A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its Catalytic Oxidation of Thioethers

Article abstract of DOI:10.1021/acs.cgd.8b01474

A neoteric hepta-nuclear Ti-oxo-cluster-substituted tetrameric tungstoantimonate [H₂N(CH₃)₂]₂₂Na₁₈{Ti₇O₆(SbW₉O₃₃)₄}₂·124H₂O (1) has hydrothermally been synthesized and tested by single-crystal/powder X-ray diffraction, IR spectra, and thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon hepta-nuclear Ti-oxo-cluster octahedron [Ti₇O₆]¹⁶⁺ enclosed in four [B-α-SbW₉O₃₃]^9- building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with H₂O₂ for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability and excellent recyclability.

Full text of DOI:10.1021/acs.cgd.8b01474

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Article
A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted
Tungstoantimonate and Its Catalytic Oxidation of Thioethers
Hai-Lou Li, Chen Lian, Da-Peng Yin, Zhi-Yu Jia, and Guo-Yu Yang
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01474 • Publication Date (Web): 30 Nov 2018
Downloaded from http://pubs.acs.org on December 1, 2018
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Crystal Growth & Design
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A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its
Catalytic Oxidation of Thioethers
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Hai-Lou Li, Chen Lian, Da-Peng Yin, Zhi-Yu Jia and Guo-Yu Yang*
MOE Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488,
China. E-mail: ygy@bit.edu.cn
Dedicated to Professor Xintao Wu on the occasion of his 80th birthday
_______________________________________________________________________________________________________________
ABSTRACT: A neoteric hepta-nuclear Ti-oxo-cluster substituted tetrameric tungsto-
antimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2∙124H2O (1) has hydrothermally been
synthesized and tested by single-cryatal/powder X-ray diffraction, IR spectrum, and
thermal analysis. The glamorous feature of this tetrameric polyoxoanion is an uncommon
hepta-nuclear Ti-oxo-cluster octahedron [Ti7O6]16+ enclosed in four [B-α-SbW9O33]9–
building units. As a heterogeneous catalyst, the investigation on catalytic oxidation with
H2O2 for multiple thioethers indicated that 1 possesses high conversion and remarkable selectivity. Additionally, 1 exhibits good stability
and excellent recyclability.
■
INTRODUCTION
vacant Keggin by aqueous solution method, for example, a cyclic tetra-
meric silicotungstate [(Ti2SiW10O39)4]24– built by four [β-Ti2SiW10O39]6–
fragments via Ti–O–Ti linkages,15 two cyclic Ti9-/T10-based trimers of
[Ti9(PO4)(PW9O38)3]18–/[Ti10(H2O)3(SiW9O37OH)3]17– with three Ti3-
oxo-cluster substituted Keggin units linked by three Ti–O–Ti bonds and
a capping group,16 a Ti2-containing sandwiched arsenotungstate17 as
s extremely interesting nanoscale polynuclear metal-oxygen
clusters polyoxometalates (POMs) have attracted great attention
A
mainly due to two aspects: 1) architectural aesthetic appreciation (metal-
centered polyhedral connections by sharing angles, edges or faces can
polymerize into a variety of configurations); 2) potential application
performance (in catalysis, electrochemistry, magnetism and material
science etc).1-4 In the huge family of POMs, tungstoantimonates (TAs),
an significant subfamily, has tremendous variety of constructions and
properties. In addition, vacant TAs can serve as multidentate inorganic
ligands to combine interesting organic moieties, functional metallic
centers or metal-oxygen clusters (such as p, d, and f blocks).2-8
well
as
a
Ti7-oxo-cluster-centred
Nomiya et al. reported some Ti-substituted
arsenotungstate
[Ti6(TiO6)(AsW9O33)4]20– 18
.
architectures, such as two oxalic acid modification tungstophosphates
[Ti2(OH)2(ox)2OPW11O39]7– and [Ti4(ox)4(H2O)4O3PW10O37]7–,19-20 and
several multi-core Ti-oxo- cluster-substituted Dawson tetrameric/trimeric
POTs {[Ti(OH)3]4Cl- (P2W15Ti3O62)4}45–, [(NH4)(P2W15Ti3O60.5)4]35–
[Ca7(CO3)(OH)(H2O)18- Ca(H2O)3(P2W15Ti3 O61)3]19– 21-23
Cronin et al.
