Coordination Chemistry Reviews 268 (2014) 83–100

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Coordination Chemistry Reviews

journal homepage: www.elsevier.com/locate/ccr

Review

Monomeric and dimeric oxido–peroxido tungsten(VI) complexes in

catalytic and stoichiometric epoxidation
Mojtaba Amini a,∗ , Mohammad Mehdi Haghdoost b , Mojtaba Bagherzadeh b,∗
a
Department of Chemistry, Faculty of Science, University of Maragheh, P.O. Box 55181-83111, Maragheh, Iran
b
Chemistry Department, Sharif University of Technology, P.O. Box 11155-3615, Tehran, Iran

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2. Homogeneous epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
3. Heterogeneous epoxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.1. Polymer-anchored catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.2. Silica-anchored catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.3. Magnetically recyclable catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

a r t i c l e i n f o a b s t r a c t

Article history: Epoxides are important materials in the production of fine chemicals. Selective oxidation of alkenes to
Received 12 November 2013 epoxides remains a challenge in synthetic chemistry. There has been considerable progress in tungsten-
Accepted 2 January 2014 catalyzed epoxidation of alkenes in recent years. This review highlights the use of monomeric and dimeric
Available online 15 February 2014
oxido–peroxido tungsten(VI) complexes as catalysts or oxidants in homogeneous or heterogeneous cat-
alytic systems for epoxidation of olefins.
Keywords:
© 2014 Elsevier B.V. All rights reserved.
Oxido–peroxido
Tungsten(VI)
Epoxidation
Homogeneous
Heterogeneous

1. Introduction

Olefin epoxidation is an important reaction for the production

of epoxides as chemical intermediates to afford useful chemicals
[1–5]. The use of transition metal complexes as catalysts in organic
synthesis is an exciting field of research, and such catalysts are
Abbreviations: 2-pybmz, 2-(2-pyridyl)benzimidazole; 3-pybmz, 2-(3- extensively utilized in a wide range of areas [5–10]. In general, in
pyridyl)benzimidazole; DCE, dichloroethane; DMF, dimethylformamide; ee, the presence of hydrogen peroxide, metals form oxido–peroxido
enantiomeric excess; dppmO2 , bis(diphenylphosphineoxide)methane; HA, complexes, which can be used in the synthesis of a number of
hydroxyapatite; HBPT, hexabuthylphosphor triamide; HMPT, hexamethylphos-
fine chemicals [11–13]. Most oxidation reactions involving molec-
phor triamide; HMS, hexagonal mesoporous silica; HPEOH, 1-(2 -hydroxyphenyl)
ethanone oxime; IL, ionic liquid; MO-LCAO, molecular orbital-linear combination ular oxygen and metal complexes proceed via inner-sphere or
of atomic orbitals; PMA, polymethacrylate; PS, polystyrene; PTC, phase-transfer addition–elimination mechanisms. Oxido–peroxido complexes of
catalyst; PW2 , [HPO4 {WO(O2 )2 }2 ]2− ; QO, 8-quinolinol; TBA, tetrabutylammonium transition metal are important intermediates for this type of acti-
cation; TBHP, tert-butylhydroperoxide; THA, tetrahexylammonium; TOF, turnover
vation, so interest in them as catalysts in oxidation reactions has
frequency; TON, turnover number; MBO, 3-methyl-3-buten-1-ol.
∗ Corresponding authors. Tel.: +98 421 2278900; fax: +98 421 2276066. increased [14–17].
E-mail addresses: mamini@maragheh.ac.ir (M. Amini), bagherzadeh@sharif.edu The chemistry of transition metal oxido–peroxido complexes
(M. Bagherzadeh). has attracted special attention owing to their importance in a

http://dx.doi.org/10.1016/j.ccr.2014.01.035
0010-8545/© 2014 Elsevier B.V. All rights reserved.
84 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100
O O 1a; L= H2O
1b; L= DMF
W
1c; L= HMPT
1d; L=Pyridine
O O
1e; L=HBPT
L
Fig. 1. W(VI) oxido–bisperoxido complexes developed by Mimoun et al. [31].
variety of industrial, pharmaceutical, and biological processes
[18,19]. Coordination to a metal center activates peroxido groups
for oxidation of a variety of substrates, so oxido–peroxido metal
complexes are important as intermediates in biological and syn-
thetic catalysis [20–23].
Oxido–peroxido complexes of molybdenum and tungsten ions
[Mo(VI) and W(VI)] with a closed-shell electronic structure and d0
configuration are of particular interest. Like molybdenum, tungsten
displays high activity in oxidation reactions, and oxido–peroxido
complexes of tungsten can be used for stoichiometric oxygen trans-
fer reactions, including epoxidation of alkenes and oxidation of
organic and inorganic substrates, and can be regarded as an envi-
ronmentally friendly alternative to traditional oxidation catalysts.
Structural studies on W(VI) complexes have shown that the
metal nucleus is more shielded in oxido–peroxido than in the
corresponding dioxido complex for similar ligands. Accordingly,
bisperoxido should be more shielded than monoperoxido com-
plexes [24]. A number of reviews have focused on synthetic and
catalytic aspects of polyoxotungstates [25–28]. In 2005, Mizuno
et al. reviewed H2 O2 -based epoxidation of olefins catalyzed by
polyoxotungstates [5]. They concluded that polyoxotungstates are
the best among simple soluble salts of metal oxides for epoxidation,
but are sometimes unsuitable for the production of acid sensitive
and/or water-soluble shorter-chain epoxides owing to the low pH
in the aqueous phase. We recently reviewed catalytic and stoichio-
metric oxidations of oxido–peroxido molybdenum(VI) complexes
[29]. In many ways the behavior of oxido–peroxido tungsten(VI)
complexes is very similar to that of molybdenum complexes [30].
However, unlike molybdenum complexes, the reactivity of tung-
sten complexes has not been studied much because of their low
solubility.
Here we review monomeric and dimeric oxido–peroxido tung-
sten(VI) catalysis of olefin epoxidation. As mentioned above, olefin
epoxidation by polyoxotungstates has recently been reviewed [5]
and is not covered here. The review is organized into two gen-
eral sections, homogeneous catalysis and heterogeneous catalysis.
Future directions for research in this area are also discussed.
2. Homogeneous epoxidation
In 1969, Mimoun et al. were the first to prepare a series
of oxido–bisperoxido W(VI) complexes of the general formula
[WO(O2 )2 Ln ] 1 (n = 1–2; L = H2 O 1a, DMF 1b, HMPT 1c, pyridine
1d, HBPT 1e) (Fig. 1) and evaluate their activity as a stoichiomet-
ric oxidant in the epoxidation of alkenes [31]. Since then, several
molybdenum and tungsten complexes with this general formula,
known as Mimoun-type complexes, have been investigated.
The use of Mimoun-type tungsten complexes as stoichiometric
oxidants was the subject of much research in the 1970s and 1980s.
In 1986, the kinetics of stoichiometric epoxidation of olefins with
1c in DCE was studied [32]. Although the molecular structure of 1c
and its molybdenum analog, [MoO(O2 )2 (HMPT)] 2, are very similar,
the oxygen transfer rates are faster from 1c than from 2 by factors
ranging from five for cyclooctene to 40 for cis-stilbene. In addition,
the two peroxido groups in 1c appear to react with the substrates at
Fig. 2. Intermediates in epoxidation of allylic alcohols by (a) hydroperoxovanadium
and titanium, and (b) 1c complexes.
different rates. In fact, 1c behaves as a mono-oxygenating reagent
toward olefins. Transfer of the first peroxide oxygen is faster than
that of the second, contrary to behavior observed for the molybde-
num analog.
Di Furia et al. reported that epoxidation of the allylic alcohols
geraniol 3a and linalool 3b with 1c at ambient temperature is
remarkably faster than for simple olefins and is regiospecific [33].
Under the experimental conditions used, highly selective and quan-
titative yields of the corresponding monoepoxides were obtained,
but the regioselectivity was opposite between geraniol and linalool.
Geraniol 3a affords the 2,3-epoxygeraniol 4a, whereas the 6,7-
epoxy derivative 4b was obtained from linalool 3b (Scheme 1).
Interestingly, the opposite regioselectivity was not observed in
the same epoxidation reactions of 3a and 3b using similar vanadium
and titanium complexes as oxidant. The hydroperoxo vanadium
and titanium complexes regiospecifically epoxidize both 3a and 3b
at the allylic double bond (Scheme 1) [34,35]. Clearly there must
be some significant difference between the two classes of oxidants.
In fact, epoxidation with hydroperoxo V and Ti complexes starts
with coordination of the substrate to the metal center to form an
alkoxohydroperoxo complex (Fig. 2a), which favors oxygen transfer
to the allylic double bond. By contrast, epoxidation with Mo and
W peroxido complexes should not involve a coordinated substrate
and the accelerating effect of the hydroxo moiety should be related
to intramolecular hydrogen bonding between the OH group of the
allylic alcohol and the peroxido groups of the tungsten complex
(Fig. 2b). This conclusion was supported by the observation that
when alcohols such as CH3 OH and CF3 CH2 OH were added to the
reaction mixture at low concentration, detectable enhancement of
the epoxidation rate of a simple olefin occurred, thus confirming
that an accelerating effect by a protic species, likely via hydrogen
bonding of the peroxido oxygen in the transition state, is involved
[33].
Mimoun-type tungsten complexes act not only as stoichiomet-
ric oxidants but also as catalysts [36]. Oxidation of cyclohexene
and 1-methylcyclohexene by H2 O2 in the presence of cat-
alytic amounts of 1c was studied at 40 ◦ C. The results showed
quantitative formation of epoxide based on H2 O2 consumed,
and indicated that under the appropriate experimental condi-
tions, W(VI) is by far a better catalyst of oxidation by H2 O2
than other metals studied so far [36]. This is because of its
high reactivity for oxidation and inherent poor activity for
decomposition of H2 O2 . Since the reaction was carried out in
acid medium, the epoxide initially formed undergoes quantita-
tive acid-catalyzed ethanolysis, yielding 2-ethoxycyclohexan-l-ol
and 2-ethoxy-2-methyl-cyclohexan-l-ol from cyclohexene and
1-methylcyclohexene, respectively [36]. The kinetic studies con-
firmed that similar to Mo(VI) oxido-bisperoxido catalytic systems
[37], 1-methylcyclohexene (more nucleophilic substrate) reacts
significantly faster, by a factor of approximately 2.5, than does
cyclohexene.
The nature of the species formed in aqueous solutions of
[WO4 ]2− in the presence of H2 O2 was studied using Raman, IR, and
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 85

