Catalytic properties of heteropoly compounds in 1,3-butadiene oxidation with hydrogen peroxide

Article abstract of DOI:10.1134/S0023158413040071

The homogeneous oxidation of 1,3-butadiene (BD) in H₂O ₂-HPC-CH₃CN (HPC = heteropoly compound) solutions has been investigated. The route of the reaction depends on the nature of the metal capable of coordinating with active oxygen in the HPC. The products of radical BD oxidation (acrolein, 3-butene-1,2-diol, 2-butene-1,4-diol, furan) form in the presence of H_3+n PMo_{12 - n} V _n O₄₀ (n = 1, 2) acids. 3,4-Epoxy-1-butene (EB) and acrolein + furan, which form in equal amounts in the presence of the (n-Bu₄N)₅PW ₁₁O₃₉Fe(OH) salt, result, respectively, from the electrophilic addition of hydrogen peroxide to BD and from radical BD oxidation on iron-oxygen complexes in the HPC composition. The reaction carried out in the presence of (n-Bu₄N)₃{PO₄[WO(O ₂)₂]₄}, (n-Bu₄N)₅Na _0.6H_1.4PW₁₁O₃₉, or (EMIm) ₅NaHPW₁₁O₃₉ yields EB with high selectivity on the reacted BD basis (up to 97%) and H₂O₂ (about 100%). The formation and conversion of the phosphotungstate peroxo complexes PW _n O _m ^α- (n = 2, 3, 4) that are active in BD epoxidation have been investigated by ³¹PNMR spectroscopy. The role of the tetrabutylammonium and ethylmethylimidazolium cations in the formation of these complexes has been demonstrated.

Full text of DOI:10.1134/S0023158413040071

ISSN 0023ꢀ1584, Kinetics and Catalysis, 2013, Vol. 54, No. 4, pp. 420–430. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © L.I. Kuznetsova, N.I. Kuznetsova, R.I. Maksimovskaya, O.S. Koshcheeva, V.A. Utkin, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 4,
pp. 442–452.
Catalytic Properties of Heteropoly Compounds
in 1,3ꢀButadiene Oxidation with Hydrogen Peroxide
L. I. Kuznetsova *, N. I. Kuznetsova , R. I. Maksimovskaya , O. S. Koshcheeva , and V. A. Utkin
Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630090 Russia
a,
a
a
b
a
a
b
*
eꢀmail: livkuzn@catalysis.nsk.su
Received August 16, 2012
Abstract—The homogeneous oxidation of 1,3ꢀbutadiene (BD) in H O –HPC–CH CN (HPC = heteropoly
2
2
3
compound) solutions has been investigated. The route of the reaction depends on the nature of the metal capable
of coordinating with active oxygen in the HPC. The products of radical BD oxidation (acrolein, 3ꢀbuteneꢀ1,2ꢀ
diol, 2ꢀbuteneꢀ1,4ꢀdiol, furan) form in the presence of H3 + nPMo12 – nVnO40 = 1, 2) acids. 3,4ꢀEpoxyꢀ1ꢀbutene
EB) and acrolein + furan, which form in equal amounts in the presence of the ꢀBu N) PW O Fe(OH) salt,
result, respectively, from the electrophilic addition of hydrogen peroxide to BD and from radical BD oxidation on
iron–oxygen complexes in the HPC composition. The reaction carried out in the presence of
Bu N) {PO [WO(O ) ] }, ( ꢀBu N) Na H PW O39, or (EMIm) NaHPW O yields EB with high selectivꢀ
(n
(
(n
4
5
11 39
(nꢀ
n
4
3
4
2 2 4
4
5
0.6 1.4
11
5
11 39
ity on the reacted BD basis (up to 97%) and H O (about 100%). The formation and conversion of the phosphoꢀ
2
2
α−
tungstate peroxo complexes PW O
P NMR spectroscopy. The role of the tetrabutylammonium and ethylmethylimidazolium cations in the formaꢀ
(n = 2, 3, 4) that are active in BD epoxidation have been investigated by
n
m
31
tion of these complexes has been demonstrated.
DOI: 10.1134/S0023158413040071
The presentꢀday common tendency to saving natꢀ of Н О2 (and, accordingly, water) and a low reaction
2
ural resources shifts researchers’ interest to liquidꢀ temperature with various solvents [3, 4]. Like oxidaꢀ
phase catalytic oxidations, for these reactions occur at tions with hydrogen peroxide on V(V), Fe(III),
low temperatures and waste smaller amounts of subꢀ Cr(III), and Ti(IV) complexes [16–19], the same
strate on the formation of deep oxidation products. In reactions over supported P–Mo(VI)–W(VI)–HPCs
[
20] take place in the presence of acid sites and may be
one of the most common types of liquidꢀphase oxidaꢀ
tion systems [1–3], the catalyst is a heteropoly comꢀ
pound (HPC) and the stoichiometric oxidizer is 30%
aqueous hydrogen peroxide. The latter is active under
mild conditions, inexpensive, and convenient to hanꢀ
accompanied by the cleavage of the C=C bond and the
formation of the corresponding aldehydes and acids.
The liquidꢀphase oxidation of 1,3ꢀbutadiene and
other conjugated dienes is poorly studied, as distinct
dle. In the HPC–H2О2 systems, oxidative oxygen from the gasꢀphase oxidation reactions over oxide catꢀ
addition takes place at C=C bonds to yield an epoxide alysts [21–23] and epoxidation reactions over Ag/
grouping. Olefin epoxidation with Н О is carried out Al O3 [1]. The only exception is the industrialꢀscale
αꢀ
2
2
2
in the presence of various HPCs containing either only synthesis of butenediol diacetate on the Pd–Te/C catꢀ
Mo(VI) or W(VI) ions or, additionally, V(V), Ti(IV), alyst manufactured by Mitsubishi Co. [24]. BD is also
Fe(III), and other transition metal ions [3–14]. The known to be oxidizable in aqueous solutions containꢀ
HPCs are used as soluble heteropoly acids (HPAs) or ing Pd(II) and a strong oxidizer. With CuCl
as the
2
as polyoxometalate (POM) salts with organic cations oxidizer, the reaction yields crotonaldehyde [25];
under the action of a СuCl –HCl–NaCl–NaI soluꢀ
in aqueous organic solutions or in twoꢀphase mixtures.
Catalysis by HPCs is based on the formation of peroxo
complexes. In cyclohexene oxidation, the radical iniꢀ
tiators present in the HPC, such as Fe(III) and Cr(III)
ions, cause cyclohexene oxygenation in the allylic
position along with epoxidation [3, 15]. High epoxidaꢀ
tion selectivity for some other unconjugated olefins
and high selectivity with respect to Н О reacted were
2
tion [26, 27] or a H PMo V O solution [28], BD
9
6
6
40
turns into furan. Information concerning BD epoxiꢀ
dation using hydrogen peroxide is limited to two
publications [29, 30]. The second one provides an
example of BD epoxidation in a solution of the HPC
[
TBA]4[
γ
ꢀSiW O (H O) ].
