Pyrazine dicarboxylate-bridged arsenotungstate: Synthesis, characterization, and catalytic activities in epoxidation of olefins and oxidation of alcohols

Article abstract of DOI:10.1039/c9dt02436k

A praseodymium(iii)-containing arsenotungstate K₁₆H₁₅Li₇[Pr₂(H₂O)₃(pzdc)As₃W₂₉O₁₀₃]₂·38H₂O (1) (pzdc = pyrazine-2,3-dicarboxylic acid) was synthesized by a conventional aqueous solution method and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single crystal X-ray diffraction. Structural analysis revealed that compound 1 was constructed by two identical subunits {Pr₂(H₂O)₃(AsW₉O₃₃)₃W₂O₄} bridged together by two pzdc ligands. In addition, compound 1 could act as an efficient catalyst for the epoxidation of olefins and oxidation of alcohols with hydrogen peroxide (H₂O₂) as the oxidant. In particular, the turnover frequency (TOF) in the oxidation of 1-phenylethanol reached up to 10170 h^-1, which is higher than that of previously reported catalysts.

Full text of DOI:10.1039/c9dt02436k

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DOI: 10.1039/C9DT02436K
ARTICLE
Pyrazine Dicarboxylate-Bridged Arsenotungstate: Synthesis,
Characterization, and Catalytic Activities in Epoxidation of Olefins
and Oxidation of Alcohols
Received 00th January 20xx,
Accepted 00th January 20xx
Xinyi Ma, Peipei He, Baijie Xu, Jingkun Lu, Rong Wan, Hechen Wu, Yuan Wang, Pengtao Ma,
DOI: 10.1039/x0xx00000x
Jingyang Niu and Jingping Wang
A praseodymium(III)-containing arsenotungstate K16H15Li7[Pr2(H2O)3(pzdc)As3W29O103]2·38H2O (1) (pzdc = pyrazine-2,3-
dicarboxylic acid) was synthesized by a conventional aqueous solution method, characterized by elemental analysis, IR
spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), and single crystal X-ray diffraction.
Structure analysis revealed that compound 1 was constructed by two identical subunits {Pr2(H2O)3(AsW9O33)3W2O4}
bridged together by two pzdc ligands. In addition, compound 1 could act as an efficient catalyst for the epoxidation of
olefins and oxidation of alcohols with hydrogen peroxide (H2O2) as oxidant. In particular, the turnover frequency (TOF) in
the oxidation of 1-phenylethanol reached up to 10170 h−1, which is higher than previously reported catalysts.
acid (H2pzdc) with multiple coordination modes,14 not only can
be used as a co-catalyst in the oxidation of alkanes and
alcohols,15 but also can act as a chelate ligand in synthetic
Introduction
Polyoxometalates (POMs) have attracted increasing interests
recently owing to their well-defined tunable structures, unique
properties and promising applications such as catalysis,
electrochemistry, photochemistry, magnetism, and biology.1
As an important subfamily of polyanionic clusters,
arsenotungstates (ATs) show a strong affinity to transition
metal (TM) ions and rare earth (RE) ions.2 Hitherto, numerous
TM-decorated ATs have been prepared.3 As early as in 1997,
Pope et al. reported a gigantic water-soluble heteropoly-
systems.16 However, little work has been devoted to RECATs
17
and H2pzdc.
topic.