C3 or hydroperoxovanadium and titanium O

OH OH

3a 4a

HO HO HO

hyd roperoxovanadium and titanium C3

O

4c 3b 4b

Scheme 1. Oxidation of geraniol and linalool by hydroperoxovanadium and titanium and 1c complexes [33–35].

NMR spectroscopy [37,38]. At pH values from 1 to 9 in solutions
containing H2 O2 /W at a ratio of 5:1, various anionic tungsten oxido-
peroxido species exist. At high pH (>7), [W(O2 )4 ]2− 5 predominates;
at intermediate pH (1.3–7), dimer [W2 O3 (O2 )4 (H2 O)2 ]2− 6 is
the major species; and at pH < 1.3 in the presence of HCl, cis-
[WO(O2 )Cl4 ]2− 7 is formed (Fig. 3). Long before the nature of these
tungsten oxido–peroxido species was known, it was observed that
[WO4 ]2− /H2 O2 systems catalyze epoxidation reactions. As early as
1959, an ␣,␤-unsaturated carboxylic acid, maleic acid, was epox-
idized in quantitative yield using H2 O2 and Na2 WO4 at pH 4–5.5
[39]. At 65 ◦ C, the epoxidation reactions required approximately
1.5 h. Under similar reaction conditions, simple olefin substrates
showed lower reactivity. For example, 2-heptene underwent epox-
idation to afford the corresponding epoxide in 55% yield in 6 h. The
Na2 WO4 /H2 O2 catalytic system can be applied successfully to all
di- and trisubstituted unsaturated acids by slight modification of
the reaction conditions [40]. In addition, [WO4 ]2− -catalyzed epox-
idation of ␣,␤-unsaturated carboxylic acids to the corresponding
epoxides was faster than for molybdate [MoO4 ]2− and vanadate
[VO4 ]3− catalysis [41,42].
Epoxidation of allylic alcohols with aqueous H2 O2 in the pres-
ence of tungstic acid (H2 WO4 ) as a catalyst has also been studied
[46–50]. In contrast to Na2 WO4 , H2 WO4 is a strong Brønsted
acid. Oxidation of olefins in acidic solution of H2 WO4 with H2 O2
leads to the formation of diols [51–53]. For selective epoxide for-
mation, the catalytic reaction should be carried out in buffered
conditions. Epoxidation of olefinic alcohols was achieved in high
yields in buffered water–substrate mixtures with hydrogen perox-
ide and H2 WO4 [48]. Under these reaction conditions, epoxidation
occurred with complete retention of the stereochemistry around
the carbon–carbon double bond, and no isomerization, cleavage of
the olefinic bond, or overoxidation to diols was observed.
Application of the [WO4 ]2− /H2 O2 catalytic system is limited to
substrates that are soluble in water or water–alcohol mixtures.
Consequently, this method is not suitable for the epoxidation of
simple olefins. An alternative approach is to run the epoxidation
reaction under phase transfer conditions. Venturello and cowork-
ers described the catalytic epoxidation of simple cyclic and acyclic
alkenes in the presence of a phase-transfer catalyst (PTC) in biphasic
8% H2 O2 /DCE [53]. For this catalytic system, 1-octene was oxidized
to 1,2-octeneoxide in 87% yield. In spite of the acidic conditions,
no hydroxylation product was detected. The reason for this is the
protective effect of the biphasic system. Furthermore, a significant
improvement in catalysis can be achieved by simultaneous use of
both Na2 WO4 and H2 WO4 as catalysts [54].
The efficiency of biphasic epoxidation by [WO4 ]2− /H2 O2
strongly depends on the type of phase transfer agent. As an
example, when a quaternary ammonium salt was immobilized on
polymer as PTC, an increase in reaction selectivity compared to a
system with non-immobilized salt was observed [55]. Changing
the PTC can even change the reaction product in some cases. For
oxidation of cyclohexene using 30% H2 O2 , Na2 WO4 , and [CH3 (n-
C8 H17 )3 N]HSO4 as the PTC, adipic acid was isolated in 93% yield
instead of epoxide [56,57].
The dimer [W2 O3 (O2 )4 (H2 O)2 ]2− 6 (Fig. 3) was the first tungsten
oxido–peroxido complex to be characterized by X-ray crystallog-
raphy [45]. In the binuclear structure of [W2 O3 (O2 )4 (H2 O)2 ]2− , the
tungsten oxido–bisperoxido units are linked through an oxo ligand
[45]. In the presence of the non-anionic monodentate and biden-
tate ligands, the W O W bonds cleave to form complexes with
separate WO5 units. Gelbard and coworkers prepared a series of
oxido–bisperoxido tungsten(VI) complexes (8b–11b) with several
neutral organophosphorus(V) and diamine ligands (8a–11a, Fig. 4).
Complexes 8b–11b, either preformed or formed in situ, were cat-
alytically active in the epoxidation reaction [58,59] (Fig. 5).
Among the catalysts investigated, the highest turnover
frequency was observed for epoxidation of allylic alcohols cat-
alyzed by 11b (TOF = 58). Interestingly, the reaction of 6 with
mono-anionic phosphonic acid ligands 12a and 13a gave the perox-
oditungstic complexes 12b and 13b, in which two WO(O2 )2 groups

2- 2- 2-
H2O
O O O
O O O
O
O O
O W O O Cl O
W
O W
O O W Cl Cl
O O
O O Cl
O
O
H2O
5 6 7

Fig. 3. W(VI) oxido–peroxido complexes 5 [43,44], 6 [45], and 7.

