figure S5) together with PXRD patterns (Figure S6) before and
oxidation of sulfide toward sulfoxide, we further studied the after catalysis demonstrated that the structure and the
avtivity of Ni(1-vIM)4Cl2 (Figure S10) and [VO(1- crystallinity of 1 was maintained during the reaction process.
6H2O 38
vIM)4]2V4O12· . As shown in Table 1, low conversion of
sulfide (28.2%) and prominent selectivity toward
corresponding sulfoxide (100%) were achieved when using
Ni(1-vIM)4Cl2 as catalyst. When [VO(1-vIM)4]2V4O12·6H2O was
used as catalyst however, the conversion of sulfide reached
above 99% with barely satisfactory selectivity (90.5%; the by-
product was sulfone). We can conclude from the above results
that the combination of {[Ni0.5(1-vIM)2]3[Ni0.5(
1-vIM)H2O]}4+ and
the [V4O12]4- cluster in 1 can produce the heterogeneous catalyst
with excellent conversion and selectivity in the oxidation of methyl
phenyl sulfide. Further, we speculate that the POVs parts in
complexes 1-4 play an important role in improving the catalytic
performance and the cation parts possibly contribute to enhance
the selectivity toward sulfoxides in sulfoxidation process.
Figure 8. Recycle experiments of
1 in sulfoxidation reaction. Reaction
conditions: methyl phenyl sulfide (5 mmol, 1 equiv.), 1 (175 μmol, 3.5 mol%),
30% aq H2O2 (5 mmol, 1.2 equiv.), 45 °C, ethanol (20 mL), 4 h.
The mild reaction conditions, excellent stability, and high
yield for the transformation of methyl phenyl sulfide to methyl
phenyl sulfoxide prompted us to extend the scope of 1 as
heterogeneous catalyst for various sulfides. As shown in Table
2, the catalytic activity is remained when electron donor or
acceptor groups with less steric hindrance are introduced in
the monophenyl sulfides (Table 2, entries 2−4). Some typical
dialkyl sulfides, such as n-butyl sulfide, and dimethyl sulfide
were also investigated to examine the generality of 1 in
sulfoxidation reactions. As shown in Table 2, entries 5−6, the
optimized conditions could be also applicable to dialkyl
sulfides, but the selectivity toward corresponding sulfoxide
was slightly lower compared with that of monophenyl sulfides.
Figure 7. Kinetics of methyl phenyl sulfide sulfoxidation reaction catalyzed by 1
(black); 1 was filtrated from the reaction mixture after 0.5 h (red). Reaction
conditions: sulfide (0.25 mmol), catalyst (8.75 μmol, 3.5 mol%), 30% aq H2O2
(0.3 mmol), 45 °C, ethanol (1 mL), 4 h.
To further elucidate the heterogeneity of complex 1 in the
oxidative system, a hot leaching test was carried out. The solid
catalyst 1 was filtrated off from the mixture after 0.5 h of
reaction (conv. 40.5%; sele. toward sulfoxide 100%), and the
filtrate was subsequently stirred at 45 °C for another 3.5 h. GC
analysis of the resulting reaction mixture showed a negligible
conversion after filtration (Figure 7). Atomic absorption analysis
showed that there were no nickel and vanadium ions in the
filtrate (S9 in the Supporting Information). All the above results
collectively confirmed that the catalytic system is
heterogeneous in nature. Furthermore, complex 1 can be
easily separated by centrifugation after the completion of the
For the sulfur mustard abatement (Bis-(2-chloroethyl)sulfide,
a chemical war agent), taken into account the high toxicity of
real agent, 2-chloroethyl ethyl sulfide (CEES), was selected as
the substrate to further study the catalytic activities of 1 in
sulfoxidation system.39 From Table 2, entry 7, we can see that
satisfactory conversion and low selectivity toward 2-
chloroethyl ethyl sulfoxide (CEESO) were obtained under the
optimized conditions. To avoid peroxidation and obtain higher
sulfoxide selectivity (2-chloroethyl ethyl sulfone (CEESO2) is
also more toxic),40 we lowered the reaction temperature to 30
°C and prolonged the reaction time to 6h and prominent
selectivity of CEESO was obtained (Table 2, entry 7).