Thus, It is still an important and challenging
H2O2 is a safe, inexpensive, readily available, relatively
nontoxic oxidant with only water as by-product.18 Therefore,
H2O2-based organic reactions are more captivating in recent
years.19 On the one hand, the epoxidation of olefins is an
important reaction in the fine chemical industry, as the
epoxides are valuable intermediates, precursors, and raw
materials for epoxy resins, pharmaceuticals, surfactants.20 On
the another hand, the oxidation of alcohols to carboxylic acids
and ketones by homogeneous and heterogeneous catalysts, is
a fundamental class of organic transformations, which has
great potential for biological systems and industrial
processes.21 For the past few decades, varieties of POMs are
generally used as effective catalysts for the oxidation of
alcohols and epoxidation of olefins.22 As early as in 1988, Ishii
and co-workers had used the classical Keggin POMs,
[PMo12O40]3– and [PW12O40]3–, as catalysts for the epoxidation
of olefins and oxidation of alcohols.23 In 2003, Mizuno and co-
tungstate anion [As12W148O524Ce16(H2O)36]76– 4
. Later, several
RE-containing ATs (RECATs) were sequentially discovered, such
as, [Gd8As12W124O432(H2O)22]60– and [(H2O)11REIII(REIII OH)(B-α-
2
AsW9O33)4(WO2)4]20– et.al.5 However, RE3+ ions are in some
cases over-reactive with POM precursors, resulting in a rapid
precipitation rather than crystallization.6 Many examples have
demonstrated that carboxylic acid ligands are frequently
employed to slow the quick reactions between the two
reactants, facilitating the assembly of various organic-
inorganic hybrid RECATs (Table S1).7–13 Nevertheless, most of
these carboxylic acid ligands are monocarboxylates or amino
acids, there are still few examples of RECATs constructed with
N-containing polycarboxylic acids. Pyrazine-2,3-dicarboxylic
workers reported
a
silicotungstate compound, [γ-
SiW10O34(H2O)2]4–, and its effectiveness was evidenced by
≥99% selectivity for epoxides, ≥99% H2O2 utilization
efficiency.24 However, the investigation of arsenotungstates in
catalysis is still rare, most likely due to the toxicity of arsenic.25
Based on the aforementioned considerations, in this work,
we selected [As2W19O67(H2O)]14–, H2pzdc and PrCl3·6H2O to
Henan Key Laboratory of Polyoxometalate Chemistry, Institute of Molecular and
Crystal Engineering, College of Chemistry and Chemical Engineering,
Henan University, Kaifeng, Henan 475004, P. R. China. E-mail: jyniu@henu.edu.cn,
jpwang@henu.edu.cn; Fax: +86-371-23886876
Electronic supplementary information (ESI) Summary of the reported ATs based on
different carboxylate ligands (Table S1); available structural figure (Fig S1–S2); the
BVS calculation, selected bond angles and distances (Table S3–S4); IR, XPRD and
TGA of 1 (Fig S3–S5); The Photoluminescence (Fig S6–S7); Catalytic properties
(Tables S5–S9 and Fig S8–S13). CCDC reference numbers 1892210 for 1. See DOI:
10.1039/x0xx00000x.
prepare
an
organic-inorganic
hybrid
(1).
RECAT
The
K16H15Li7[Pr2(H2O)3(pzdc)As3W29O103]2·38H2O
compound 1 can not only act as a high-performance catalyst in
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Crystal Structure
View Article Online
DOI: 10.1039/C9DT02436K
Single crystal X-ray diffraction analysis reveals that compound
1 crystallizes in the triclinic space group P1. The polyanion
38−
[Pr4(H2O)6(pzdc)2As6W58O206
two identical
]
(Fig. 1a) is constructed from
with the formula
subunits
{Pr2(H2O)3(AsW9O33)3W2O4} (Fig. 1b), which are linked each
other by two pzdc ligands constituting a staggered pattern (Fig.
S1). The subunit 1b is built by three trilacunary {B-α-AsW9O33}
fragments, which is combined with two {WO6} octahedras
(W10, W20) and a Pr3+ ion via O−W−O and O−Pr−O bonds
(W10−O: 1.911(19)−2.153(17) Å, W20−O: 1.877(17)−2.20(2) Å).
All {B-α-AsW9O33} units are derived from the disassembly-
reassembly of [As2W19O67(H2O)]14− precursor.26
Scheme 1 The preparation process of 1.
the epoxidation of olefins in n-butyl alcohol solvent, but also
shows efficient conversion in the direct oxidation of secondary
alcohols to the corresponding ketones with only one
equivalent of 30% H2O2 aqueous solution.