86 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100

Fig. 4. Ligands 8a–14a and W(VI) oxido–bisperoxido complexes 8b–14b [58–60].

are connected by the phosphonic acid ligand (Fig. 4). Under similar
reaction conditions, the TOF obtained with 12b (TOF = 88) was even
higher than that with 11b. The authors attributed this finding to the
hydrophilic and hydrophobic (amphiphilic) behavior of 12b. Com-
plex 12b has both ionic character and a hydrophobic counter-cation
(Q+ ). During epoxidation it is essentially concentrated in the organic
phase, where the catalytic reaction takes place. After each catalytic
cycle, it returns to the aqueous H2 O2 phase to regenerate the cat-
alytically active bisperoxido complex. However, as mentioned later,
it seems to be more appropriate to relate the high activity of 12b
directly to the Lewis acidity of the metal centers.
In the same year, the activity of 14b was examined in cat-
alytic epoxidation of a number of cyclic and linear alkenes in
a biphasic H2 O2 –benzene mixture [60]. Comparison between
12b and 14b reveals that the latter exhibits lower activi-
ties. Obviously, the presence of the phenyl rings decreases
the catalytic ability of the complex but the reason is not yet
clear.
Complexes 15a–c were active species in olefin oxidation and
formed epoxides as primary products. The tungsten complex 15a
reacted much faster than the corresponding molybdenum com-
plex [61]. The exact reaction conditions and epoxidation results
were not described by the authors, but they mentioned that
the yield and turnover number for epoxidation depend on the
[W]/[ligand]/[PPh4 ] ratio [62]. Noyori et al. published a detailed
review of the use of H2 O2 , [WO4 ]2− , and WO3 precursors and an
onium salt as a PTC in the oxidation of various organic compounds
[63], so this is not repeated here.
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 87

R3 OH

R4 R1

R2 H2O
H2O
O
W
O R3 OH
I
H2O
R4 R1
R4 R1
2 3 R2
R R
a
O H
HOOH O
+
HO 50 <a<70o
o
W

O
W

R3 OH

O
R4 R1

Fig. 5. W(VI) oxido–bisperoxido complexes 15a–c [61,62]. R2

For non-surfactant amphiphilic sugars, such as sucrose, l-
arabinose, and methyl or ethyl ␤-d-fructopyranoside, instead of
onium salts, epoxidation of allylic alcohols by H2 O2 in the presence
of [WO4 ]2− salts occurred in neutral aqueous solution [64]. In this
catalytic system, an amphiphilic carbohydrate enhances the solu-
bility of the allylic alcohol in water. For example, both geraniol and
nerol substrates have low solubility in pure water but are highly
soluble in 1 M sucrose solution. Using [WO4 ]2− salt as a catalyst
and H2 O2 as a terminal oxidant, complete conversion of isophorol
(3,5,5-trimethyl-2-cyclohexen-1-ol) to its corresponding epoxide
was achieved for reactions in the presence of carbohydrates. In the
absence of carbohydrates, epoxidation of acyclic alcohols gave mix-
tures of erythro and threo epoxides, but epoxidation in glycosidic
aqueous media proceeded with remarkable stereo-discrimination
in favor of erythro-enriched epoxy alcohols. Hydrophobic interac-
tions between the most hydrophobic face of the substrate and that
of the sugar additive are responsible for the stereo-discrimination
observed.
In 1986, Mimoun et al. prepared [Ph3 PCH2 Ph]2 [6] (Fig. 3) and
used it as an effective catalyst for epoxidation of alkenes in a
water–organic mixture [65]. In this catalytic system, epoxidation
proceeds in the organic phase, where the tungsten complex resides
because of the lipophilicity of the Ph3 PCH2 Ph cation. Similar to
other reports [33], allylic alcohols were rapidly epoxidized but con-
jugated double bonds were not very reactive toward epoxidation.
Mizuno and coworkers showed that the potassium salt of dimer
6 (K2 [6], Fig. 3) could act as an effective catalyst for chemo-, regio-
, and diastereo-selective and stereospecific epoxidation of allylic
alcohols using H2 O2 in water without PTCs such as onium salts
[66,67]. Oxidation of 1-propen-3-ol in water using complex K2 [6]
as a catalyst proceeds smoothly with a high rate of conversion
and selectivity (TON = 4900). Retention of the dimer structure of
6 was suggested by IR, UV/Vis, and 183 W NMR spectra of recovered
catalysts [66].
The stereochemistry observed for catalytic epoxidation of 1,3-
allylic alcohols by K2 [6] was rather surprising [68]. Catalytic
Scheme 2. Mechanism for epoxidation of allylic alcohols by K2 [W2 O3 (O2 )4 (H2 O)2 ]
dimer [68].
epoxidation of 1,3-allylic strained alcohols proceeded diastereos-
electively to give the threo diastereoisomer preferentially, but the
erythro selectivity was higher for allylic alcohols without 1,3-allylic
strain. The stereochemical results suggest that the dihedral angle
between the ␲ plane of the C C double bond and the hydroxyl
group of the allylic alcohol in the transition-state geometry is
50–70◦ (Scheme 2). On the basis of these results, in addition to
kinetic and spectroscopic results, the authors proposed a mech-
anism for catalytic epoxidation of allylic alcohols by 6 [18]. In
this mechanism the allylic alcohol substrate coordinates to the
tungsten center by dislodging water that is already coordinated
(metal–alcoholate binding mechanism) (Scheme 2). This mecha-
nism is incompatible with the mechanisms proposed by Di Furia
et al. for epoxidation of allylic alcohols by [WO(O2 )2 (HMPT)] (1c,
Fig. 2b) [33]. The mechanism suggested by Di Furia et al. involves
hydrogen bond formation between the substrate and the peroxido
groups the of tungsten complex (hydrogen-bonding mechanism).
We surmise from the results that the distinction between these
two mechanisms lies in the existence or absence of an easily
replaceable ligand. The water ligand of the K2 [W2 O3 (O2 )4 (H2 O)2 ]
complex can be easily replaced by allylic alcohols, whereas the
HMPT ligand of the [MoO(O2 )2 (HMPT)] complex cannot be replaced
by other monodentate ligands. Competitive epoxidation of homoal-
lylic and allylic alcohols catalyzed by [SeO4 {WO(O2 )2 }2 ]2− 16 also
revealed that a metal–alcoholate species is not formed in the tran-
sition state for 16-catalyzed epoxidation of allylic alcohols because
the W atoms in 16 does not contain an easily replaceable ligand
(hydrogen-bonding mechanism) [69].
Preliminary coordination of the substrate to the W(VI)
bisperoxido complex was also proposed for epoxidation of cis-1-
propenylphosphonic acid [70]. However, 13 C NMR showed that
␣,␤-unsaturated carboxylic acids cannot coordinate to the W(VI)
center of the bisperoxido complex prior to oxygen transfer. This
88 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100
Fig. 6. W(VI) oxido–bisperoxido complexes 17a and 17b [74].
indicates the role of the functional group conjugated to the olefinic
double bond in the epoxidation mechanism.
Deprotonation of the OH bond of an allylic alcohol followed
by proton transfer to the peroxido ligand occurs when the allylic
alcohol coordinates to the tungsten ion (Scheme 2). The epoxy alco-
hol and tungsten dioxido-monoperoxido complex are formed via
an oxygen transfer reaction. Then the H2 O2 oxidizes the dioxido
species back to bisperoxido, which reenters the cycle and contin-
ues the process [68]. The same mechanism was also identified in the
oxidation of sulfides [71,72] and bromide ions [73] by monomeric
and dimeric oxido-peroxido tungsten(VI) complexes.
In 2000, the chiral oxido–bisperoxido W(VI) complexes 17a
and 17b (Fig. 6) were successfully used by Yoon et al. in
the catalytic epoxidation of styrene derivatives using TBHP as
a terminal oxidant [74]. In particular, catalytic epoxidation of
trans-␤-methylstyrene at room temperature using 17b afforded
(1S,2S)-trans-methylstyrene oxide in 41% yield and 63% ee. How-
ever, for styrene as substrate the chemical yield (29%) and
enantioselectivity (4%) were quite low. The authors noted that
tungsten complexes 17a and 17b were more active than molyb-
denum(VI) analogs in the epoxidation reaction. This finding seems
to conflict with many studies that have reported higher catalytic
activity of tungsten compared to molybdenum peroxido complexes
[29]. In 2006, Jimtaisong and Luck reported that W-based diox-
ido and oxido–peroxido catalysts gave higher epoxide conversions
than Mo-based catalysts in H2 O2 systems. By contrast, Mo-based
catalysts were more reactive than the W counterparts in TBHP
systems [75]. Such considerable differences may result from the
different ability of the molybdenum and tungsten catalysts to acti-
vate TBHP and H2 O2 . W(VI) is better able to activate H2 O2 than
Mo(VI) is, whereas Mo(VI) is more active in epoxidation with TBHP
than W(VI) is.
Almost all of the tungsten peroxido complexes show higher
reactivity for stoichiometric epoxidation than chromium and
molybdenum counterparts. The activation energy calculated for
ethylene epoxidation with Mimoun-type [MO(O2 )2 (OP(CH3 )3 )]
complexes decreases from Cr (23.1 kcal/mol) to Mo (17.9 kcal/mol)
to W (15.4 kcal/mol). Density functional theory (DFT) analysis
reveals that the donation/backdonation (d/b) ratio, which is a mea-
sure of the electronic character of the oxidants, should be a measure
of the epoxidation activity in such complexes [76]. The d/b ratio and
therefore the electrophilicity increases in the order Cr < Mo < W.
Since oxido–peroxido complexes of VIb transition metals attack
olefins in an electrophilic manner [77], the epoxidation reactivity
of these complexes correlates with their electrophilicity.
In another study, Rösch and co-workers suggested a linear
correlation between the O O  * -orbital energy level and the activa-
tion barrier for ethylene epoxidation with [MO(O2 )2 (NH3 )] (M = Cr,
Mo, W) complexes: the higher the energy of the ␴* (O O) orbital,
the higher is the activation barrier [78]. The superior catalytic
O O O O
O O O O O
O
W W O W
O O W
O O O O
O
O O O O
O
25 26
Fig. 7. Dinuclear oxido–peroxido W(VI) complexes 25 and 26 [20].
activity of peroxido W(VI) complexes is not limited only to epoxida-
tion reactions. In 1994, Reynolds et al. reported that the bisperoxido
tungsten complex [WO(O2 )2 (C2 O4 )]2− 18 oxidizes bromide ions at
a faster rate than the molybdenum(V1) counterpart does [79].
Various W(VI) complexes (19–24) containing oxido, peroxido,
and 8-quinolinol ligands were prepared by Bhattacharyya et al.
[80,81]. The preparation procedure is shown in Scheme 3. Stoi-
chiometric epoxidation of alkenes was carried out using 20 and
22 complexes in acetonitrile. When 20 was allowed to react stoi-
chiometrically with cyclopentene in a 1:1 ratio, complex 21 formed
in addition to cyclopentene oxide. Under similar reaction condi-
tions, 22 reaction with cyclopentene in molar ratios of 1:1 and
1:2 led to significant amount of epoxide and complexes 23 and 24,
respectively.
All complexes 19–24 were catalytically active for olefin epoxida-
tion. Comparative studies for epoxidation of cyclohexene revealed
that the catalytic activity increases in the order 23 < 20 < 22 < 19.
Compared to monoperoxido tungsten catalysts (20 and 23), the
bisperoxido complexes (19 and 22) showed significantly higher
catalytic activity. Using complex 22 as a catalyst, epoxidation of
cyclohexene at room temperature in the presence of H2 O2 as oxi-
dant and NaHCO3 as promoter yielded cyclohexene oxide with TOF
as high as 5460 h−1 . Catalyst 22 without NaHCO3 as co-catalyst
showed very low activity. It is known that H2 O2 and bicarbonate
react in an equilibrium process to produce peroxymonocarbon-
ate (HCO4 − ), which is a more reactive nucleophile than H2 O2 and
speeds up epoxidation reactions [82,83]. The authors noted that the
epoxidation rate depends strongly on the substrate concentration,
bicarbonate concentration, and reaction temperature.
Two dinuclear oxido–peroxido W(VI) com-
plexes, (TBA)2 [{WO(O2 )2 }2 (␮-O)] ((TBA)2 [25]) and
(TBA)2 [{WO(O2 )2 }2 (␮-O2 )] ((TBA)2 [26]; Fig. 7), were synthe-
sized by Hazarika et al. [73]. In principle, the structure of anion 25
is similar to the well-known dinuclear oxido–peroxido W(VI) com-
plex 6 (Fig. 3), except that in 25 the aqua ligands are eliminated.
Reaction of 25 with H2 O2 gives 26, which contains three different
peroxido ligands (␩2 , ␩1 :␩2 , and ␩1 :␩1 ). In acetonitrile media,
stoichiometric epoxidation of various alkenes with (TBA)2 [26]
produced quantitative amounts of the corresponding epoxides,
but stoichiometric epoxidation with (TBA)2 [25] hardly proceeded.
Complex 25 alone was only able to epoxidize allylic alcohols.
IR, Raman, and UV–vis spectroscopic studies revealed that 26
is converted to 25 by reaction with olefin and 26 can easily be
regenerated by reaction of 25 with H2 O2 . Taken together, these
results are consistent with 26 as the active oxidant and 25 as the
precursor. The oxidation ability of 26 is interesting, since (␩1 :␩1 -
peroxido)dimetal complexes are usually inactive for oxygenation
of organic substances.
Although the dinuclear oxido–peroxido W(VI) anion 25 is not an
active oxidant, the THA salt of this anion is an efficient catalyst for
oxidation of alkenes with H2 O2 in acetonitrile [85]. Under the con-
ditions used, cis-cyclooctene was completely transformed to the
corresponding epoxide after 4 h of reaction at reflux temperature
(TON = 600). Catalytic epoxidation by anion 25 was dramatically
accelerated by a factor of approximately 60 on addition of HNO3
or HClO4 [86]. Mizuno et al. showed that a tetranuclear W(VI)
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 89