,
.
Ti-oxo-clusters (TOCs) as one of the most important types of cluster
materials have a surge in recent reports on chemical, energy and
environmental sciences.9 Nevertheless, the majority of relevant reports
are mainly concentrated on organic TOCs, in which the N, O atoms of
the organic ligands are beneficial to structural stability and construction.
Since Ti4+ ion is susceptible to hydrolyze, inorganic aqueous TOCs are
difficult to obtain. Using vacant POMs as multidentate inorganic ligands
to stabilize TOCs and further make TOCs-substituted POMs are full of
meaning and challenge,10 which is due to the terminal hydroxyl oxygens
of the Ti atoms easily form Ti–O–Ti bonds by intermolecular
dehydration, therefore, Ti-substituted POMs are prone to generate
oligomeric constructions.11 Ti-containing POMs as an important area
have drawn immense attention in the past few decades.12 Some
examples of Ti-containing polyoxotungstates (POTs) have been
unremittingly discovered. The first Ti-containing POT [ClTiW11PO39]4–
corresponding to a mono-Ti substituted tungstophosphate, was reported
in 1983 by Knoth et al.13 In 1993, Finke and co-workers reported a
reported two Ti-embedded sandwiched POTs [TiO(SbW9O33)2]16– and
[Ti4(H2O)10(AsTiW8O33)2]6– in 2010.24 Li and co-workers made two
Ti-substituted organic–inorganic hybrid POTs in 2015.25
It is quite clear that most of the previous literature about Ti-containing
POMs were synthesized by conventional aqueous solution at ambient
temperature. Furthermore, the configurations of TOC-containing TAs
have been reported rarely. Herein, a novel hepta-nuclear-TOC-
substituted POT, [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2∙124H2O (1)
has been made, which is first Ti7-oxo-cluster-substituted TA tetramer
built by four trivacant Keggin [B-α-SbW9O33]9− fragments and an
octahedronal [Ti7O6]16+ cluster.
Compound 1 was hydrothermally made in the molar ratio of
Na9[B-α-SbW9O33]·19.5H2O, Na2WO4·2H2O, [H2N(CH3)2]·Cl, Li2CO3
and TiOSO4 is 1.1:1.0:8.1:5.6:2.0. It should be particularly pointed out
that the WO42– plays a subtle role in the experiment, although it does not
appear in the final product, the yield of 1 is very low in the absence of
WO42– anion. Additionally, when the usage amount of WO42– anions is
higher than 0.500 g, it is liable to gain the isopolytungstate. Furthermore,
the amount of precursor is a vital factor: the usage amount in the range
hexa-nuclear TOC-sandwiched silicotungstate [Si2W18Ti6O77]14– 14
Kortz and co-workers made some great achievements of Ti-substituted
.
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Crystal Growth & Design
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of 1.700−2.300 g is favor to the formation of 1. Finally, the usage
both from the center Ti3O6 [Ti-O: 1.728(19)-1.741(17) Å], and the
bottom four µ-O atoms come from two [B-α-SbW9O33]9– fragments
[Ti-O: 1.933(14)-1.954(14) Å]. In addition, the length of each side of the
octahedronal [Ti7O6]16+ cluster is about 5.2 Å, and the distance between
the Ti atoms of the six vertices of the octahedron and the central Ti atom
is close to 3.7 Å (Figure 1d).
1
2
3
4
5
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amount of TiOSO4 also has a great influence on the experiment, which
is beneficial to form 1 in the range of 0.180−0.240 g, and the optimal
dosage is 0.198 g. Apart from aforementioned usage amount aspects,
the pH is also an important factor that must be taken into consideration
in the reaction system for the formation of product. It is difficult to get 1
when the pH is higher than 4.5 or lower than 3.6, and the optimum
acidity is 4.0. Here, we control the pH of the reaction system by
introducing Li2CO3 and adding diluted HCl. The pH of after reaction is
4.4.
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Figure 2. (a), (b) The 2-D network packing and the simplified packing of 1.
Figure 1. (a) The TA polyoxoanion of 1a. (b) The simplified architecture of 1a. (c) The
hepta-nuclear-TOC [Ti7O6]16+ fragment. (d) The simplified architecture [Ti7O6]16+
.