6 | J. Name., 2012, 00, 1-3
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Table 2. Selective oxidation of various sulfides to sulfoxides catalyzed by 1.a
Entry
Substrates
Products
Conv. (%)
Sele. (%)b
98.6
96.7
98.7
98.8
1
2
95.2
87.5
92.4
99.2
99.5
93.5
83.7
3
4
5
6
7
c
-
93.5
82.5
94.5
95.6d
aReaction conditions: sulfide (1 mmol, 1 equiv.), 1 (35 μmol, 3.5 mol%), 30% aq H2O2 (1.2 mmol, 1.2 equiv.), 45 °C, ethanol (4 mL), 4 h. bSelectivity to
corresponding sulfoxide. The byproduct is sulfone determined by GC-MS. cGC is not suitable for analyzing the compound with too low boiling point.
dTemperature: 30 °C; Reaction time: 6 h.
It is rare to synthesize sulfoxide or sulfone by oxidizing conversion of methyl phenyl sulfide (>99%) and selectivity
sulfides using the same oxidant with high selectivity.41 Given toward corresponding sulfone (98.5%) were obtained under
the high activity and selectivity of 1 for transformation of the optimized conditions. As shown in Table 3, entries 1-4,
sulfides to sulfoxides, we further examined its utility of methyl phenyl sulfide and monophenyl sulfides several
preparation of sulfones via oxidation of sulfides. The functional groups such as -OCH3, -Cl, -NO2, were oxidized to
exploratory experiments started still using methyl phenyl afford the corresponding sulfones in almost quantitative yields.
sulfide as the model substrate. In order to improve the Moreover, the dialkyl sulfides n-butyl sulfide and dimethyl
conversion of methyl phenyl sulfide and the selectivity toward sulfide worked perfect giving the sulfones with high conversion
methyl phenyl sulfone, increasing the amount of H2O2 and (97.4% for n-butyl sulfide) and selectivity (95.5% for n-butyl
prolonging the reaction temperature is needed. At the same sulfone and 93.7% for dimethyl sulfone) (Table 3, entries 5-6).
time, it is necessary to extend the reaction time. The high
Table 3. Selective oxidation of various sulfides to sulfones catalized by 1.a
Entry
Substrates
Products
Conv. (%)
Sele. (%)b
98.5
>99
1
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>99
98.2
2
>99
>99
97.4
97.2
96.5
95.5
93.7
3
4
5
6
c
-
aReaction conditions: sulfide (1 mmol, 1 equiv.), 1 (35 μmol, 3.5 mol%), 30% aq H2O2 (3.0 mmol, 3 equiv.), 65 °C, ethanol (4 mL), 5 h. bSelectivity to
corresponding sulfone. The byproduct is sulfoxide determined by GC-MS. cGC is not suitable for analyzing the compound with too low boiling point.
were obtained. Yield: 46% (based on NH4VO3). Anal. calcd. (%)
(found) for C40H50N16Cu2V4O13: C, 37.13 (36.85); H, 3.90 (4.16); N,
17.32 (17.11); Cu, 9.82 (9.57); V, 15.75 (15.58). IR (KBr, cm-1):
3417 (m), 3107 (m), 2924 (m), 1646 (s), 1503 (w), 1414 (w), 1380
(w), 1331 (w), 1286 (m), 1231 (m), 1104 (s), 1004 (w), 925 (s),
788 (s), 654 (m), 600 (w), 511 (Cu-N, w).
Synthesis of [Co(1-vIM)H2O][VO3]2 (3): When we try to
improve the crystal quality of complex 4 by reducing the amount
of CoCl2·6H2O, 1-vIM and adjustting the synthetic conditions as
following: NH4VO3 (0.0939 g, 0.8 mmol) and CoCl2·6H2O (0.0952
g, 0.4 mmol) were added to 10 mL water. Then 1-vIm (100 μL)
was added. The resulting mixture was stirred for 1 h and then
heated at 120 °C for 72 h. Fortunately, block pale blue crystals of
3 were obtained when cooling to room temperature. Yield: 54%
(based on NH4VO3). Anal. calcd. (%) (found) for C5H8N2CoV2O7: C,
16.28 (16.02); H, 2.19 (2.32); N, 7.59 (7.36); Co, 15.97 (15.75); V,
27.61 (27.39). IR (KBr, cm-1): 3447 (m), 3122 (m), 1646 (w), 1616
(w), 1513 (w), 1404 (w), 1281 (w), 1242 (m), 1098 (m), 990 (m),
916 (s), 877 (m), 788 (s), 640 (s), 561 (Co-N, w).