O
O O
O O O
H W crystallization N
O O H from acetonitrile O W
excess H2O2 O O
H2WO4.2H2O N N
CH3COOH (4 M) O
N

19 20

O O O
O
O O O
O
N
O W O W O excess H2O2 O W
PPh4 O PPh4 O
N N O
O N

21
23 22

O O
W
PPh4 O
N

24

Scheme 3. Stepwise synthesis of catalysts 19–24 [80].

peroxido complex was synthesized by reaction of 25 with an acid.

protic aprotic
The tetranuclear complex has three equivalents of active oxygen
for epoxidation of cyclooctene and its TOF is much greater than for
other di- and tetranuclear peroxotungstates [87].
Immobilization of catalysts in a room-temperature (RT) ionic + N () [W2O11] N () [W2O11]
5 +
liquid (IL) is a promising approach to achieve recyclable catalysts HN 5
N
[88,89]. Using the anionic peroxotungstate complexes described
2 2
above as an anion component of IL, it is possible to obtain a recy- [HHIm]2[25] [HMIm]2[25]
clable catalyst for epoxidation of alkenes. With this approach, two
protic and two aprotic ionic liquid containing [W2 O11 ]2− anion 25
(Fig. 8) were used as catalysts for epoxidation of cyclooctene in dif-
ferent media [90]. An interesting point is that the solvents had a
significant effect on the reaction efficiency and repeatability. The
catalysts exhibited better catalytic performance in polar organic + N () [W2O11] + N () [W2O11]
solvents, which makes H2 O2 utilization quite advantageous, but the 11 11
HN N
conversion rapidly decreased after the first cycle in organic solvents
2 2
(catalyst leaching). Use of mixed solvents addressed the problem of [HDIm]2[25] [DMIm]2[25]
catalyst recovery; for CH3 OH–H2 O, cyclooctene conversion remain
as high as 99.6% with > 99% selectivity, even after six consecutive Fig. 8. Ionic liquids containing anion 25 [90].
cycles.
90 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100

O O
N O N O O
O W
W O
O O N
O N
O O
O O
R

27a; R=H 27e

27b; R=Me (ortho)
27c; R=Me (meta)
27d; R=Me (para)

O
O O
O W
O O O
N O
O O O
W
O
O N
PPh4

28

29

O O
O M
O O
PPh4
N
OH

M=W 30
M=Mo 31

Fig. 9. Oxido–bisperoxido W(VI) complexes 27–31 studied by Bhattacharyya and coworkers [91,92].