Alternatively, polyanion 1a can also be described as six {B-α-
AsW9O33} fragments that support a distorted [Pr4(H2O)6W4O8
(pzdc)2]16+ unit (Fig. 2a). In the distorted [Pr4(H2O)6W4O8
(pzdc)2]16+ unit, all symmetrical Pr3+ ions are located at a plane
and they display distinct different geometry configurations
(Fig. 2b). Pr1 exhibits a ten-coordinated environment, and
displays a distorted bicapped square antiprismatic geometry.
Pr1 is linked by a μ3-O and three μ2-O atoms from {B-α-
AsW9O33} fragments (Pr1−O: 2.401(17)−2.503(17) Å), four μ2-O
atoms from a pzdc ligand (Pr1−O: 2.672(18)−2.73(19) Å), and
two aqua oxygen atoms (Pr1−O(W) 2.59(2)−2.649(17) Å),
respectively. The coordination geometry of Pr2 is different
from that of Pr1. It is nine-coordinated and careful inspection
of the bond angles indicates that the coordination geometry is
best described as distorted monocapped square antiprismatic.
Pr2 is defined by a μ3-O and five μ2-O atoms from {B-α-
AsW9O33} fragments (Pr2−O: 2.499(18)−2.53(2) Å), a μ2-O atom
and a N atom from a pzdc ligand (Pr2−O: 2.541(17) Å, Pr2−N:
2.67(2) Å), and a terminal water aqua oxygen atom (Pr2−O:
2.480(18) Å), respectively. According to the bond valence sum
(BVS) calculation,27 the oxidation states of all Pr, As and W
Results and discussion
Synthesis
The synthesis of 1 was achieved from the reaction of
K14[As2W19O67(H2O)], PrCl3·6H2O and H2pzdc in a molar ratio of
1 : 2.4 : 3 in 60 °C aqueous solution with stirring for 1 h
(Scheme 1). In this reaction system, some important reaction
factors should be emphasized: (i) taking account of the
resemblance of RE3+ ions, other RE3+ ions have also been tried,
but only Ce3+ obtained a novel crystal structure in the identical
situation.17c Thus, It is fascinating for us to go through in-depth
exploration of this reaction; (ii) compound 1 could not be
isolated outside the pH range of 3.0−4.5. At the pH value of
4.0, the crystal quality is the best, and we can achieve the
highest yield; (iii) necessity to add LiCl solution into the
reaction mixture because it can promote the formation of 1 by
increasing the solubility of the polyanion building blocks.9c, d
Fig. 1 (a) Combination polyhedral/ball-and-stick representation
Fig. 2 (a) Combination polyhedral/ball-and-stick representation
of distorted unit [Pr4(H2O)6W4O8 (pzdc)2]16+, atoms with A in
their labels are symmetryically generated. A: -x-1, 1-y, -z; (b)
The coordination environments of Pr1 and Pr2. Right: ball-and-
stick repressentation of polyanion 1a; Colour code: WO6 (blue
octahedra); As (pink); Pr (bright green); C (black); N (deep blue);
O (red)
38−
of polyanion [Pr4(H2O)6(pzdc)2As6W58O206
]
(1a), Lattice
water molecules, H+, K+ ions are omitted for clarity; (b)
Combination polyhedral/ball-and-stick representation of
subunit {Pr2(H2O)3(AsW9O33)3W2O4} (1b). Colour code: WO6
(blue octahedra); As (pink); Pr (bright green); C (black); N (deep
blue); O (red).
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atoms exhibit +3, +3 and +6, respectively. In addition, the BVS when H2O2/substrate ratio was varied from 1:1 to 3:1, the
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DOI: 10.1039/C9DT02436K
value of the terminal O31 atom connected with the W4 atom conversion slightly changed upon further increase of the
is 1.03 and the terminal O93 atom connected with the W26 H2O2/substrate ratio. It demonstrated that H2O2 loading has a
atom is 0.98, suggesting that O31 and O93 is monoprotonated vital impact on the reaction optimization process (Fig. 3c).31
A
(Table S2).
series of temperature were tested, the highest conversion was
observed at 65°C (Fig. 3d).