10 34 2 2
In this work, we studied BD oxidation in Kegginꢀ
2
2
achieved in the presence of disubstituted Fe(III) or type HPC–H2О2 systems, varying the HPC composiꢀ
V(V) silicotungstic HPCs at a very low concentration tion. The catalysts that we examined have different
420

CATALYTIC PROPERTIES OF HETEROPOLY COMPOUNDS
421
redox properties and different capacities to form perꢀ
The
compound
oxo complexes active in epoxidation reactions [31– [(C H )(CH )C H N ] [PW O Fe(OH)] (BMImꢀ
4
9
3
3
3
2 5
11 39
3
9]. We investigated how the BD oxidation route PW Fe) was synthesized in a similar way using
11
depends on the nature of the active metal ions of HPC, Fe(NO3)3 and BMImBF4 solutions.
including V(V), Fe(III), Cu(II), and W(VI). The
For C H N PW O Fe (M = 3446.3) anal. calcd.
%): C, 13.9; H, 2.22; N, 4.06. Found (%): C, 13.6; H,
.25; N, 4.01.
40
76 10
11 40
results of this study enabled us to compare the roles of
radical and peroxide species of oxygen in BD oxidaꢀ
tion.
(
2
The IR spectrum of this compound (in KBr) is
consistent with the reported structure of PW Fe [41]:
11
ν
= ~1090 (w sh), 1063, 959, 886, 804, ~750 (w sh),
EXPERIMENTAL
–1
706 cm .
Chemicals
The synthesis and identification of the salts
The following chemicals were used: Н РМо12О40
Н О (reagent grade, Reakhim), unstabilized ~34%
hydrogen peroxide solution (specialꢀpurity grade, Reaꢀ
⋅
(
(
(
n
ꢀBu N) {PO [WO(O ) ] }
11 39
(TBAꢀPW4),
3
4
ꢀBu N) Na H PW O
3
4
2 2 4
n
n
EMIm) NaHPW O
(
TBAꢀPW11),
and
2
4
5
0.6 1.4
(
EMImꢀPW11
)
were
5
11 39
khim), (C H ) NBr (Reakhim), highꢀpurity CH CN described in our earlier work [42]. The synthesis of
4
9 4
3
III
(
1
brand 0, Kriokhrom), 1,3ꢀbutadiene (Aldrich),
(nꢀBu N) PW O Fe(OH) (TBAꢀPW Fe ) was
ꢀbutylꢀ3ꢀmethylimidazolium tetrafluoroborate (Aldꢀ described in [15].
4 5 11 39 11
rich), and 1ꢀbutylꢀ3ꢀmethylimidazolium hexafluoroꢀ
phosphate (Aldrich).
1,3ꢀButadiene Oxidation
The oxidation of BD with hydrogen peroxide was
Preparation of Heteropoly Compounds
investigated under static conditions at atmospheric
pressure in the temperature range from 20 to 60
The commercial heteropoly acid Н РМо12О40
⋅
3
°С.
1
4Н О (Н РМо12) was purified by extraction with
2 3
The reaction solution usually contained 2 mL of
ether; Н РМо VО
⋅
13Н О (Н РМо V
)
and
4
Н РМо V О
11
40
2
4
11
CH CN (in some cases, a mixture of CH CN and an
3
3
⋅
9Н О (Н РМо V2) were obtained via a
5
10
2
40
2
5
10
imidazolium salt), 10–20 mg of an HPC (~5 mol),
µ
standard procedure [40].
and 0.1–0.2 mL of ~34% aqueous Н О2 (1–2 mmol).
2
To
synthesize A HPC sample and a solution of hydrogen peroxide in
[
(C H )(CH )C H N ] [PW O Cu(H O)] (EMImꢀ acetonitrile were placed in a temperatureꢀcontrolled
2 5 3 3 3 2 5 11 39 2
PW Cu)
, aqueous solutions of equimolar amounts of 28ꢀmL Pyrex reactor fitted with two Teflon stopcocks
11
–
4
and a magnetic stirrer. The reactor was purged with
BD and sealed, and the stirrer was turned on. For meaꢀ
suring the volume of gas taken up, the reactor was conꢀ
nected via one of the stopcocks with an argonꢀfilled
measuring burette containing a sealing liquid. The
Na [PW O ] (pH 4.0, 2.5 mL, 5.8
×
10 mol) and
7
11 39
Сu(NO3)2 were mixed and an EMImBr solution
10 mol) was then added. The resultꢀ
ing precipitate was washed with water until it tested
negative for Br– and contained no NO3 ions (as was second stopcock served as the sampler for GC analysis
–3
(
0.6 mL, 2.9
×
−
–1
checked by measuring absorbance at
ν
−
= 1384 cm ) of the solution during the reaction.
NO3
and was then dried at 60
°
С
.
The catalytic activity of the HPCs in Н О2 decomꢀ
position in an argon atmosphere was estimated as the
amount of gas (О2) released.
2
For C H N PW O Cu (M = 3314.7) anal. calcd.
30
57 10
11 40
(
%): C, 10.86; H, 1.73; N, 4.22. Found (%): C, 10.7;
H, 1.80; N, 4.18.
Reaction solutions were analyzed on a Kristall
2
000 M chromatograph with a flameꢀionization
The IR spectrum of this compound (in KBr) was
consistent with the structure of the metalꢀsubstituted
TM
detector and an SPB –1000 capillary column
0.53 mm 30 m) in a temperatureꢀprogrammed
(
×
polyoxometalate ion PW Cu [41]:
ν
= 1100, 1058
11
mode. The furan, acrolein, 3,4ꢀepoxyꢀ1ꢀbutene,
3ꢀbuteneꢀ1,2ꢀdiol, and 2ꢀbuteneꢀ1,4ꢀdiol yields were
determined using the corresponding calibration relaꢀ
tionships. Reaction products were identified by the
GCꢀMS method. The hydrogen peroxide concentraꢀ
tion was determined iodometrically by adding 0.1 mL
of the reaction solution to 5 mL of acetic acid and 0.5 g
of potassium iodide. The mixture was left standing for
(
P–O), 952 (W=O), 884, 811, 742, 696 (W–O–W,
–1
W–O–Cu) cm .
The
compound
BMImꢀ
was synthesized in the same way, but
BMImBF4 was used as the precipitant.
For C H N PW O Cu (M = 3455.0) anal. calcd.
[
(C H )(CH )C H N ] [PW O Cu(H O)]
(
4
9
3
3
3
2 5
11 39
2
PW Cu
)
1
1
40
77 10
11 40
(
%): C, 13.9; H, 2.24; N, 4.05. Found (%): C, 13.8;
10 min, 50 mL of water was then added, and the resultꢀ
H, 2.23; N, 4.01.
ing solution was titrated with a 0.04 N thiosulfate soluꢀ
= 1100, 1060, 954, 883, 806, tion. The organic peroxide content of the reaction
products was determined in the same way, but the mixꢀ
IR spectrum (KBr):
42, 695 cm .
ν
–1
7
KINETICS AND CATALYSIS Vol. 54
No. 4
2013

422
KUZNETSOVA et al.