Complexes 27a–e showed very similar catalytic activity for
H2 O2 epoxidation of olefins, but 27e was the most active. Thus,
the electron-donating methyl group did not change the catalyst
efficiency. Using 3–4 equivalents of H2 O2 as a terminal oxidant
and in the presence of NaHCO3 as a promoter, 27e showed high
catalytic activity and excellent selectivity for cyclohexene epox-
idation (TON = 4300). A unique feature of this catalytic system is
the very high catalytic selectivity. For almost all olefinic substrates,
epoxide selectivity was 100%. Reaction of an aqueous solution of
Na2 WO4 and an ethanolic solution of hydroxamic acid ligand pro-
duced dioxido W(VI) complex 28 (Fig. 9), which showed lower
catalytic efficiency (TON = 3700) than 27a–e. An attempt to reach
the bisperoxido [WO(O2 )2 (hydroxamato)] complex failed; instead,
the catalytically active complex, [PPh4 ][WO(O2 )2 (C6 H5 COO)] 29,
was formed (Fig. 9). Under identical conditions, this anionic oxido-
bisperoxido complex displayed the higher catalytic performance
for the epoxidation than did 27a-e catalysts (TON = 4450). There is
an important conclusion, that the bisperoxo tungsten complexes
generally give better results than the monoperoxido complexes in
the epoxidation reaction.
Using the same approach, Bhattacharyya et al. reported that
PPh4 [MO(O2 )2 (HPEOH)] complexes (M = W 30, M = Mo 31) (Fig. 9)
with 1-(2 -hydroxyphenyl) ethanone oxime as ligand are effective
olefin epoxidation catalysts with H2 O2 as the oxidizing agent [92].
The rate of catalytic epoxidation of cyclic olefins was almost the
same for both complexes. The tungsten compound showed higher
reactivity toward less reactive substrates such as linear olefins in
comparison to the molybdenum compound. In the case of alcohol-
functionalized olefins, this difference was more marked [92]. Both
complexes were capable of furnishing stoichiometric epoxidation.
Mizuno et al. reported on synthesis of a novel selenium-
containing binuclear peroxido tungsten(VI) complex,
(TBA)2 [SeO4 {WO(O2 )2 }2 ] ((TBA)2 [16]) (Fig. 10) [69]. The complex
obtained was not characterized by X-ray analysis but was used
in H2 O2 oxidation of olefins to epoxides [69,93]. Oxidation of
3-methyl-3-buten-1-ol (a homoallylic alcohol) with only one
equivalent of H2 O2 in the presence of (TBA)2 [16] was carried
out at ambient temperature and the corresponding epoxide was
obtained in excellent yield. Catalyst (TBA)2 [16] showed TOF as
high as 150 h–1 for 10-mmol-scale epoxidation of homoallylic
alcohols. The catalytic activity of (TBA)2 [16] was also compared
to that of similar complexes containing XO4 n– ligands (X = S, P, As,
and Si). Among the catalysts tested, the most promising results
were obtained for (TBA)2 [16]. The epoxide yield decreased with
the bond length between the W atom and the O atom of the
XO4 n− ligand (Se > S > As > P > Si). The same trend was previously
observed for stoichiometric epoxidation of (R)-(+)-limonene [94].
DFT calculations suggested that the long SeO W bond length
results in weak interaction between the SeO4 n− ligand and the
dimeric WO(O2 )2 unit, low Lewis acidity of the W centers, and high
catalytic activity for epoxidation. The (TBA)2 [16] catalyst could be
recycled without any decrease in catalytic activity.
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100
Fig. 10. Proposed structure of the anion part of 16, 32, and 33 [69,95].
The same group reported on a series of DFT studies to iden-
tify the exact mechanism for (TBA)2 [16] catalysis of epoxidation
(Scheme 4) [93]. According to their suggested mechanism, an
alkene is oxidized to the corresponding epoxide via nucleophilic
attack of the C C bond by one oxygen atom of the peroxido ligand.
The catalytic cycle is then started again by regenerated anion 16
with reaction of the peroxido complex and H2 O2 . The activation
barriers calculated indicate that the oxygen atoms of the bridging
peroxido groups, in particular the oxygen atom bound to a sin-
gle tungsten atom (O1) (Fig. 10), are primarily involved in olefin
epoxidation. In an ab initio MO-LCAO study in 1997, Fantucci et al.
showed that ethylene oxidation by [H2 PO4 {WO(O2 )2 }2 ]− complex
32 (Fig. 10) occurs via the same mechanism [95]. The tendency
of the oxygen atoms of the peroxido groups of 32 to react with
ethylene increases in the order O2 < O3, 4 < O1.
Although the above-mentioned mechanism is generally
accepted, studies have revealed contradictory results regarding
the active structure of the tungsten peroxido complexes. While
many studies postulate that the W(O2 ) three-membered ring is
the active group [68,93,95], a few propose that the WOOH group,
which forms via reaction of W(O2 ) with H2 O2 , is the active group
Scheme 4. Mechanism for epoxidation in the presence of W(VI) complex 15 as
reported by Mizuno et al. [93].
91
[96]. In a recent study, two possible active structures including
peroxo ring and hydroperoxo structures have been investigated
using DFT [97], but the results could not give a clear-cut answer to
the question of which is the true active structure. In our opinion,
there is a strong possibility that both active structures can be
involved simultaneously in the oxygen transfer step.
The Brégeault group showed that the [H2 PO4 {WO(O2 )2 }2 ]−
complex 32 (Fig. 10) is an effective catalyst and a stoichiometric
oxidant for epoxidation of (R)-(+)-limonene at room temperature
[98]. With this complex (0.25 mmol), stoichiometric oxidation of
(R)-(+)-limonene (1.5 mmol) in DCM led to the formation of monoe-
poxides (0.45 mmol). This means that half the peroxido ligand can
transfer an oxygen atom to the C C bond. It seems that only bridg-
ing peroxido ligands are involved in the oxygen transfer reaction.
The same research group found that a very similar anionic com-
plex, [HPO4 {WO(O2 )2 }2 ]2− 33 (Fig. 10), was an efficient catalyst for
epoxidation with H2 O2 in the presence of a phase–transfer agent
in a biphasic H2 O2 –CH3 Cl mixture [94,99].
In contrast to extensive studies on the catalytic properties
of bisperoxido complexes of W(VI), there are few studies on
the catalytic activity of W(VI) monoperoxido complexes. The
[WO(O2 )L(CH3 OH)] complex 34 (Fig. 11) was the first Schiff base-
W(O2 ) complex used as a catalyst for epoxidation [100]. Complex
34 showed high activity for a wide range of olefins in the presence
of H2 O2 /NaHCO3 as oxidant, and catalyzed selective epoxidation
of different linear and cyclic alkenes at room temperature. The
catalytic activity of complex 34 for epoxidation was almost iden-
tical to that of the molybdenum analog [MoO(O2 )L(CH3 OH)], and
depended strongly on the reaction conditions [12].
Table 1 summarizes some of the catalytic properties of
monomeric and dimeric oxido–peroxido W(VI) complexes. More
details on the reaction conditions can be found in the relevant
references.
3. Heterogeneous epoxidation
A major drawback of homogeneous catalysts is difficult recovery
from the reaction medium. Precipitation with subsequent recov-
ery, for example by distillation of the reaction products, which
is an energy intensive process, is typically needed for reuse of
homogeneous catalysts. Recognition of this inherent limitation of
homogeneous catalyst led to a surge in activity to develop het-
erogeneous catalysts. The aim is to combine the advantages of
homogenous catalysts (activity and selectivity) with the facility of
heterogeneous systems for catalyst recycling.
3.1. Polymer-anchored catalysts
Several heterogeneous tungsten(VI) peroxido catalysts have
shown good performance in epoxidation reactions. In 1992,
 92
Table 1
Summary of results for stoichiometric and catalytic oxidation of olefins by W(VI) oxido–peroxido complexes.

W complex Substrate Reaction conditions Epoxide Ref. Remarks

yield (%)

1c Cyclooctene DCE, 20 ◦ C, 30 min (stoichiometric 80 [32] Superior oxidizing ability of W(VI) over Mo(VI)
oxidation)
1c Cyclohexene H2 O2 /EtOH:H2 O, 40 ◦ C, CH3 SO3 H 98 [36] Subsequent ethanolysis of the epoxide ring occurs
(0.05 M)
8b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1.3 h 88 [59] Complex generated in situ
8b 2-Propen-1-ol H2 O2 /DCE:H2 O,70 ◦ C, 3 h 12 [58] Highest TOF observed for 12b
11b 2-Propen-1-ol H2 O2 /DCE:H2 O, 70 ◦ C, 1 h 53 [58]
11b Cinnamyl alcohol H2 O2 /dioxane, 70 ◦ C, 24 h 34 [58]
12b 2-Propen-1-ol H2 O2 /DCE:H2 O, 70 ◦ C, 0.5 h 40 [58]
12b Cinnamyl alcohol H2 O2 /dioxane, 70 ◦ C, 23 h 28 [58]
13b 2-Propen-1-ol H2 O2 /DCE:H2 O, 70 ◦ C, 9 h 50 [58]
14b Cyclohexene H2 O2 /benzene:H2 O, 75 ◦ C, 3 h 8 [60] Low epoxide yield.
[Ph3 PCH2 Ph]2 [6] Cyclooctene H2 O2 /DCE:H2 O, 50 ◦ C, 15 h 88 [65] Reaction is run in nearly neutral conditions and no need to buffer the aqueous