Color codes: WO6: red; TiO5/TiO6/Ti4+: bright yellow; antimony: bright green. A:
-1-x+y, -2-x, z. B:-2-y, -1+x-y, z.
Additionally, an interesting feature is that each 1a anion (simplified
as tetrahedron (red color) shown in Figure 2) is linked to surrounding
three same ones via three hexa-coordinate Na1+ cations, each Na1O6
octahe- dron connects two 1a polyanions with apical opposite direction
(Figure 2). In the Na1O6 group, four O atoms are derived from two 1a
clusters and the other two O atoms are from coordination water
molecules. Specifically, six Na1+ ions and three pairs of 1a with
opposite direction give birth to a ring, and the outer ring diameter is
about 47.37 Å, and the inner ring diameter is approximately 14.40 Å
(Figure S2).
Selective oxidation of organic thioethers has attracted a topical
interest due to the sulfones and sulfoxides owning versatile utilities
(biochemistry, chemical industry and medicinal chemistry).27 H2O2 is
generally considered to be a “green” oxygen donor and is therefore a
preferred oxidant in organic oxidation reactions.28 The most fascinating
application value of POMs is to act as a catalyst because POMs possess
redox properties, flexible acidity and high stability etc.29 Recalling
previous reports, in the presence of Ti-containing POMs as a catalyst,
organic thioethers can be efficiently oxidized by H2O2 to obtain sulfones
and sulfoxides.30 In this catalytic experiment, 1 was investigated as a
heterogeneous catalyst in the oxidation of various aromatic thioethers by
H2O2 oxidant under 3 mL acetonitrile solvent (Scheme S1). The
products of thioethers oxidation were recognized by GC-MS spectra and
the selectivity of sulfoxide and sulfone as well as the conversion of
The structural analysis demonstrates that 1 crystallizes in the trigonal
space group R-3m and the molecular structure has two extraordinary
tetrameric polyoxoanions {Ti7O6(B-α-SbW9O33)4} (1a, Figure 1a), 22
[H2N(CH3)2]+, 18 Na+ and 124 H2O. BVS calculation26 reveals that the
W, Sb and Ti atoms are in the +6, +3 and +4 oxidation states,
respectively (Table S2). The tetrameric 1a consists of an uncommon
Ti7-oxo-cluster and four [B-α-SbW9O33]9– fragments and this hepta-
nuclear TOC [Ti7O6]16+ is packed into four trivacant fragments, in which
four [B-α-SbW9O33]9– fragments are evenly distributed around the
octahedronal [Ti7O6]16+ (Figure 1b) and each [B-α-SbW9O33]9– fragment
is linked to three pent-coordinate TiO5 groups of [Ti7O6]16+ via six µ-O
atoms. In addition, in [B-α-SbW9O33]9– fragment the W-O distances are
in the range of 1.699(17)-2.38(2) Å, and the Sb-O bond lengths vary
from 1.974(18) to 1.999(17) Å. In [Ti7O6]16+, although three Ti4+ cations
are unique, only show two coordination modes, a hexa-coordinate
octahedron and a pent-coordinate tetragonal pyramid (Figure 1c). The
central Ti3 atom shows hexa-coordinate octahedron, which is linked to
six Ti atoms (3 Ti1 and 3 Ti2) situated in the apex of the octahedron via
six µ-O atoms (Ti–O: 1.948(17)–1.966(19) Å). The coordination
environments of other six pent-coordinate tetragonal pyramid Ti atoms
are similar and the apex oxygen atoms of each tetragonal pyramid are
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Crystal Growth & Design
thioethers was identified by GC spectra (Figure S6,7).
found that the substituent on the aromatic ring occupying the ortho-
position resulted in a low selectivity of sulfone. This phenomenon is
consistent with the literature.6 Finally, under the same reaction
conditions, we also studied the catalytic oxidation of benzothiophene. It
is clear that the conversion and selectivity of benzothiophene was lower
than that of other aromatic thioethers.