Experimental
Materials and methods
All chemicals were purchased from commercial suppliers and
used without further purification. The metal content of the
complexes 1-3 was measured by inductively coupled plasma
(ICP) on an ICP-6000 analyzer. C, H, and N analyses of the neat
complexes were conducted on Perkin-Elmer 240C elemental
analyzer. The FT-IR spectra were recorded as KBr pellets in the
range 4000–400 cm-1 on Nicolet 170 SXFT/IR spectrometer. The
PXRD pattern was collected by using a Rigaku D/max-2550
diffractometer with Cukα radiation. The reaction products were
analyzed by GC-MS (Agilent 7890A-5975C at an ionization
voltage of 1200 V) and GC (Shimadzu GC-2014C with a FID
detector equipped with an Rtx-1701 Sil capillary column).
Synthetic procedures
Synthesis of [Ni2(1-vIM)7H2O][V4O12]·H2O (1): NH4VO3 (0.0939 g,
Synthesis of [Co4(1-vIM)14][V4O12]2·6H2O (4): When we use
the similar synthetic procedure to that of complex 1 except that
CoCl2·6H2O (0.1904 g, 0.8 mmol) was used to replace NiCl2·6H2O,
block dark red crystals [Co4(1-vIm)14][V4O12]2·6H2O with poor
quality were obtained as reported on our previous work.27 Yield:
45% (based on NH4VO3). Anal. calcd. (%) (found) for
C70H95N28Co4V8O30: C, 34.29 (34.02); H, 3.91 (4.11); N, 16.00
(15.82); Co, 9.61 (9.54); V, 16.62 (16.48). IR (KBr, cm-1): 3443 (m),
3126 (m), 1648 (w), 1618 (w), 1515 (w), 1335 (w), 1286 (w),
1237 (m), 1110 (m), 983 (m), 958 (s), 920 (m), 882 (s), 778 (s),
647 (s), 564 (Co-N, w).
0.8 mmol) and NiCl2·6H2O (0.1902 g, 0.8 mmol) were added to
10 mL water. Then 1-vIM (200 μL) was added. The resulting
mixture was stirred for 1 h and then heated at 120 °C for 72 h
under hydrothermal conditions. When cooling to room
temperature, block pale blue crystals were obtained. Yield: 65%
(based on NH4VO3). Anal. calcd. (%) (found) for
C35H48N14Ni2V4O15: C, 34.29 (34.05); H, 3.95 (4.22); N, 15.99
(15.75); Ni, 9.57 (9.31); V, 16.62 (16.44). IR (KBr, cm-1): 3416 (m),
3112 (m), 1650 (s), 1533 (w), 1498 (s), 1426 (w), 1381 (w), 1336
(m), 1279 (s), 1234 (s), 1092 (s), 1046 (w), 1005 (w), 930 (s), 797
(s), 655 (m), 594 (w), 513 (Ni-N, w).
Crystallography
Synthesis of [Cu2(1-vIM)8][V4O12]·H2O (2): The synthetic
procedure was similar to that of complex 1 except that
CuCl2·2H2O (0.1363 g, 0.8 mmol) was used to replace NiCl2·6H2O.
Crystallographic data for complexes 1-3 were conducted on a
Bruker Smart APEX II CCD diffractometer with a graphite-
monochromated Mo Ka radiation (λ = 0.71073 Å). Absorption
When cooling to room temperature, block dark purple crystals
8 | J. Name., 2012, 00, 1-3
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corrections were applied using multi-scan technique with the For sulfoxides: substrate (1 mmol), catalyst (35 μmVoiel,w3A.r5ticmle oOlnl%ine)
DOI: 10.1039/D0DT03015E
SADABS program. The structures were solved and refined by and 30 % aq H2O2 (1.2 mmol) were stirred at 45 °C in ethanol (4
SHELXS-2014 and SHELXL-2014 program packages.42,43 mL) for 4 h. For sulfones: substrate (1 mmol), catalyst (35 μmol,
Crystallographic data and structure refinement for 1-3 are 3.5 mol %) and 30 % aq H2O2 (3.0 mmol) were stirred at 65 °C in
summarized in Table 4. The crystallographic data have been ethanol (4 mL) for 5 h. The reaction mixture was heated slowly
deposited with the Cambridge Crystallographic Data Centre to the desired temperature in a Wattecs Parallel Reactor. After
(CCDC) as entries 2021866 (1), 2021864 (2) and 2021865 (3).