M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100

solution; allylic alcohols very rapidly epoxidized
K2 [6] 2-Propen-1-ol H2 O2 /H2 O, 32 ◦ C, 10 h 95 [66] Efficient epoxidation in water without using phase transfer catalysts
K2 [6] 2-Hexen-1-ol H2 O2 /H2 O, 32 ◦ C, 5 h 98 [67]
(TBA)2 [25] MBO H2 O2 /CD3 CN, 32 ◦ C, 8 h 16 [69] H2 O2 efficiency only 23%
(THA)2 [25] Cyclooctene H2 O2 /CH3 CN, reflux, 4 h 100 [85] Same results obtained under N2 atmosphere
(TBA)2 [25] Cyclooctene CH3 CN, RT, 42 h (stoichiometric 2 [84] Stoichiometric epoxidation with 26 gave the corresponding epoxides and 25
oxidation)
(TBA)2 [26] Cyclooctene CH3 CN, RT, 42 h (stoichiometric 97 [84]
oxidation)
[HHIm]2 [25] Cyclooctene H2 O2 /CH3 OH:H2 O, 55 ◦ C, 4 h 54.4 [90] Catalysts can be easily recovered
[HDIm]2 [25] Cyclooctene H2 O2 /CH3 OH:H2 O, 55 ◦ C, 4 h 100 [90] and reused
[HMIm]2 [25] Cyclooctene H2 O2 /CH3 OH:H2 O, 55 ◦ C, 4 h 26.6 [90]
[DMIm]2 [25] Cyclooctene H2 O2 /CH3 OH:H2 O, 55 ◦ C, 4 h 100 [90]
(TBA)2 [SO4 {WO(O2 )2 }2 ] MBO H2 O2 /CD3 CN, 32 ◦ C, 8 h 69 [69] Catalytic activity of the dinuclear peroxo-tungstates with
(TBA)2 [HAsO4 {WO(O2 )2 }2 ] MBO H2 O2 /CD3 CN, 32 ◦ C, 8 h 12 [69] XO4 n− ligands: Se > S > As > P > Si; the low Lewis acidity of
(TBA)2 [33] MBO H2 O2 /CD3 CN, 32 ◦ C, 8 h 6 [69] W in 16 results in high catalytic activity for epoxidation
(TBA)2 [15a] MBO H2 O2 /CD3 CN, 32 ◦ C, 8 h 1 [69]
(TBA)2 [16] cyclohexene H2 O2 /CH3 CN, 50 ◦ C, 40 min 88 [93]
(TBA)2 [SO4 {WO(O2 )2 }2 ] cyclohexene H2 O2 /CH3 CN, 50 ◦ C, 40 min 18 [93]
(TBA)2 [HAsO4 {WO(O2 )2 }2 ] cyclohexene H2 O2 /CH3 CN, 50 ◦ C, 40 min 4 [93]
(TBA)2 [33] cyclohexene H2 O2 /CH3 CN, 50 ◦ C, 40 min 2 [93]
(TBA)2 [15a] cyclohexene H2 O2 /CH3 CN, 50 ◦ C, 40 min 1 [93]
17a styrene TBHP/CCl4 , 60 ◦ C, 5 h 28 [74] Small enantiomeric excesses
17b styrene TBHP/CCl4 , 60 ◦ C, 5 h 29 [74]
WCl2 (O)(O2 )dppmO2 Cyclooctene H2 O2 /EtOH, 70 ◦ C, 6 h 98 [75] Lower reactivity for W- than for Mo-based catalysts in the presence of TBHP; the
W(O)(O2 )2 dppmO2 Cyclooctene H2 O2 /EtOH, 70 ◦ C, 6 h 90 [76] former showed superior reactivity to the latter for H2 O2 as the oxidant
19 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 50 min 93 [80] High yield, high TON, short reaction time
20 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 50 min 72 [80]
22 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 50 min 90 [80]
23 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 50 min 68 [80]
27a Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 76 [91] Significant decrease in catalytic efficiency in
27b Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 80 [91] the absence of NaHCO3 ; anionic complexes
27c Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 82 [91] showed the highest catalytic activity
27d Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 78 [91]
27e Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 86 [91]
28 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 74 [91]
29 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 89 [91]
30 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 96 [92] Mo and W complexes almost equally effective as epoxidation catalysts; for alcohol,
31 Cyclohexene H2 O2 :NaHCO3 /CH3 CN, RT, 1 h 99 [92] sulfide, and amine oxidation, W slightly more potent than Mo catalyst
34 Cyclohexene H2 O2 :NaHCO3 /CH2 Cl2 :CH3 OH, RT, 93 [100] Efficient catalysts in regard to epoxide yield and TON.
74.5 min
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 93

Fig. 11. Molecular structure of complex 34. Figure reproduced from reference [100] with the permission of the copyright holders.

tungsten(VI) peroxido complexes were immobilized for the first
time on functionalized gel and macroporous-type PS through pyri-
dine, pyridine-N-oxide, phosphine oxide (35a–e), phosphonic acid
(36a–d), and phosphonamide (37a,b and 38a,b) ligands (Fig. 12)
[101,102]. Cyclohexene epoxidation by H2 O2 was successful with
all five catalyst types. Catalyst screening revealed that the best TOF
was obtained with 38a. Cyclohexene epoxidation in dioxane solu-
tion at 70 ◦ C catalyzed by heterogeneous 38a gave cyclohexene
oxide as the main product, as well as the corresponding diol (∼20%).
Catalyst 38a could be recycled three times without a significant
decrease in catalytic activity.
The same research group reported on epoxidation with PMA-
based peroxido W(VI) catalysts (Fig. 13) [103]. PMA, which is more
polar than PS, changes the relative diffusion rate of the olefin and
H2 O2 inside the beads and the hydrophilic–hydrophobic balance
around the catalytic site. Under reaction conditions similar to those
used for catalysts 35–38 [102], the heterogeneous catalyst 39a
(Fig. 13) led to efficient catalysis of cyclohexene epoxidation and
TOF values >1000 were obtained. In the case of catalyst 39b, 13% diol
formation was observed owing to the acidity of the macroporous
PMA support. Under similar reaction conditions, the homogeneous
catalyst WO(O2 )2 (HMPT) 1c (Fig. 1) led to a lower TOF value of
75. The higher catalytic activity of heterogeneous catalysts seems
to be accounted for by the lipophilic–hydrophilic balance inside
the polymer, allowing good diffusion of both polar H2 O2 and non-
polar olefin [103]. In this case the support is not inert in catalysis
and its properties can play an important role. The characteristics
can be tuned by appropriate modification of the support surface
to obtain an optimal hydrophilic–hydrophobic balance for efficient
mass transfer of reagents.
In 2000, Gelbard briefly reviewed work on alkene epox-
idation with peroxido tungsten(VI) catalysts immobilized on
organophosphoryl-functionalized polymers [104]. Gelbard et al.
also reported on cyclohexene epoxidation with peroxotungstic
species supported on PMA ammonium resins 40a–e (Fig. 13) [103].
Compared to 39a and 39b, catalysts 40a–e exhibited poorer activity
and selectivity toward the epoxy product.
In an identical approach, dimer 6 (Fig. 3) was electrostatic-
ally immobilized on amberlite IRA-900 (catalyst 41) [105,106].

R
PS P
R
O O PS PO3(WO5)2 (Q+)2
O
W
O O
O
35a; PS= BioBeads, R= Ph 36a; Q=Oct3MeN
35b; PS= BioBeads, R= octyl 36b; Q=Bu4N
35c; PS= XAD4, R= octyl
35d; PS= XAD4, R= Ph
35e; PS= XAD16, R= Ph

NMe2 Me NMe2

PS P PS CH2N P
NMe2 NMe2
O O O O
O O
W W
O O O O
O O
37a; PS= Phosphonic resin LES63 38a; PS= BioBeads SX1
37b; PS= BioBeads SX1 38b; PS= Duolite A369