Table 1. Yield of the products of 1,3ꢀbutadiene oxidation with hydrogen peroxide in the presence of phosphomolybdovaꢀ
nadic HPAs
Crotonaldeꢀ
Fur
Acr
1,2ꢀdiol 1,2ꢀox 1,4ꢀdiol 1,4ꢀox S1,4, %
mol
Temperature,
hyde
Entry
HPA
°
C
µ
1
2
3
4
5
50
20
40
50
50
H PMo O
0.15
0.86
0
~0
3.7
5.1
12
0.13
0.90
0
0
0.22
1.2
27
19
14
20
19
3
12 40
H PMo VO
0.73 12
0
1.1
7.5
4
11
40
40
40
H PMo VO
30
238
282
99
59
3.5
3.3
3.0
13
4
11
H PMo VO
59
23
42
17
15
5.0
8.4
3.3
4
11
H PMo V O
10 2 40
5
Reaction conditions: HPA, 20 mg (~10
h.
μ
mol); CH CN, 2 mL; ~34% aqueous H O , 0.2 mL (2 mmol); BD atmosphere; reaction time,
3
2 2
2
ture to be analyzed was kept for 1 h at 60
gen atmosphere.
°
С
in a nitroꢀ of the catalysts with respect to the formation of BD
1,4ꢀoxygenation products (furan, 2ꢀbuteneꢀ1,4ꢀdiol,
and 1,4ꢀoxo products of its oxidation) was about 20%
relative to the total amount of GCꢀdetectable prodꢀ
ucts and varied slightly from one HPA to another
RESULTS AND DISCUSSION
(
Table 1). Figure 1 illustrates the kinetics of accumuꢀ
1
,3ꢀButadiene Oxidation Catalyzed
lation of BD oxidation products in the presence of
Н РМо VО40. After 1 h, the formation of acrolein
slowed down markedly, which was due to the high
conversion of Н О2 (curves ). The amounts of 1,2ꢀ
and 1,4ꢀdiols began to decrease (curves ) because
of the further oxidation of these compounds. Selectivꢀ
ity in terms of Н О2 consumed in product formation in
the presence of H PMo VO was ~40%. The low
yield of the products per unit amount of hydrogen perꢀ
oxide reacted is typical of the P–Mo–V–HPC cataꢀ
lyzed oxidation of other hydrocarbons as well, because
the oxidation process is accompanied by Н О2 decomꢀ
position [31, 32].
by H3 + nPMo12 – nVnO40 (n = 0, 1, 2) Heteropoly Acids
4
11
Phosphovanadomolybdic HPAs are oxidizers
capable of generating radical oxygen species in the
presence of Н О2. An adequately studied process is the
oxidation of alkylaromatic compounds in HPA–H2О2
systems [4, 31, 32, 43]. We investigated BD oxidation
with hydrogen peroxide catalyzed by P–Mo–V–HPAs
in CH CN solution. The BD oxidation products were
furan, (Fur), acrolein (Acr), 3ꢀbuteneꢀ1,2ꢀdiol
1,2ꢀdiol), and 2ꢀbuteneꢀ1,4ꢀdiol (1,4ꢀdiol). Small
amounts of crotonaldehyde, methyl vinyl ketone,
acrylic acid, 4ꢀvinylꢀ1ꢀcyclohexene, 3ꢀcyclohexeneꢀ
1, 2
2
2
4, 5
2
4
11
40
3
(
2
1
ꢀcarboxaldehyde, and, possibly, furanone were also
Monoolefin oxidation catalyzed by vanadium(V)
compounds is believed to be due to the action of the
radical species
detected. The diols could undergo further oxidation
into 1,2ꢀox and 1,4ꢀox products, which, according to
GCꢀMS data, included aldoalcohols + ketoalcohol
(m/е 86) and dialdehyde + ketoaldehyde (m/е 84).
O
Iodometric titration demonstrated that there were no
peroxide compounds of BD [44] in the solution after
the reaction.
VIV
O
,
which forms on vanadium ions [16]. It was observed
In the presence of Н РМо О at 50 С, the yield [16] that oxidation by vanadium(V) picolinate peroxo
°
3
12 40
of BD oxidation products was low (Table 1, entry 1). complexes in CH CN is accompanied by the decomꢀ
3
In the reaction catalyzed by the V(V)ꢀcontaining acid position of peroxide groups with O2 evolution. The
H PMo VO40, the yield of the products detectable by oxidation process yielded products of monoolefin
4
11
GC was significantly higher (Table 1, entries 2–4). cleavage at the double bond and smaller amounts of
The amount of products increased with an increasing epoxides. It was hypothesized that the epoxides were
temperature owing to the increasing rate of Н О2 primary products and underwent further oxidation.
2
decomposition catalyzed by H PMo VO40. In the The conversion of the olefins into epoxides followed
4
11
presence of Н РМо V О [45], which is a stronger by the hydrolysis and oxidative cleavage of the latter,
5
10
2
40
oxidizer than Н РМо VO40, the product yield was which can give diols as intermediates, was also considꢀ
4
11
lower (Table 1, entry 5), apparently because the prodꢀ ered in the investigation of reactions on acid catalysts
ucts underwent further oxidation. The selectivity S1,4 containing Cr–HPC or P–Mo–W–HPC [18, 20],
KINETICS AND CATALYSIS Vol. 54
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2013

CATALYTIC PROPERTIES OF HETEROPOLY COMPOUNDS
423
even though no diols were identified among the
2
1
monoolefin oxidation products [17–20]. At the same
time, an alternative mechanism was suggested for the
radical cleavage of the double bond of the olefin in an
iron salen complex; in this mechanism, O /H O or Н О2
2
2
2
molecules are involved in the catalytic cycle [17].
A specific feature of BD oxidation by hydrogen perꢀ
oxide in the presence of a P–V–Mo–HPC is the formaꢀ
tion of 1,2ꢀ and 1,4ꢀaddition products, including diols,
although no significant amounts of epoxide are detected.
The data available on this reaction suggest that BD oxiꢀ
dizes under the action of radical oxygen species coordiꢀ
nated to vanadium via the formation of EB as the primary
product. EB is rapidly hydrated on strong Brønsted acid
sites of the HPC, turning into 1,2ꢀ and 1,4ꢀdiols [46].
The subsequent oxidative conversions of the diols in the
HPC–H2О2 system yield the complete set of products, as
is shown in Scheme 1.
1
.0
.5
0
100
0
50
3
4
1
,3ꢀButadiene oxidation with H O catalyzed
5
2
2
6
by P–Mo–V–HPC
0
1
2
3
H O
2
H O
2
2
Time, h
Fig. 1.
(
1
) Hydrogen peroxide conversion and (
2
–
6
)
amounts of 1,3ꢀbutadiene oxidation products versus reacꢀ
O
tion time: (
(5) 2ꢀbuteneꢀ1,4ꢀdiol, and (6
conditions: H PMo VО
2
) acrolein, (
3
) furan, (
) crotonaldehyde. Reaction
13Н О, 20 mg (10 mol);
4) 3ꢀbuteneꢀ1,2ꢀdiol,
V
VIV
(
HPA) V = O
O
C C C C
⋅
µ
4
11
40
2
~34% aqueous H O , 0.2 mL (2 mmol); CH CN, 2 mL;
2
2
°
3
BD atmosphere; 50 C.