1
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Firstly, methyl phenyl sulfide (MPS) was employed as a substrate to
oxidize to acquire methyl phenyl sulfoxide (MPSO) and methyl phenyl
sulfone (MPSO2) in the case of 1 as a catalyst in 3 mL acetonitrile
solution. The results exhibited that the substrate was completely
disappeared (the conversion was 100 %) and the selectivity of MPSO2
was 32% at 35°C (Table S3). Under the same conditions, the parallel
tests were conducted, exhibiting that the conversion of MPS in the
introduction of {SbW9}, TiOSO4 and in the absence of catalyst was
97%, 12% and 10% respectively, and the selectivity of MPSO2 was
20%, 0 and 0 respectively. Hence, parallel test results indicate that
compound 1 is an excellent catalyst.
However, under above experimental conditions, the selectivity of
MPSO2 is still relatively low in the presence of compound 1. Therefore,
we further optimized the experimental condition by adjusting the
reaction temperature. When the reaction temperature up to 50°C, other
conditions remained unchanged (2.8 molar ratio for O/S, l h reaction
time, 1000 molar ratio for S/C and 3mL MeCN), the conversion of
MPS and the selectivity of MPSO2 were both 100% (Table 1, entry 1).
In addition, under the same experimental conditions, we also
investigated the oxidation catalysis of different aromatic thioethers. We
examined the steric hindrance effect, as shown in Table 1 (entries 2–4),
when the steric hindrance increased, although the conversions of
substrates were still 100%, the selectivity of sulfone was low, 59%
(entry 2), 79% (entry 3) and 98% (entry 4). The effect of different
substituents on the sulfone product was also taken into account. As
shown in Table 1 (entries 5–7), the stronger the electron-withdrawing
group, the lower the selectivity. Comparing entry 7 and 8 in Table 1
Under the above conditions, although the conversion of most
aromatic thioethers was higher than 98%, the selectivity was relatively
low. We slightly augmented the O/S molar ratio and increased the
reaction temperature aiming at optimizing selectivity (Table 2). Here,
under the optimal conditions of 60°C, 3 O/S molar ratio, 1 h reaction
time, 3 mL acetonitrile and 1000 S/C molar ratio, the conversion of
most aromatic thioethers was greater than 99%, and the selectivity of
almost all sulfones were 100% (Table 2, entries 1–6). The selectivity of
2-bromothioanisole was still relatively low under above optimal
conditions although which was improved. We extended the reaction
time for the purpose of increasing the selectivity of 2-bromophenyl
methyl sulfone, when which was extended from 1 h to 3 h, the
selectivity increased from 41% to 71% (Table 2, entry 7). Similar to the
conditions of 2-bromothioanisole, when the reaction time was up to 3 h,
the conversion of benzothiophene and the selectivity of sulfone were
both above 90% (Table 2, entry 7).
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Furthermore, the cyclic test was conducted to evaluate the stability of
catalytic performance of 1 during catalytic oxidation of MPS under the
same conditions. In this heterogeneous catalytic system, the catalyst was
Table 2. Selective oxidation of various aromatic thioethers to sulfones using
catalyst 1 [a]
Time.
(h)
Temp.
(oC)
Cov. [b]
(%)
Selectivity (%)[c]
Entry
Substrate
Table 1. Selective oxidation of various aromatic thioethers to sulfones using
catalyst 1 [a]
RRꞌSO/RꞌRSO2
Cov.[b]
(%)
Selectivity (%)[c]
1
2
3
4
5
6
1
1
1
1
1
1
60
60
60
60
60
60
100
100
100
99
0
0
0
0
0
0
100
100
100
100
100
100
Time.
(h)
Temp.
(oC)
Entry
Substrate
RRꞌSO/RꞌRSO2
1
2
3
4
5
6
7
8
1
1
1
1
1
1
1
1
50
50
50
50
50
50
50
50
100
100
100
100
98
0
100
59
79
98
88
52
79
8
41
21
2
100
100
12
48
21
92
1
2
3
1
3
100
100
100
51
59
45
29
6
41
55
71
94
99
98
7
60
100
100
8
60
92
1
[a] Catalytic conditions: substrate (0.5×10–3 mol), the molar ratio of oxidizer
and substrate is 3, the molar ratio of substrate and catalyst is 1000, MeCN (3
mL), 60°C. [b] Conversion based on substrate consumption and determined by
GC-FID using an internal standard technique. [c] The selectivity of sulfones
was authenticated by GC-MS.