Epoxidation of olefins
The kinetics of compound 1 in epoxidation of cis-
cyclooctene reaction was performed under the optimised
conditions. The conversion and ln(Ct/C0) are plotted against
the reaction time in Fig. 3e, where C0 and Ct are the initial cis-
cyclooctene concentration and the concentration of cis-
cyclooctene at time t, respectively. The linear fit of the data
revealed that the catalytic reaction followed pseudo-first-
order kinetics for epoxidation of cis-cyclooctene (R2 = 0.998).
The rate constant k was determined to be 0.6939 h−1 based
onthe equations (1) and (2). The epoxidation of cis-cyclooctene
could be completed with a conversion of 97% in 4 h. It can be
seen that the compound 1 afforded a high TOF of 485 h–1 in
the epoxidation of cis-cyclooctene, which was higher than
previously reported arsenotungstate-based catalysts, such as
The epoxidation of olefins is one of processes in industrial and
synthetic chemistry.28 According to the previous reports, POMs
as catalysts displayed great catalytic performances in the
epoxidation of olefins,29 hence, compound 1 was employed as
a homogeneous catalyst towards the epoxidation of cis-
cyclooctene in the presence of 30% H2O2. The blank
experiment confirmed that the reaction proceeded sluggishly
without 1. The catalytic activities of [As2W19O67(H2O)]14−
,
H2pzdc, PrCl3·6H2O and simple physical mixtures of theirs for
the epoxidation of cis-cyclooctene were also investigated, all
showed inferior conversions. These results showed PrCl3·6H2O
had a slight effect on activity, and polyanions played maior
role in this transformation. Therefore, we speculated that the
polyanion have transformed into the active peroxotungstates
in the reaction process.15, 1c Importantly, H2pzdc can promote
the formation of catalytically active substances, thereby
exhibiting high catalytic activities for catalytic reactions (Table
S5).15a
[(MnIIOH2)2MnII (As2W15O56)2]16–
(64.6
h–1)
and
2
[H4{(AsW9O33Zn(H2O)W5O11(N(CH2PO3)3)}2(μ2-O)2]10– (116.3 h–
1) (Table S6).32 Whilst, the conversion and ln(Ct/C0) are plotted
against the reaction time at 35, 45, 55, 65 and 75 °C,
respectively (Fig. S8). The fit of the data revealed that the
In order to further optimize the reaction conditions, the
influences of solvent, amount of catalyst, H2O2/substrate ratio
and reaction temperature were investigated. The highest
conversion was achieved in n-butyl alcohol compared with
other solvents. The observed difference can be attributed to
solvation effect and different interactions between cis-
cyclooctene and the solvents (Fig. 3a).30 An increase in the
amount of catalyst from 0.04 to 0.08 mol% improved the
conversion of the reaction by approximately 8% (Fig. 3b). For
effective H2O2 loading, the conversion remarkably improved
Fig. 3 The effect of different factors in the epoxidation of cis-cyclooctene : (a) different solvents; (b) diferent amounts of catalyst;
(c) diferent H2O2/substrate ratios; (d) different temperatures; (e) The kinetic profiles of the epoxidation of cis-cyclooctene under
the optimised condition. Reaction conditions: 1 mmol of cis-cyclooctene, 0.05 mol% of catalyst, 2 mL of n-butyl alcohol, 3 mmol
of 30% H2O2, 65 °C, 4 h. Top right corner : schematic diagram of the catalytic epoxidation of cis-cyclooctene.