C C C C
O
О , mL
2
20
1
1
1
1
1
1
8
6
4
2
0
8
6
4
2
HPA, H O
2
2
2
3
1
,2ꢀdiol, 1,4ꢀdiol,
1,4ꢀox,
Fur
1,2ꢀox,
Acr
Scheme 1.
4
Interaction between 1,3ꢀButadiene and H O2
in the Presence of Imidazolium Salts of Cu(II)ꢀ
and Fe(III)ꢀSubstituted Phosphotungstate Anions
2
0
20
40 60 80 100 120 140 160 180 200
Time, min
Metalꢀsubstituted phosphotungstates in CH CN
3
solution differ in terms of the properties they show in the
catalytic decomposition of hydrogen peroxide and
hydrocarbon substrate oxidation and in the formation of
intermediate peroxide complexes [15, 47, 48]. We studꢀ
ied the conversions of Н О and BD in solutions of the
Fig. 2. Volume of oxygen released due to H O decompoꢀ
2
2
sition in the presence of (
and ( (BMIm) [PW O Cu(H O)] in the solvents
) CH CN, (
1) (EMIm) [PW O Cu(H O)]
5 11 39 2
2
2–4)
5
11 39
(
1
,
2
3) CH CN + 60 wt % BMImBF , and (4)
3
4
3 4
BMImBF . Reaction conditions: solvent volume, 2 mL;
2
2
amount of catalyst, 19 mg (5.5
H O , 0.2 mL (1.5 mmol); 50 C.
µ
mol); ~34% aqueous
following ethylmethylimidazolium and butylmethylimiꢀ
dazolium salts: (EMIm) [PW O Cu(H O)],
BMIm) [PW O Cu(H O)]
°
2
2
5
11 39
2
(
,
and
5
11 39
11 39
2
sition with О2 evolution (Fig. 2, curves
1, 2). This proꢀ
(BMIm) [PW O Fe(OH)]. The imidazolium salts of
5
5
–
the [PW O Cu(H O)] anion in CH CN solution, cess likely occurs without the formation of intermediꢀ
11
39
2
3
like the TBA salts [15], catalyze rapid Н О decompoꢀ ate oxygen complexes. Replacing part of the solvent
2
2
KINETICS AND CATALYSIS Vol. 54
No. 4
2013

424
KUZNETSOVA et al.
with BMImBF4 inhibits Н О2 decomposition (Fig. 3,
Products, mmol
(а)
2
curves
3
,
4
). Apparently, the imidazolium cation interꢀ
0
.5
.4
.3
.2
.1
•
acts rapidly with the ОН radical [49]. In the presence
of (BMIm) [PW O Fe(OH)], no H O decomposiꢀ
5
11 39
2
2
0
0
0
0
tion occurred in both CH CN and a CH CN +
3 3
BMImBF4 mixture, for there was no oxygen evolution.
In the experiments involving BD, Н О2, and the
1
2
5–
salts of the [PW O Cu(H O)] anion, the oxidation
11
39
2
products furan, acrolein, and EB formed only in trace
amounts both in acetonitrile alone and in the acetoniꢀ
trile + BMImBF4 or acetonitrile + BMImPF6 mixꢀ
ture. Hydrogen peroxide in this case was consumed
almost entirely (Table 2, entries 1–4) via its decompoꢀ
sition and, possibly, other side reactions. When BD
and (BMIm) [PW O Fe(OH)] were present in
2
5
11 39
0
50
100
100
100
150
(b)
200
200
200
250
250
250
300
, min
CH CN, the Н О2 conversion was low (Table 2,
3
2
τ
entries 5, 6), and so was the amount of the resulting
products. In entry 6, a small amount of 1ꢀbutylꢀ3ꢀ
methylꢀ2,4,5ꢀtrioxoimidazolidine, an oxidation prodꢀ
Products, mmol
0.5
0.4
0.3
0.2
0.1
+
uct of the BMIm cation, was detected by GCꢀMS.
5–
The activity of the TBA salt of the [PW O Fe(OH)]
11 39
anion in the hydrogen peroxide oxidation reactions is
known to be due to the formation of an intermediate
iron peroxo complex in the polyoxometalate anion; this
–1
complex absorbs visible light in the 18000–26000 cm
1
2
range [15, 47]. We ascertained that, with the BMIm salt,
this “red” complex does not form in noticeable
amounts under the reaction conditions. This is the
likely reason why there were no BD oxidation products.
Under the same conditions, the TBA salt of the
5–
[
PW O Fe(OH)] anion catalyzed the formation of
11 39
0
50
150
(c)
300
, min
furan, acrolein, and EB (Table 2, entry 7). The
other reaction products, namely, 3ꢀbuteneꢀ1,2ꢀ
diol, 2ꢀbuteneꢀ1,4ꢀdiol, and methyl vinyl ketone,
were in minor amounts. Selectivity in terms of Н О
τ
Products, mmol
0.5
0.4
0.3
0.2
0.1
2
2
1
consumed in the formation of BD oxidation products
was ~70%. No phosphotungstates free of paramagꢀ
netic Fe(III) ions were detected in the Н О2ꢀcontainꢀ
2
ing reaction solution. (Otherwise, they would have
31
shown themselves as narrow P NMR signals in the
chemical shift range from +5 to –15 ppm.) Therefore,
the observed catalytic activity should be attributed to
5–
the [PW O Fe(OH)] anion. Accordingly, the forꢀ
11
39
mation of EB as a product of the electrophilic oxidaꢀ
tion of BD is due to the formation and fairly high staꢀ
bility of the Fe(III) peroxo complex in the HPC
2
(
Scheme 2). The rate of the hydration of the resulting
EB into diols in the presence of the neutral salt
ТBА) [PW O Fe(OH)] was substantially lower than
0
50
150
300
Time, min
(
5
11 39
in the presence of the H3 + nPMo12 – nVnO40 acids [46];
as a consequence, EB accumulated during the reacꢀ
tion up to ~50% of the total amount of BD oxidation
products. The oxidation of BD into acrolein and furan
possibly includes preliminary EB hydration steps
yielding 1,2ꢀ and 1,4ꢀdiols. Next, the vicꢀdiol underꢀ
goes oxidative cleavage [50] to yield acrolein, and 1,4ꢀ
diol undergoes oxidative cyclization into furan. These
Fig. 3. Amounts of the resulting (
) acrolein as a function of reaction time in the presence of
phosphotungstates: (a) TBAꢀPW4 (10 mg, 5.3 mol),
mol), and (c) EMImꢀPW11
mol). Reaction conditions: ~34% aqueous
1) 3,4ꢀepoxyꢀ1ꢀbutene and
(2
µ
(
(
b) TBAꢀPW11 (20 mg, 5.1
17 mg, 5.0
µ
µ
H O , 0.2 mL (1.9 mmol); CH CN, 2 mL; BD, 26 mL
2
2
3
(
1 mmol); 50 C.