9
1
50
11
55
45
[a] Catalytic conditions: substrate (0.5×10–3 mol), the molar ratio of oxidizer
and substrate is 2.8, the molar ratio of substrate and catalyst is 1000, MeCN (3
mL), 50°C. [b] Conversion based on substrate consumption and determined by
GC-FID using an internal standard technique. [c] The selectivity of sulfones
was authenticated by GC-MS.
collected by filtration at the end of each experiment, and then reused for
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■
ACKNOWLEDGEMENTS
1
2
3
4
This work was supported by the NSFC (no. 21571016, 21831001 and
91122028) and the NSFC for Distinguished Young scholars (no.
20725101).
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(Figure S8), demonstrating that 1 does not change after the catalytic
reaction and has a good stability.
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■
CONCLUSIONS
resolved assembly of
a
series of the largest scandium-containing
In summary, a novel Ti7-oxo-cluster-substituted TA has been
polyoxotungstates. Dalton Trans. 2017, 46, 6848-6852.
prepared, in which the hepta-nuclear TOC, [Ti7O6]16+, connects four
[B-α- SbW9O33]9– fragments via 24 µ-O atoms. Interestingly, 6 Na+
cations and 6 polyanions join each other to give birth to a ring. To
acquire further insight into the thermal stability of 1, IR spectra at
different temperatures were recorded, indicating that 1 is stable below
400oC. Additionally, we used 1 as a catalyst to carry out oxidation
catalysis tests on different aromatic thioethers, showing the most
aromatic thioethers’ conversions and sulfone selectivities are 100%
under the conditions of 3 O/S molar ratio, 1000 S/C molar ratio, 1 h
reaction time, 60oC reaction temperature and 3 mL acetonitrile solvent.
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ASSOCIATED CONTENT
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Wheel [{β-Ti2SiW10O39}4]24-. Angew. Chem. Int. Ed. 2004, 43, 3485-3488.
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19-Tungstodiarsen ate (III) [Ti2(OH)2As2W19O67(H2O)]8– :Synthesis, Structure,
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Supporting Information
PXRD patterns, IR spectra, the related structure figures, TG curve,
crystallographic data and structure refinements for 1 and the related
catalytic experiments of 1.
Accession Codes
1869713 for 1 contains the supplementary crystallographic data for
this article.
(19) Hayashi, K.; Takahashi, M.; Nomiya, K. Novel Ti–O–Ti bonding
species constructed in a metal-oxide cluster. Dalton Trans. 2005, 3751-3756.
(20) Hayashi, K.; Murakami, H.; Nomiya, K. Novel Ti−O−Ti Bonding
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: ygy@bit.edu.cn. Fax: +86-10-68918572. (G.-Y. Yang)
Species Constructed in
a Metal−Oxide Cluster: Reaction Products of
Bis(oxalato) oxotitanate(IV) with the Dimeric, 1,2-Dititanium(IV)-Substituted
Keggin Polyoxotungstate. Inorg. Chem. 2006, 45, 8078-8085.
(21) Sakai, Y.; Yoza, K.; Kato, C. N.; Nomiya, K. Tetrameric,
Trititanium(III) -Substituted Polyoxotungstates with an –Dawson Substructure
as Soluble Metal-Oxide Analogues: Molecular Structure of the Giant
“Tetrapod” [(a-1,2,3-P2W15Ti3O62)4{µ3-Ti-(OH)3}4Cl]45–. Chem. Eur. J. 2003,
ORCID
Guo-Yu Yang: 0000-0002-0911-2805
Notes
The authors declare no competing financial interest.
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Cavity of Tetrameric Polyoxometalate, Composed of Four Trititanium(IV)-
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A New Hepta-Nuclear Ti-Oxo-Cluster-Substituted Tungstoantimonate and Its
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Hai-Lou Li, Chen Lian, Da-Peng Yin, Zhi-Yu Jia and Guo-Yu Yang*
A new Ti7-oxo-cluster substituted tungstoantimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2∙124H2O
has been made and catalytic oxidation of aromatic thioethers have also been investigated.
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Hai-Lou Li, Chen Lian, Da-Peng Yin, Zhi-Yu Jia and Guo-Yu Yang*
A new Ti7-oxo-cluster substituted tungstoantimonate [H2N(CH3)2]22Na18{Ti7O6(SbW9O33)4}2·124H2O has
been made and catalytic oxidation of aromatic thioethers have also been investigated.
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