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catalytic reaction also followed pseudo-first-order kinetics at efficiently converted to the corresponding epoxide with 97%
different temperatures. The calculated activation energy (Ea) conversion and 51% selectivity (entry 7). As for the
using the Arrhenius equation (3) for the epoxidation of cis- epoxidation of linear terminal alkenes, the reaction of 1-
cyclooctene was 52.54 kJ·mol−1.
octene resulted in approximately 76% conversion and 54%
Sequentially, various olefins were tested to examine the selectivity (entry 8), and the corresponding by-product was
substrate scope of the present catalyst. As shown in Table 1, a confirmed (Fig. S11). With respect to linear internal alkenes,
conversion of between 74% and 100% was obtained in the cis-2-octene afforded approximately 72% conversion and 89%
epoxidation of cyclic olefins and aromatic olefins (entries 1−6). selectivity (entry 9).
Specifically, the epoxidation of cyclic olefins afforded 100%
Oxidation of alcohols
and 87% conversion, respectively (entries 1 and 2). However,
their selectivities were relatively low due to the production of
other by-products, such as cyclohexenone, 1-methyl-
cyclohexanediol (Fig. S9). Furthermore, the catalyst was also
proven to be effective for the epoxidation of aromatic olefins,
where corresponding aromatic aldehydes and acids were
detected as the main by-products by GC-MS (Fig. S10). The
reaction system resulted in a styrene of 80% conversion and
57% selectivity for 15h (entry 3). However, 2-methylphenylene
exhibited a relatively lower conversion and a higher selectivity
in the same reaction time, for comparison with styrene.
The efficiency of compound 1 was further evaluated in
oxidation of alcohols. To identify the optimised
oxidationconditions of reaction, a catena of solvent, amount of
catalyst and H2O2/substrate ratio were explored carefully (Fig.
S12). After screening the reaction parameters, the optimal
reaction conditions could be determined: 0.2 mol% of catalyst,
1 mmol of 1-phenylethanol, 3 mL of DMF and 1 mmol of 30%
H2O2 at 65 °C for 1 h. In the meantime, we also investigated
Nevertheless, 4-methylphenylene showed
a
superior
conversion (entries 4 and 5). The 2,3-dimethyl-2-butene was
Table 1 Oxidation of various alkenes catalyzed by 1a
Entry
Substrate Time/h
8
Product
Con. b/% Sel./%
1
100
87
80
84
55
74
97
76
72
32
57
57
52
88
70
51
54
89
2
3
4
5
6
7
8
9
9
15
13
15
12
5
15
6
Fig. 3 (a) The oxidation of 1-phenylethanol by compound 1 at
different temperatures. Reaction conditions: 1 mmol of 1-
phenylethanol, 0.2 mol% of catalyst, 3 mL of DMF, 1 mmol of
30% H2O2, 1 h; (b) The Arrhenius plot for the oxidation of 1-
phenylethanol using compound 1 at 35, 45, 55, 65 and 75 °C.
a Reaction conditions: 1 mmol of substrate, 0.05 mol% of catalyst, 2
mL of n-butyl alcohol, 3 mmol of 30% H2O2, 65 °C, 4 h; b Determined
by GC analyses based on the initial substrate.
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Table 2 Oxidation of various alcohols catalyzed by 1a
Time/h Yieldb/%
0.03 min−1 for 55 °C, 0.05 min−1 for 65 °C and 0.07 min−1
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DOI: 10.1039/C9DT02436K
°C based on the equations (1) and (2), respectively.
Furthermore, Ea was determined based on the Arrhenius
equation (3) in the temperature range of 35–75 °C, and it was
found to be 43.88 kJ·mol−1.
Entry
1
Substrate
Product
12
1
70
93
99
37
88
90
16
98
45
52
50
70
Encouraged by the effciency of compound 1 for the
oxidation of 1-phenylethanol, sequentially, various alcohols
were tested. Most secondary alcohols containing electron-
donating or electron-withdrawing groups all obtained good
yields, whether at the para or meta position. While, the yields
of alcohols whose substituent groups at the ortho position
were very low, presumably because of the steric effect (Table
2, entries 1−8).33 Applying optimum conditions to aliphatic
alcohols, only medium yields were observed (entries 9 and 10).