°
KINETICS AND CATALYSIS Vol. 54
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2013

CATALYTIC PROPERTIES OF HETEROPOLY COMPOUNDS
425
Table 2. Yield of the products of 1,3ꢀbutadiene oxidation with hydrogen peroxide in the presence of salts of metalꢀsubstiꢀ
tuted phosphotunstate anions
Product yield,
µ
mol
H O
conversion
2
2
Entry
Catalyst
Solvent
Time, h
Fur
Acr
EB
1
2
3
4
5
EMImꢀPW Cu CH CN
0.5
0.5
3
0
0.4
0.4
10.6
2.3
5.1
4.6
17
0.2
0.4
0
97
98
62
70
8
11
3
BMImꢀPW Cu CH CN
0
11
3
BMImꢀPW Cu CH CN + 60 wt % BMImBF
0.7
0
11
3
4
BMImꢀPW Cu CH CN + 34 wt % BMImPF
1.5
3
0.9
1.3
0.7
11
3
6
BMImꢀPW Fe CH CN
0.4
1.8
1.26
11
3
6*
BMImꢀPW Fe CH CN + 60 wt % BMImBF
3
3
11
3
4
7
TBAꢀPW Fe
CH CN
3
18
9
1
1
3
Note: Reaction conditions: solvent, 2 mL; catalyst, 5.5
= 60 C.
μ
mol; ~34% aqueous H O , 0.2 mL (1.66 mmol); BD atmosphere;
T
= 50°C.
2
2
*
T
°
oxidative conversions, like the similar reactions on existence of different active oxygen species in the iron
porphyrin complexes [51], are possible owing to the complexes in HPC (Scheme 2).
1
,3ꢀButadiene oxidation with H O catalyzed by (TBA) [PW O Fe(OH)]
2 2 5 11 39
BD
EB
Acr,
Fur
EB
H O , –H O
2
–OH–
HPC) FeIII (OH)
2
2
(HPC) FeIII
(HPC) FeIV
(HPC) FeV
=O
(
–
OOH
–
O
OH–
Scheme 2.
1
,3ꢀButadiene Oxidation with Hydrogen Peroxide
oxidation products, determined by GC, is close to
90% (Table 3).
Catalyzed by Phosphotungstates
Table 4 presents balance data for BD oxidation into
EB in relation to the HPC composition and catalyst
The oxidation of BD with hydrogen peroxide was
studied in the presence of HPCs weakly accelerating
and Н О2 concentrations. The amount of reacted BD
2
Н О decomposition and forming peroxo complexes
2
2
derived from gas uptake data was close to the amount
active in electrophilic oxygen addition [33–39]. The
following phosphotungstates were synthesized for
of reacted Н О2 in most experiments and, within the
2
measurement error, was consistent with the amount of
the resulting products. In entries 1–7, at a fairly high
this purpose:
(nꢀBu N) {PO [WO(O ) ] } (TBAꢀPW ),
4 3 4 2 2 4 4
(
n
ꢀBu N) Na H PW O
(TBAꢀPW11)
,
and Н О2 concentration in the solution (~1 mol/L), selecꢀ
4
5
0.6 1.4
11 39
2
(
EMIm) NaHPW O (EMImꢀPW ). In this HPC
5
11 39
11
tivity in terms of hydrogen peroxide consumed in BD
formation (SH2O2 ), defined as the ratio of the amount
series, we investigated the effects of the polyoxometaꢀ
late anion and organic cation compositions on cataꢀ
lytic activity [42].
of BD to the amount of Н О2 reacted, varied with catꢀ
2
alyst composition between 60 and 78%. The rest of the
Н О2 apparently decomposed or reacted with the solꢀ
In acetonitrile solutions containing TBAꢀPW4,
TBAꢀPW11, or EMImꢀPW11 and aqueous hydrogen
2
vent [52, 53]. Reducing the Н О2 concentration to
2
peroxide, BD oxidized at 20–60
butene. Acrolein, furan, and diols formed only in trace 100%. In all experiments, a high EB selectivity of
amounts (Table 3). The BDꢀtoꢀEB selectivity (SEB) at
90% was observed, which implied a small proportion
various temperatures and Н О conversions into the of the radical BD oxidation products. In experiment
°
С into 1,2ꢀepoxyꢀ3ꢀ ~0.5 mol/L (entries 8–10) brought SH2O2 close to
≥
2
2
KINETICS AND CATALYSIS Vol. 54
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2013

426
KUZNETSOVA et al.
Table 3. Yield of the products of 1,3ꢀbutadiene oxidation with hydrogen peroxide in the presence of phosphotungstates
Amount of
Product yield, mmol
×
102
H O
2 2
converꢀ
sion, %
Temꢀ Amount of
peraꢀ catalyst,
~
34% H O
S
%
EB
,
SH2O2,
%
2
2
Entry
Catalyst
ture,
°
C
µmol
mL mmol EB Acr Fur 1,2ꢀdiol 1,4ꢀox
1
2
3
4
TBAꢀPW4
20
20
60
60
5.3
5.1
0.2 2.12 5.9 0.6 0.10
0.2 2.12 2.2 0.2 0.05
0.1 0.92 51.2 6.0 0.05
0.1 0.86 64.5 6.2 0.20
0.40
0
0.06
0
83
90
88
91
–
–
–
–
TBAꢀPW11
TBAꢀPW11
EMImꢀPW11
10
10
0.40
0
0.3
0.2
63
84
88
90
Note: Reaction conditions: CH CN, 2 mL; BD atmosphere.
3
Table 4. Effects of the phosphotungstate composition and catalyst and hydrogen peroxide concentrations on butadiene epꢀ
oxidation
H O , mmol
2
2
Amount
of catalyst,
mol
BD reacted,
mmol
Total amount
of products
Entry
Catalyst
SEB, %
S
,
%
H O
2
amount
reacted
2
µ
initial amount
1
2
3
TBAꢀPW4
5.3
1.91
1.91
1.94
1.98
1.93
1.99
2.79
1.01
0.96
1.03
0.72
0.99
0.25
0.12
0.28
0.22
0.16
0.46
0.22
0.13
0.09
0.16
0.36
0.38
0.23
0.09
0.19
0.18
0.10
0.24
0.13
0.14
0.08
0.14
0.46
0.36
0.21
0.09
0.22
0.16
0.10
0.33
0.18
0.15
0.08
0.1
93
93
95
94
86
89
87
90
96
97
98
98d
78
67
TBAꢀPW11
5.1
5.0
2.3
2.6
EMImꢀPW11
75
4a EMImꢀPW11
70
5
6
7
8
9
TBAꢀPW4
TBAꢀPW4
TBAꢀPW4
TBAꢀPW4
TBAꢀPW11
60
11
63
5.3
5.3
5.1
2.3
5.0
71
~90
78
1
1
0a EMImꢀPW11
1a, b EMImꢀPW11
Second cycle
~100
~100
~100d
0.365
0.75c
Note: Reaction conditions: ~34% aqueous H O ; BD, 26 mL (1 mmol); CH CN, 2 mL; 50 C; reaction time, 2 h.
°
2
2
3
a
b
c
d
Reaction time of 5 h.
Reaction conducted in a BD atmosphere.
After two reaction cycles.
Calculated from the amounts of the resulting products and H O consumed in two reactions cycles.