Fig. 12. Peroxido tungsten(VI) catalysts immobilized on organophosphoryl-

functionalized PS [102]. Fig. 13. Polymethacrylate-based peroxido W(VI) catalysts [103,104].
94 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100
Fig. 14. W(VI), Mo(VI), and V(V) peroxido complexes immobilized on PS through the chelating ligands 2-pybmz and 3-pybmz [107].
Amberlite IRA-900 resin is a macroreticular PS containing quater-
nary ammonium groups. The catalyst was used for cyclooctene
oxidation by H2 O2 and provided a moderate yield of the corre-
sponding epoxide (19%, 16 h). Catalyst screening studies revealed
that 41 did not consume the oxidant in a very efficient manner.
Peroxido complexes of W(VI), Mo(VI), and V(V) were immo-
bilized on PS crossed-linked with 5% divinylbenzene using the
chelating ligands 2-pybmz and 3-pybmz to give PS-[MO(O2 )2 (L)]
(M = W, Mo, and V) (Fig. 14) [107]. For styrene epoxidation by H2 O2 ,
the vanadium catalysts showed the best results in terms of activ-
ity and selectivity toward the desired epoxide product. Use of 42a
and 43a as catalysts for styrene oxidation in refluxing acetonitrile
resulted in poor catalytic activity (8–9.5% conversion). Selectivity to
the epoxide was also poor, and benzaldehyde was identified as the
main product. When TBHP was used as the oxygen source, the for-
mation of epoxide predominated, but the styrene conversion was
still less than 10%.
The catalytic activity of the polybenzimidazole grafted W(VI)
peroxido complexes 44a and 44b (Fig. 15) was measured for cyclo-
hexene epoxidation with H2 O2 in dioxane [103]. The epoxidation
activity and selectivity of the catalysts were poor. Catalyst 44a, for
instance, showed TOF as low as 44 h–1 and 44b led to slightly better
results (TOF = 74 h–1 ).
3.2. Silica-anchored catalysts
Immobilization of W(VI) peroxido complexes on silica supports
is another approach to obtain novel heterogeneous catalysts for
olefin epoxidation. Brégeault et al. demonstrated this approach
in the preparation of the heterogeneous olefin epoxidation cata-
lysts via electrostatic anchoring of the [HPO4 {WO(O2 )2 }2 ]2− anion
33 on siliceous supports (pure beads, 45a; and mesoporous Si-
MCM-41, 45b) [108]. Here, the anionic complex is electrostatically
fixed to Si-OH2 + groups on the silica surface. 31 P NMR revealed
Fig. 15. Two polybenzimidazole-grafted W(VI) peroxido complexes [104].
that 33 was immobilized on the silica surface without significant
deformation, but different immobilized species were observed for
Si-MCM-41. For the complex supported on silica beads, H2 O2 epox-
idation of cyclooctene in H2 O/t-BuOH at RT led to the formation of
cyclooctene oxide in 99% yield.
Like silica beads, the titanium silicate (TS-1) surface can anchor
anionic oxido–peroxido W(VI) complexes. Brégeault et al. tested
the [HPO4 {WO(O2 )2 }2 ]2− anion 33 supported on TS-1 (catalyst
46a) in the epoxidation of (R)-(+)-limonene [109]. The substrate
conversion obtained was rather good (75%), but the epoxide selec-
tivity was not high (53%) and substantial amounts of diol were
also produced. Overoxidation to diol was attributed to the Brønsted
acidity of the support surface. For anion 33 grafted onto phosphate-
modified TS-1 (catalyst 46b) complete conversion of substrate was
achieved within 6 h, but only a trace of epoxide was observed. 1,2-
Diol was obtained as the major product in 53% yield.
A heterogeneous W(VI) peroxido catalyst was synthesized by
covalent anchoring of WO5 on phosphoramide-grafted silica, K10
montmorillonite, and hectorite (Fig. 16) [110]. In this study, the
ligands and tungsten complex are covalently bonded to the sur-
face. The catalysts were treated with a solution of HCl and a hot
solution of H2 O2 to remove electrostatically bound W(VI) species.
The catalytic activity and selectivity of the catalysts depended on
the nature of both the support and the ligand. The catalytic activ-
ity of 47a in the oxidation of cyclohexene in water/dioxane solvent
was the highest (TOF = 140 h−1 ). In a similar process, catalysts 47b
and 47c had TOF of 42 h−1 and 124 h−1 , respectively. In general
TOF for the supports varied in the order bead-shaped silica > K10
montmorillonite > sol–gel-prepared amorphous silica > hectorite.
The neutrality of the surface and the bond strength between the
ligand and the support may contribute to this behavior. Under sim-
ilar reaction conditions, all catalysts showed poor performance in
the oxidation of conjugated aromatic alkenes such as styrene and
␤-methylstyrene (TOF < 8 h−1 ). Recycling experiments for catalysts
recovered by hot filtration revealed significant decreases in cat-
alytic activity and selectivity. Elemental analyses for the recovered
materials revealed that the tungsten content decreased by 3–10%
after each use.
In 2004, Liu et al. elegantly synthesized a hybrid cat-
alyst by immobilizing the oxido–peroxido W(VI) compound
{HPO4 [W(O)(O2 )2 ]2 } 33 on the surface of HMS and exchanging Pd
ions into the HMS channels (catalyst 50) (Fig. 17) [111]. The hybrid
catalyst showed 34.1% propylene conversion and 83.2% selectiv-
ity for propylene oxide for oxidation of propylene using molecular
oxygen as an oxidant at 100 ◦ C. Acetone, acrolein, propionaldehyde,
propane, and C4 –C6 hydrocarbons were obtained as by-products.
Remarkably, HMS-immobilized {HPO4 [W(O)(O2 )2 ]2 } (without Pd
ions) displayed high selectivity for epoxide product but the sub-
strate conversion was only 1.7%. This highlights the importance of
Pd ions in the catalyst structure. Interestingly, oxygenated com-
pounds formed from methanol co-oxidation (such as formic acid
and formaldehyde) were detected in small amounts after catalytic
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100
Fig. 16. Heterogeneous W(VI) oxido–bisperoxido catalysts used by Gelbard et al. [110].
reaction, indicating that a proportion of the methanol solvent was
co-oxidized during propylene oxidation. This finding is consistent
with a mechanism in which Pd2+ reduction by methanol generates
Pd0 , which then activates molecular oxygen to oxidize methanol to
a hydroxymethyl hydroperoxide (HOCH2 OOH) intermediate [112].
The HOCH2 OOH intermediate probably plays a role in regenerating
the O O bonds of the immobilized W(VI) complex.
Although the homogeneous catalyst
(Pd(OAc)2 + {HPO4 [W(O)(O2 )2 ]2 }2− 33) showed higher con-
version than that over the hybrid catalyst but the hybrid catalyst
could be reused five times by a simple filtration method without
loss of the catalytic activity and selectivity.
In the same year, Parvulescu et al. reported successful immo-
bilization of WO(O2 )2 units on HA [113]. To this end, HA was
suspended in different concentrations of H2 [25] solution either
at room temperature or in an autoclave at 90 or 120 ◦ C (Table 2).
The shift in 31 P CP/MAS NMR spectrum and FT-IR data for the HA-
supported tungsten catalysts suggest that the tungsten complex
is anchored via OH groups of the HA. The catalysts were tested
in heterogeneous epoxidation of cyclohexene. In all cases, the
Fig. 17. Model of hybrid catalyst 50 [111].
95
corresponding diol was the main reaction product. Even catalyst
51b, which exhibited the highest catalytic activity and selectivity,
only showed 30% epoxide selectivity. The authors noted a slight
increase in epoxide selectivity and TOF in the second catalytic
cycle. In addition, catalysts 51a, 51b, and 51e were lipophilized
and buffered by partial exchange of the remaining H+ with Bu4 N+ .
The catalytic activity and selectivity of the buffered catalysts were
lower than for 51a–e.
A tungsten(VI) oxido–peroxido complex was also deposited on
a HA support using a suspension of HA in a DCM solution of
[AliQ]2 [W2 O11 ] (catalyst 51f) [113]. Oxidation of cyclohexene with
catalyst 51f and H2 O2 as oxidant did not reach completion (20%
after 10 h) and the epoxide selectivity was only 4%.
Fraissard et al. designed heterogeneous catalysts 52–60 for
epoxidation of cyclooctene and (R)-limonene based on function-
alized silica Si(CH2 )3 Q+ [Q = NH3 , NEt3 , NC5 H5 , PPh3 ] with
different surface lipophilicity and [HPO4 {WO(O2 )2 }2 ]2− anion 33
(Fig. 18) [114]. Using 52 or 57 as a catalyst and H2 O2 as a terminal
oxidant, complete conversion of cyclooctene to cyclooctene oxide
was achieved in t-BuOH (TOF 35 h−1 for 52 and 8.8 h−1 for 57).
Catalysts 54 and 55 showed conversion of 50% and 66%, respec-
tively, within 24 h (TOF 2.6 h−1 for both). Other solids were less
active. Comparison of results for heterogeneous catalysts 52–60
revealed that the structure of the onium salt has only a minor
Table 2
Preparation conditions and tungsten content for catalysts 51a–e [113].
Catalyst Preparation temperature (◦ C) W content (%)
51a 90 3.54
51b Room temperature 3.65
51c 120 3.30
51d 120 3.80
51e 120 2.95
96 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100

Fig. 18. Heterogeneous W(VI) catalysts used by Fraissard et al. [114].

impact on catalyst performance, but the preparation method and
lipophilicity of the support have considerable effects on catalyst
activity and reusability. Catalysts with a hydrophilic support sur-
face (52, 55, 57, and 59) displayed high catalytic activity in the
first run, but were rapidly deactivated. Conversely, supports with a
lipophilic surface gave catalysts that were less active but relatively
more stable in the consecutive runs. Catalysts 54, and 56 based
on these supports were quite stable in three consecutive runs. The
hydrophilic surface of catalyst can contribute to the poisoning by
adsorption of polar epoxides and deactivated species and lead to
faster catalyst deactivation. The end-capping SiMe3 fragments
on the catalyst surface should result in greater stability of PW2
anions toward poisoning. Nevertheless, end-capping reduce the
accessibility of the active sites to some degree and lead to less active
catalyst.
A mesoporous SBA-15 material containing oxido–bisperoxido
W(VI) complexes of the type [WO(O2 )2 L] (L = pyrazolylpyridine
61a, ethylenediamine 61b, imidazole 61c, and 4,4 -bipyridine 61d)
was synthesized via a post-grafting route (Fig. 19) [115]. All four W-
containing solids were active catalysts for oxidation of cyclooctene
using hydrogen peroxide as an oxidant, although only 61a showed
acceptable reusability. For 61b–d, a sharp decrease in catalytic
activity was noted after the first run, probably due to a change in
the coordination environment of the tungsten active sites during
the catalytic reaction. Comparison of the results showed that the
catalytic activity varied in the order, 61a (TOF 143 h−1 ) > 61d (TOF

Fig. 19. The heterogeneous W(VI) oxido-bisperoxido catalysts 61a–d [115].