completion, the catalyst was simply retrieved by filtration and
then washed with ethanol (ca. 3 × 5 mL). The resulting mixture
was analyzed by GC-MS and GC.
Catalytic oxidative sulfoxidation process
Table 4. Crystallographic data for complexes 1-3.
1
2
3
Formula
C35H48N14Ni2V4O15
1226.05
Triclinic
P-1
C40H50N16Cu2V4O13
1293.80
Triclinic
P-1
C5H8N2CoV2O7
368.94
Monoclinic
P21/c
Mr
Crystal
system
Space group
T(K)
298(2)
298(2)
298(2)
a (Å)
12.6684(17)
15.0479(19)
15.759(2)
68.329(2)
66.587(2)
73.633(2)
2529.6(6)
2
10.8101(18)
15.577(3)
17.012(3)
84.690(3)
76.443(3)
74.492(3)
2682.1(8)
2
12.057(3)
5.8528(14)
15.556(4)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3)
98.297(4)
90
1086.2(4)
4
Z
Dcalc.(g/cm-3)
1.610
1.602
2.256
F(000)
1248
1312
724
R1
0.0521
0.0574
0.0200
0.0568
0.0231
0.0586
1.306
[I>2σ(I)]
wR2
0.1422
0.1630
[I>2σ(I)]
R1(all data)
0.0651
0.0799
wR2
(all data)
0.1537
0.1805
GOOF
1.043
1.045
CCDC No.
2021866
2021864
2021865
Importantly, 1 can be simply recovered and recycled without losing
its catalytic activity. The rational controlling synthesis of other
hybrid POVs and the use of them in other catalytic reactions are in
progress.
Conclusions
In summary, we successfully prepared three new inorganic-organic
hybrid POVs 1-3 by rationally controlling the hydrothermal
synthetic conditions using 1-vIM as the N-donor ligand. The
different final crystal structure of 3 compared with that of 1 and 2
indicate that the amount of 1-vIM is a crucial factor in the
synthetic procedure of inorganic-organic hybrid POVs. All hybrid
POVs show high heterogeneous catalytic activity and selectivity in
the oxidation of sulfides to produce sulfoxides or sulfones
respectively. Specifically, 1 show high activity and prominent
selectivity toward CEESO in the CEES abatement reaction.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
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26. S. Jääskeläinen, I. O. Koshevoy, S. Suvanto, T. Ryhänen and P.
We gratefully acknowledge support from the National Natural
Science Foundation of China (No. 21871026, 21671019,
21871125), the Natural Science Foundation of Shandong
Province (No. ZR2017LB002) and the Undergraduate Science
and Technology Innovation Project of Shandong Provence (No.
S201910453070).
View Article Online
Hirva, New J. Chem., 2020, 44, 12762.DOI: 10.1039/D0DT03015E
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For Table of Contents only
Three inorganic-organic hybrid polyoxovanadates [Ni2(1-vIM)7H2O][V4O12]·H2O (1),
[Cu2(1-vIM)8][V4O12]·H2O (2) and [Co(1-vIM)H2O][VO3]2 (3) have been
synthesized and fully characterized. Complex [Ni2(1-vIM)7H2O][V4O12]·H2O (1), as a
heterogeneous catalyst exhibit extraordinary catalytic performance (conv. of sulfides
up to 98.6 %, sele. toward sulfoxides up to 99.5 %; conv. of sulfides up to >99 %, sele.
up to 98.5 % for sulfones) in the sulfoxidation reactions using H2O2 as oxidant.
Noticeably, complex 1 is stable in the catalytic recycling test and can be reused at
least three times without losing its activity.