2
2
1
1, after 50% conversion was reached in 5 h, another ence of the HPC. At the same time, the activity of TSꢀ1
reaction cycle was started by adding a new portion of was higher, namely, 193 mol EB per mole of Ti in 1 h
Н О until its total concentration of ~0.5 mol/L and the [29] as against 110 mol EB per mole of ꢀSiW10 in 9 h
γ
2
2
reaction was continued for another 5 h. After the second [30] and 15–90 mol EB per mole of phosphotungstate
cycle, the total amount of products was twice larger and in 2–5 h (Table 4).
SEB and
S
were the same as in the first cycle.
H O
2
2
Figure 3 plots kinetic curves illustrating EB accuꢀ
mulation and the formation of the main byꢀproduct—
acrolein—in the presence of the three phosphotungꢀ
states. At the early stages of the reaction (over ~1 h),
the EB formation rate is higher than its steadyꢀstate
value. According to their steadyꢀstate activity, the catꢀ
alysts can be arranged in the following order:
A similar H O2 consumption selectivity was observed
in BD oxidation on a [TBA]4[ ꢀSiW O (H O) ] cataꢀ
lyst in CH CN at a lower hydrogen peroxide concenꢀ
tration (0.16 mol/L) and [BD] > [H O2] [30]. Note for
2
γ
10 34 2 2
3
2
comparison that, in BD oxidation on the catalyst TSꢀ1
[
29], the BD formation selectivity SH2O2 was only 46%
(TBA) {PO [WO(O ) ] }
≈
(TBA) Na H [PW O ]
<
3
4
2 2 4
5
0.6 1.4
11 39
at [H O2] = 0.23 mol/L, much lower than in the presꢀ (EMIm) NaH[PW O ]
.
2
5
11 39
KINETICS AND CATALYSIS Vol. 54
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2013

CATALYTIC PROPERTIES OF HETEROPOLY COMPOUNDS
427
The variation of the composition of the catalysts
31
during the reaction was monitored by P NMR specꢀ
troscopy. This enabled us to correlate the EB formaꢀ
tion rate with the composition of the peroxo comꢀ
plexes forming in the reaction solutions in the initial
stage and under nearꢀsteadyꢀstate conditions. The
(а)
phosphotungstate peroxo complexes forming in Н О2
2
solutions were identified in earlier works [36–39, 42].
31
The P NMR spectra of the reaction solutions are
presented in Fig. 4. In СН СN containing aqueous
(b)
3
Н О2, TBAꢀPW4 retains its composition (spectrum a).
2
The signal at = 3.5 ppm is due to the peroxo complex
δ
7
−
PW12
{
PO [WO(O ) ] }3–. The PW O anion in TBAꢀPW11
4 2 2 4
11 39
and
EMImꢀPW11
disproportionates
into
3
−
3–
{PO [WO(O ) ] } , PW O (spectra c, e), and polyꢀ
4 2 2 4
12 40
tungstate ions. Under the reaction conditions, TBAꢀ
(c)
(d)
PW4 or TBAꢀPW turns mainly into the peroxo anion
11
2–
{
PO [WO(O ) ] }
4
(δ
= 0.4 ppm; spectra b, d). In the
2 2 2
case of EMImꢀPW11, a large proportion of the
3–
{
PO [WO(O ) ] } complex persists and the peroxo
4 2 2 4
α−
complex PW O is present (δ ≈ 2 ppm; spectra f, g).
3
m
At the early stages of the reaction (within 1 h), the
amount of EB forming on each of the three catalysts
correlates with the concentration of the peroxo anion
3–
{
PO [WO(O ) ] } that has resulted from the reaction
(e)
4
2 2 4
between the initial HPC and Н О2. It was demonꢀ
2
strated in our earlier work [42] that, even if the peroxꢀ
2–
otungstate anion [W O (O ) (H O) ] actually forms
2
3
2 4
2
2
(
f)
via phosphotungstate disproportionation [36], it is
much less active toward BD. The peroxo anion
2–
{
PO [WO(O ) ] } synthesized as was described by
4 2 2 2
Salles et al. [37] turned out to be three times less active
3–
(g)
than {PO [WO(O ) ] } . This is consistent with the
4
2 2 4
fact that the activity of TBAꢀPW4 in the steady state is
lower by a factor of about 3. The steadyꢀstate activity
of TBAꢀPW11 per unit concentration of
PW4
PW2
PW3
2–
{
PO [WO(O ) ] } was two times higher than that of
4 2 2 2
(h)
TBAꢀPW4. This suggests that, under catalytic condiꢀ
tions, tungstate ions are favorable for regeneration of
3–
0
–5
, ppm
–10
–15
the more active peroxo anion {PO [WO(O ) ] }
,
4
2 2 4
which is rapidly consumed (Scheme 3). EMImꢀPW11
shows a higher steadyꢀstate activity because it generꢀ
δ
ates larger amounts of the peroxo anion
α−
3–
{
PO [WO(O ) ] } and, apparently, PW O .
4 2 2 4
3 m
The data listed in Table 5, obtained for the reaction
catalyzed by EMImꢀPW11, illustrate the effect of imiꢀ
dazolium salts on BD oxidation with hydrogen peroxꢀ
Fig. 4. 31P NMR spectra: (a) TBAꢀPW (10 mmol/L) in
4
the absence of BD, (b) TBAꢀPW 2 h after the addition of
4
BD, (c) TBAꢀPW11 (2.3 mmol/L) in the absence of BD,
(
d) TBAꢀPW 2 h after the addition of BD, (e) EMImꢀPW
ide. As the EMImBF concentration was increased
11 11
4
(2.3 mmol/L) in the absence of BD, (f) EMImꢀPW 2 h after
11
from 1.5 to 20%, the amount of the resulting EB
decreased (entries 2, 3), while a high EB yield was
attained in the presence of BMImPF6 (entry 4). This
distinction can be explained by the transformation of
the catalyst in the reaction solution, as was done for
the (BMIm) PW O salt, which is inactive in the
the addition of BD, (g) the same 3.5 h after the addition of
BD, and (h) TBAꢀPW solution (10 mmol/L) after proꢀ
4
longed storage [42] (this spectrum is presented for compariꢀ
son and indicates the presence of all of the three identified
peroxo complexes). Reaction conditions: [H O ] =
2
2
1
mol/L; CH CN : ~34% aqueous H O = 10 : 1 (vol/vol);
3 2 2
3
12 40
reaction temperature of (a, h) 25 and (b–g) 50°C.
KINETICS AND CATALYSIS Vol. 54
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2013

428
KUZNETSOVA et al.
Table 5. Effects of EMImBF4 and EMImPF6 admixtures on the yield of the products of butadiene oxidation with hydrogen
peroxide in the presence of EMImꢀPW11
Fur
Acr
EB
mmol
1,2ꢀdiol 1,4ꢀdiol
Admixture
concentration, wt %
Entry Admixture
,
SEB, % SH2O2 %
×
102
1
2
3
4
*
EMImBF4
EMImBF4
EMImBF4
EMImPF6
0
1.5
20
20
0.08
0.08
0.04
0.12
0.68
0.44
0.22
0.26
15.4
8.2
0.05
0.1
0
94
94
94
97
70
0
0
0
–
3.8
0
96
13.2
0
~100
Note: Reaction conditions: catalyst, 2.3
1 mmol); 50 C; reaction time, 2 h.