We also investigated the effect of ring size on the reaction of
cyclic alcohols, a positive relationship between the ring size
and the yield was observed (entries 11 and 12).
2
3
1
4
12
1
5
6
1
Effect of different heteroatoms on catalytic reactions
In order to explore the effect of heteroatoms on catalytic
activity，a comparison of the catalytic activity of isomorphic
K14[P2W19O67(H2O)] (P2W19) and K14[As2W19O67(H2O)] (As2W19)
for the epoxidation of olefins and oxidation of alcohols, and
the results indicated that P2W19 is more active than As2W19
under identical experiment conditions. The reactivities are
strongly dependent on the kinds of heteroatoms.34 Therewith,
some Keggin polyanions H3XW12O40 (X = P, As, Ge and Si) were
also envisaged as the catalysts, the yields of epoxides
decreased in the order of P (65%) > As (25%) >Ge (19%) > Si
(13%) (Table S9).
7
12
1
8
9
4
10
11c
12
4
12
12
Conclusions
In conclusion, a praseodymium (III)-containing arsenotungstate
bridged by pzdc ligands has been successfully synthesized
through a self-assembly process. The compound 1 shows high
efficiency both the epoxidation of olefins and oxidation of
a
Reaction conditions: 1 mmol of substrate,0.2 mol% of catalyst, 3 alcohols using 30% H2O2 as the oxidant. The kinetic profiles
b
mL of DMF, 1 mmol of 30% H2O2, 65 °C,1 h; Determined by GC were studied under the optimised condition. Especially, the
analyses based on the initial substrate; c Reaction conditions for the TOF (10170h−1) for the oxidation of 1-phenylethanol was
entries 11 and 12: same as above, but in 3 mL CH3CN.
higher than previously reported catalysts. Thus,
arsenotungstates have a huge potential in catalytic reaction,
the effect of the reaction time on the oxidation of 1- which needs to be further explored.
phenylethanol by compound 1 (Fig. 4). The yield increased as a
function of the reaction time. When the reaction temperature
reached 65 °C, the yield did not increase anymore. Thus, the
Experimental Section
compound 1 displayed 100% yield for the oxidation of 1-
phenylethanol within 1 h, and the TOF for the oxidation of 1-
phenylethanol reached up to 500 h–1. Simultaneously, the
reaction process was monitored at 75 °C, giving a 33.9% yield
within 1 min. In this case, the TOF (10170 h−1) was higher than
a previously reported catalyst (9690 h−1) by our group (Table
S8). The linear fit of the data revealed that the catalytic
reaction followed pseudo-first-order kinetics at 35, 45, 55, 65
and 75 °C, respectively (Fig. S13). The observed rate constant k
was confirmed to be 0.01 min−1 for 35 °C, 0.02 min−1 for 45 °C,
Material and physical measurements
K14[As2W19O67(H2O)] was synthesized according to the
literature and confirmed by IR spectrum.35 All other chemical
reagents were purchased and used without further
purification. Elemental analyses (C, H and N) were conducted
on a PerkinElmer 2400-II CHNS/O analyzer; K, Li, Pr, As and W
were performed on a PerkinElmer Optima 2000 ICP-OES
spectrometer. IR spectra were recorded on a Bruker-Vertex 70
FT-IR spectrometer using a solid sample pelletized with KBr
pellets in the range of 4000−450 cm–1. Thermogravimetric
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analyses (TGA) was carried out on
a
Mettler−Toledo program using direct methods and refined with the SHELXL
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TGA/SDTA851e thermal analyzer with a heating rate of 10 refinement package using least squares DmOiIn: i1m0.1is0a3t9i/oCn9.DT0In24t3h6eK
°C·min−1 from 25 to 800 °C in flowing nitrogen. Powder X-ray final refinement, all the non-hydrogen atoms were refined
diffraction (PXRD) was obtained on a Bruker AXS D8 Advance anisotropically. All H atoms of the pzdc groups and water
diffractometer instrument with Cu Kα radiation (λ = 1.54056 Å) molecules were directly refined using a riding model. The
in the angular range 2θ = 5°−50° at 293K. Photoluminescence partial lattice water molecules were located by using a Fourier
37
properties were measured on
a
FL980 fluorescence map, and the remaining lattice water molecules were
spectrophotometer. The GC chromatograms data were determined by the result of TGA analyses. Li+ ions were
obtained on a Bruker 450-GC (flame ionization detector).