Reaction time of 5 h.
µ
mol; (CH CN + EMImX), ~2 mL; ~34% aqueous H O , 0.2 mL (1.8 mmol); BD, 26 mL
3 2 2
(
°
*
absence of BMImPF [8]. We demonstrated that, Н О2 solution does not decelerate the process, and the
6
2
3
40
−
EB formation rate remains high. As is clear from the
data presented in Table 5, the favorable effect of
BMImPF6 consists in the enhancement of EB selecꢀ
tivity (SEB) from 94 to 97% via hampering the radical
side processes. A particularly pronounced increase in
unlike the salt of the PW O anion, the salts of the
1
2
7
−
PW O anion in CH CN + aqueous Н О solution
1
1
39
3
2
2
rapidly generate catalytically active peroxo complexes.
Because the participation of water molecules is necesꢀ
sary for the transformation of the phosphotungstate
anions, the replacement of CH CN in this solution
with hydrophilic BMImBF4 strongly slows down perꢀ
EB selectivity on the Н О2 basis (up to ~100%) relaꢀ
2
3
tive to the selectivity observed for the pure solvent is
achieved by replacing 20% of the CН CN with an imiꢀ
oxo complex formation (according to NMR data),
causing a decrease in the EB formation rate. Addition dazolium salt (entries (1, 3, 4) at the equally high Н О
3
2
2
of hydrophobic BMImPF6 to the CH CN + aqueous concentration (~1 mol/L).
3
Transformations of the TBAꢀPW catalyst (
1
) in a CH CN solution containing aqueous H O
11
3
2
2
and (2,
3) in the BD epoxidation reaction (
2) at its early stages and (3) in the steady state
1
2
3
BD
EB
EB
BD
H O
2
2
6
–
[
HPW O ]
11 39
3–
2–
{
PO [WO(O ) ] }
4
[PW4]
[PW2]
{HPO [WO(O ) ] }
4 2 2 2
2 2 4
5
–
[
H PW O ]
11 39
2
H O
2
H O
2 2
2
WO , [PW12O40]3–, H O
x
2
Scheme 3.
CONCLUSIONS
The acid H PMo VO can form radical species
4 11 40
coordinated to the vanadium ion that are active both in
Н О2 decomposition and in radical BD oxidation
yielding acrolein, furan, and 1,2ꢀ and 1,4ꢀdiols. The
The catalytic properties of the HPCs in BD oxidaꢀ
tion with hydrogen peroxide depend on the nature of
their active metal ion—V(V), Fe(III), or W(VI). In
acetonitrile + aqueous Н О solution, there is a correꢀ
2
selectivity of the catalysts in terms of Н О2 consumed
2
2
2
in the formation of oxidation products is ~40%.
lation between the formation of active oxygen comꢀ
plexes in the catalytic system, the Н О decomposiꢀ
tion rate, and the composition of the BD oxidation sition, which is catalyzed by the [PW O Cu(H O)]
The free radicals resulting from rapid Н О2 decompoꢀ
2
2
2
5–
11
39
2
products, which include acrolein, furan, 3ꢀbuteneꢀ anion, do not yield selective BD oxidation products.
,2ꢀdiol, 2ꢀbuteneꢀ1,4ꢀdiol, and EB. The salt (TBA) PW O Fe(OH) shows low activity in
1
5
11 39
KINETICS AND CATALYSIS Vol. 54
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2013

CATALYTIC PROPERTIES OF HETEROPOLY COMPOUNDS
429
Н О decomposition and catalyze BD oxidation into 15. Kuznetsova, N.I., Detusheva, L.G., Kuznetsova, L.I.,
2
2
both acrolein (containing furan and 1,2ꢀ and 1,4ꢀdiols)
and EB owing to the formation of active iron–oxygen
Fedotov, M.A., and Likholobov, V.A., Kinet. Catal.,
992, vol. 33, no. 3, p. 415.
1
complexes in the HPC. The selectivity of this catalyst 16. Mimoun, H., Saussine, L., Daire, E., Postel, M.,
in terms of Н О consumed in the formation of oxidaꢀ
tion products has a larger value of ~70%.
Fisher, J., and Weiss, R., J. Am. Chem. Soc., 1983, vol. 105,
no. 10, p. 3101.
2
2
EB forms with high selectivity (SEB of up to 97%, 17. Dhakshinamoorthy, A. and Pitchumani, K., Tetraheꢀ
dron: Asymmetry, 2006, vol. 62, no. 42, p. 9911.
SH2O2 close to 100%) in the presence of phosphotungꢀ
1
8. Saedi, Z., Tangestaninejad, S., Moghadam, M.,
Mirkhani, V., and Mohammadpoor, I., Catal. Comꢀ
mun., 2012, vol. 17, no. 1, p. 18.
9. Adam, W., Corma, A., Martinez, A., and Renz, M.,
Chem. Ber., 1996, vol. 129, no. 12, p. 1453.
0. Brooks, C.D., Huang, L., McCarron, M., and
state anions, which are practically inactive in Н О2
2
decomposition. In this case, the oxidation products
contain only small amounts of acrolein, furan, and
1
2
2
2
2
2
2
31
1
,4ꢀ and 1,2ꢀdiols. Using the P NMR method, we
were able to monitor the formation and transformaꢀ
α−
tion, under the reaction conditions, of PW O peroxo
n
m
Johnstone, A.W., Chem. Commun., 1999, no. 1, p. 37.
1. Centi, G. and Trifiro, F., J. Mol. Catal., 1986, vol. 35,
complexes active in BD epoxidation. The imidazolium
cation exerts a favorable effect on the formation of these
complexes and on the selectivity of the reaction by inhibꢀ
iting the side radical reactions of BD.
no. 2, p. 255.
2. Trifiro, F. and Jiru, P., Catal. Today, 1988, vol. 3, no. 3,
p. 519.
3. Schroeder, W.D., Fontenot, C.J., and Schrader, G.L.,
J. Catal., 2001, vol. 203, no. 2, p. 382.
4. Takehira, K., Mimoun, H., and De Roch, I.S.,
REFERENCES
1. Monnier, J.R., Appl. Catal., A, 2001, vol. 221, nos. 1–2,
J. Catal., 1979, vol. 58, no. 2, p. 155.
p. 73.
5. Hotanahalli, S.S. and Chandalia, S.B., J. Appl. Chem.
970, vol. 20, p. 323.
,
2. BlankoꢀBrieva, G., CapelꢀSanchez, M.C., Pilar de
Frutos, M., PadillaꢀPolo, A., CamposꢀMartin, J.M.,
1
and Fierro, J.L.G., Ind. Eng. Chem. Res., 2008, vol. 47, 26. US Patent 4172838, 1979.
no. 21, p. 8011.
2
2
2
7. US Patent 4243593, 1981.
3
4
5
. Mizuno, N., Yamaguchi, K., and Kamata, K., Coord.
Chem. Rev., 2005, vol. 249, nos. 17–18, p. 1944.
8. US Patent 4298531, 1981.
9. Zang, X., Zang, Z., Suo, J., and Li, Sh., Catal. Lett.
,
. Mizuno, N. and Kamata, K., Coord. Chem. Rev., 2011,
vol. 255, nos. 19–20, p. 2358.
2000, vol. 66, no. 3, p. 175.
3
0. Kamata, K., Katani, M., Yamaguchi, K., Hikichi, H.,
and Mizuno, N., Chem. Eur. J., 2007, vol. 13, no. 2,
p. 639.
. Mirkhani, V., Moghadam, M., Tangestaninejad, S.,
MohammodpoorꢀBaltork, I., Shams, E., and Rosouli, N.,
Appl. Catal., A, 2008, vol. 334, no. 1, p. 106.
31. Neumann, R. and de la Vega, M., J. Mol. Catal., 1993,
6
. Zhao, W., Ma, B., Hua, H., Zhang, Y., and Ding, Y.,
Catal. Commun., 2008, vol. 9, no. 14, p. 2455.
vol. 84, no. 1, p. 93.
3
2. Nomiya, K., Yanagibayashi, H., Nozaki, C., Kondoh, K.,
Hiramatsu, E., and Shimizu, Y., J. Mol. Catal. A:
Chem., 1996, vol. 114, nos 1ꢀ3, p. 181.
7
. Gharah, N., Chowdhury, K., Mukherjee, M., and
Bhattacharyya, R., Trans. Met. Chem., 2008, vol. 33,
no. 5, p. 635.
33. Kuznetsova, L.I., Maksimovskaya, R.I., and
8
. Liu, L., Chen, C., Hu, X., Mohamood, T., Ma, W.,
Lin, J., and Zhao, J., New J. Chem., 2008, vol. 32, no. 2,
p. 283.
Fedotov, M.A., Izv. Akad. Nauk SSSR, Ser. Khim.,
1985, no. 2, p. 488.
3
3
3
4. Venturello, C., D’Aloisio, R., Bart, J.C.J., and Ricci, M.,
J. Mol. Catal., 1985, vol. 32, no. 1, p. 107.
5. Ishii, Y., Jamawaki, K., Yoshida, T., Ura, T., and
9
. Zhang, Z., Zhao, W., Ma, B., and Ding, Y., Catal. Comꢀ
mun., 2010, vol. 12, no. 4, p. 318.
1
0. Zhao, W., Ding, Y., Zhang, Z., Ma, B., and Qiu, W.,
Ogawa, M., J. Org. Chem., 1987, vol. 52, p. 1868.
React. Kinet. Mech. Catal., 2011, vol. 102, no. 1, p. 93.
6. Aubry, C., Chottard, G., Platzer, N., Bregeault, J.ꢀM.,
Thouvenot, R., Chauveau, F., Huet, C., and Ledon, H.,
Inorg. Chem., 1991, vol. 30, no. 23, p. 4409.
7. Salles, L., Aubry, C., Thouvenot, R., Robert, F.,
DoremieuxꢀMorin, C., Chottard, G., Ledon, H.,
Jeannin, Y., and Bregeault, J.ꢀM., Inorg. Chem., 1994,
vol. 33, no. 5, p. 871.
1
1. Li, H., Yunxiang, Q., Yinyin, Y., Wenwen, Z., Ting, C.,
Yu, S., Huan, L., Bo, F., and Zhenshan, H., New J.
Chem., 2011, vol. 35, no. 9, p. 1836.
3
1
1
1
2. Yan, L., Jun, W., Dunru, Z., Mingjue, Z., Pingping, Z.,
Zhouyang, L., and Jun, H., Green Chem., 2011, vol. 13,
no. 7, p. 1636.
3. Antonova, N.S., Carbo, J.J., Kortz, U., Kholdeeva, O.A., 38. Duncan, D.C., Chambers, R.C., Hecht, E., and
and Poblet, J.M., J. Am. Chem. Soc., 2010, vol. 132,
Hill, C.L., J. Am. Chem. Soc., 1995, vol. 117, no. 2,
no. 21, p. 7488.
p. 681.
4. Gharnati, L., Doring, M., and Arnold, U., Curr. Org. 39. Dengel, A.C., Griffith, W.P., and Parkin, B.C.,
Synth., 2009, vol. 6, no. 4, p. 342.
J. Chem. Soc., Dalton Trans., 1993, no. 18, p. 2683.
KINETICS AND CATALYSIS Vol. 54
No. 4
2013

430
KUZNETSOVA et al.
40. Polotebnova, N.A., Nguen Van Cheu, and Kal’niboꢀ 47. Kuznetsova, L.I., Detusheva, L.G., Fedotov, M.A., and
lotskaya, V.V., Zh. Neorg. Khim., 1973, vol. 18, no. 2,
p. 413.
Likholobov, V.A., J. Mol. Catal. A: Chem., 1996,
vol. 111, nos. 1–2, p. 81.
4
4
4
1. Maksimov, G.M., Kustova, G.N., Matveev, K.I., and 48. Kuznetsova, N.I., Kuznetsova, L.I., and Likholobov, V.A.,
Lazarenko, T.P., Koord. Khim., 1989, vol. 15, no. 6,
J. Mol. Catal. A: Chem., 1996, vol. 108, nos. 1–3, p. 135.
p. 788.
4
5
5
9. Behar, D., Gonzalez, C., and Neta, P., J. Phys. Chem. A
,
2. Kuznetsova, L.I., Kuznetsova, N.I., Maksimovskaya, R.I.,
Aleshina, G.I., Koscheeva, O.S., and Utkin, V.A.,
Catal. Lett., 2011, vol. 141, no. 10, p. 1442.
2001, vol. 105, no. 32, p. 7607.
0. Wang, A. and Jiang, H., J. Org. Chem., 2010, vol. 75,
no. 7, p. 2321.
3. Kozhevnikov, I.V., Catalysis for Fine Chemical Synthesis
vol. 2: Catalysis by Polyoxometalates, Chichester: Wiley,
002.
,
1. Metelitsa, D.I., Modelirovanie okislitel’noꢀvosstanoviꢀ
tel’nykh fermentov (Modeling of Redox Enzymes),
Minsk: Nauka i Tekhnika, 1984.
2
4
4
4
4. Hendry, D.G., Mayo, R.F., and Scheutzle, D., Ind.
52. Kozlov, Yu.N., Nizova, G.V., and Shul’pin, G.B., Russ.
J. Phys. Chem., 2004, vol. 78, no. 2, p. 184.
Eng. Chem. Res., 1968, vol. 7, no. 2, p. 136.
5. Odyakov, V.F., Kuznetsova, L.I., and Matveev, K.I., Zh.
Neorg. Khim., 1978, vol. 23, no. 2, p. 457.
6. Mel’nik, L.V., Srednev, S.S., Rybina, G.V., Meshechꢀ
kina, F.E., Shevchuk, F.S., and Danilova, A.S., Pet.
Chem., 2007, vol. 47, no. 3, p. 201.
53. Kozlov, Yu.N., Nizova, G.V., and Shul’pin, G.B.,
J. Mol. Catal. A: Chem., 2005, vol. 227, nos. 1–2, p. 247.
Translated by D. Zvukov
KINETICS AND CATALYSIS Vol. 54
No. 4
2013