determined based on the result of elemental analysis. A
summary of the crystal data and structure refinements is listed
in Table 3.
Preparation of K16H15Li7[Pr2(H2O)3(pzdc)As3W29O103]2·38H2O
K14[As2W19O67(H2O)] (0.125 mmol, 0.66 g) was dissolved in 15
mL of water, then H2pzdc (0.375 mmol, 0.198 g), PrCl3·6H2O
Typical procedure for the oxidation reactions
(0.3 mmol, 0.1066 g) and LiCl (2.359 mmol, 0.10 g) were added Epoxidation of olefins: 0.5 μmol of catalyst, 1 mmol of olefin, 2
step by step with stirring at room temperature. After ten mL of n-butyl alcohol and 3 mmol of 30% H2O2 were charged in
minutes, the pH of mixture was adjusted to 4.0 by the addition a reaction tube, the mixture was stirred at 338 K for 4 h. The
of 1 M LiOH solution. Subsequently, the mixture was heated at products of the reaction were monitored by GC-FID and
60 °C for 1 h, and then the clear filtrate was kept at ambient identified by GC-MS.
temperature. The green stick crystals were isolated after two
Oxidation of alcohols: 2 μmol of catalyst, 1 mmol of alcohol,
weeks. Yield: 0.81 g (64.80% based on Pr). Anal.calcd (%) for 3 mL of DMF (CH3CN) and 1 mmol of 30% H2O2 were charged
C12H107As6K16N4O258Pr4W58Li7: C, 0.79; H, 0.72; N, 0.42; K, 3.60; in a reaction tube, the mixture was stirred at 338 K for 1 h. The
Li, 0.30; As, 2.65; Pr, 3.53; W, 63.37. Found: C, 0.86; H, 0.64; N, products of the reaction were monitored by GC-FID and
0.33; K, 3.73; Li, 0.29; As, 2.68; Pr, 3.36; W, 63.52. FT-IR (KBr, identified by GC-MS.
cm–1): 3400(br), 1625(m), 1451(m), 1399(m), 1365(w), 946(s),
862(s), 793(s), 716(s).
Conflicts of interest
There are no conflicts to declare.
X-ray crystallography
A suitable sample of 1 was selected and sealed in a capillary.
The X-ray data were collected on a Bruker Apex II CCD
Acknowledgements
diffractometer with
a graphite-monochromator Mo Kα
radiation (λ = 0.71073 Å) as the source of radiation at 296(2) K.
Intensity data were corrected for Lorentz and polarization
effects as well as for multi-scan absorption. Using Olex2,36 the
structure was solved with the SHELXS-1997 structure solution
We gratefully acknowledge financial support from the National
Natural Science Foundation of China (Grants 21571050,
21573056, 21771053 and 21771054), Natural Science
Foundation of Henan Province (Grants 132300410144 and
162300410015).
Table 3 Crystallographic data for 1
1
Empirical formula
Formula weight
Crystal system
Space group
Temperature/K
a [Å]
b (Å)
c [Å]
α (deg)
β(deg)
C12H4As6K16N4O251Pr4W58
16522.25
Triclinic
P-1
296.15
19.538(5)
21.762(6)
23.710(6)
101.789(5)
104.044(4)
114.608(4)
8265(4)
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The catalytic properties and polyanionic structure of the pyrazine dicarboxylate-bridged
arsenotungstate