 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 97

Fig. 20. Dimer 6 immobilized on silica modified with ionic liquid [119,120].

109 h−1 ) > 61c (TOF 54 h−1 ) > 61b (TOF 17 h−1 ). The heterogeneous
catalyst 61a could be recycled six times without any loss of activity
because of the strong binding between WO(O2 )2 and the chelating
ligand [115].
For selective oxidation of olefins to epoxides via heterogeneous
W(VI) catalysis, the acidity of the support should first be con-
sidered [102,110]. If a highly acidic support is used, the epoxide
can undergo ring opening and further oxidation to give various
products. Vafaeezadeh et al. reported on catalytic oxidation of
cyclohexene to adipic acid with hydrogen peroxide over 1-butyl-
3-methylimidazolium tungstate ([BMIm]2 WO4 ) IL supported on
silica sulfamic acid, without any formation of epoxide or diol prod-
ucts [116]. In such a catalytic system, the epoxide is formed first
and then reacts with the silica-supported acid catalyst in solution
to form adipic acid [117,118].
Mizuno et al. used dimer 6 (Fig. 3) immobilized on IL-modified
SiO2 (62) (Fig. 20) as an efficient heterogeneous epoxidation cata-
lyst with hydrogen peroxide [119,120]. The catalytic activity of 62
for epoxidation is comparable to that of the homogeneous analog
[n-C12 H25 N(CH3 )3 ]2 [6] under the same conditions. This result indi-
Fig. 21. Oxido–bisperoxido W(VI) catalysts 63a and 63b [121].
cates that a homogeneous W(VI) catalyst can be immobilized with
retention of catalytic activity on IL-modified silica as a support.

3.3. Magnetically recyclable catalysts

oxidation of allylic alcohols and obtained the corresponding epox-
ides with excellent chemoselectivity. The catalyst could be recycled
Recent interest has focused on the use of magnetic nanoparticles
up to five times with just a minimum decrease in catalytic activity,
as for immobilization of homogeneous catalysts. The active cat-
after which the chitosan was destroyed, the catalyst was lost in the
alytic species, an IL-type oxido–bisperoxide tungsten(VI) complex,
reaction solution, and the recovery efficiency gradually decreased.
was immobilized via either hydrogen bonding (63a) or covalent
Table 3 summarizes results for catalytic epoxidation of alkenes
Si O linkage (63b) on silica-coated Fe3 O4 nanoparticles (Fig. 21)
by heterogeneous W(VI) oxido–peroxido catalysts. Interested read-
[121]. Immobilization of the IL via hydrogen bonding led to a sharp
ers are referred to the original articles for details on the reaction
increase in the tungsten complex loading. Both 63a and 63b were
conditions.
used as heterogeneous catalysts for epoxidation of a wide vari-
The main difference between heterogeneous and homogeneous
ety of olefins with H2 O2 as the oxygen source. For catalyst 63b,
catalysts is that every single catalytic entity in a homogeneous cata-
cyclooctene was completely converted to the cyclooctene oxide
lyst can act as a single active site. Therefore, homogeneous catalysts
within 3 h in H2 O/CH3 OH (1:10). Similarly, catalyst 63a displayed
are intrinsically more active and selective compared to heteroge-
excellent activity for alkene epoxidation and could be reused in
neous catalysts. The main advantages of heterogeneous catalysts
water/methanol up to a remarkable ten times with consistent activ-
are their simple separation and reutilization, but a major drawback
ity. Interestingly, the solvent has a significant effect on recovery of
is leaching of the catalyst during use and recycling, which lead to
the catalyst. The conversion dramatically decreased after the first
deactivation.
cycle when pure methanol or ethanol was used as the solvent. It
seems that water molecules help to stabilize hydrogen bond inter-
actions between the terminal Si OH groups of the silica layer and
silanol functionalities in the IL [122]. A catalytic system with 63a
could be used for epoxidation of several olefins and allylic alcohols
under mild conditions.
In an alternative approach, Lu et al. prepared and character-
ized a novel magnetically recyclable catalyst in which protonated
[W2 O11 ]2− was immobilized in a network of cross-linked chitosan
with a Fe3 O4 magnetic core (64, Fig. 22) [123]. This heteroge-
neous catalyst showed high conversion of 72–88% for the oxidation
of cyclic and linear alkenes when H2 O2 was used as the oxi-
dant (71–86% selectivity). The authors also used the catalyst for Fig. 22. Magnetically recyclable catalyst 64 [123].
98 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100

Table 3
Summary of results for catalytic epoxidation of alkenes by heterogeneous oxido–peroxido W(VI) catalysts.

W complex Substrate Reaction conditions Epoxide Ref. Remarks

yield (%)

35a Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1 h 54 [102] Best TOF was obtained with 38a
35b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1 h 56 [102]
35c Cyclohexene H2 O2 /dioxane, 70 ◦ C, 3 h 44 [102]
35d Cyclohexene H2 O2 /dioxane, 70 ◦ C, 3 h 60 [102]
35e Cyclohexene H2 O2 /dioxane, 70 ◦ C, 4 h 77.5 [102]
36a Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1 h 88 [102]
36b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 23 h 71 [102]
37a Cyclohexene H2 O2 /dioxane, 70 ◦ C, 3 h 55 [102]
37b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1.5 h 15 [102]
38a Cyclohexene H2 O2 /dioxane, 70 ◦ C, 0.5 h 59 [102]
38b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 1 h 65 [102]
40a Cyclohexene H2 O2 /dioxane, 70 ◦ C, 50 min 38 [103] Lipophilic–hydrophilic balance inside the
40b Cyclohexene H2 O2 /dioxane, 70 ◦ C, 4 h 84 [103] polymeric beads allows good diffusion of all
40c Cyclohexene H2 O2 /dioxane, 70 ◦ C, 4 h 65 [103] reactants and product
40d Cyclohexene H2 O2 /dioxane, 70 ◦ C, 4 h 68 [103]
40e Cyclohexene H2 O2 /dioxane, 70 ◦ C, 3 h 54 [103]
41 Cyclooctene H2 O2 /CH3 CN, 50 ◦ C, 16 h 19 [105] Low-efficiency catalyst
42a Styrene H2 O2 /CH3 CN, 80 ◦ C, 6 h Trace [107] Oxidative cleavage of double bond
42a Styrene TBHP/CH3 CN, 80 ◦ C, 6 h 3 [107] and formation of benzaldehyde
43a Styrene H2 O2 /CH3 CN, 80 ◦ C, 6 h Trace [107]
43a Styrene TBHP/CH3 CN, 80 ◦ C, 6 h 2 [107]
44a Cyclohexene H2 O2 /dioxane, 70 ◦ C 27 [107]
44b Cyclohexene H2 O2 /dioxane, 70 ◦ C 42 [104] Catalyst can be reused five times without any loss of reactivity
45a Cyclooctene H2 O2 /t-BuOH, RT, 24 h 99 [108] High leaching of W complex, low catalyst stability
46a (R)-Limonene H2 O2 /acetone, RT, 24 h 40 [109] Brønsted acidity of the support surface converted the
46b (R)-Limonene H2 O2 /acetone, RT, 24 h Trace [109] epoxide to diol
47a Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 96 [110] Nature of the support has a significant effect on the
47b Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 97 [110] epoxidation reaction efficiency
47c Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 86 [110]
47d Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 25 [110]
48 Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 92 [110]
49 Cyclohexene H2 O2 /dioxane, 60 ◦ C, 6 h 91 [110]
50 Propylene O2 /CH3 OH, 100 ◦ C, 6 h 28 [111] Selectivity for epoxide over the solid catalyst was similar to
that over a homogeneous catalyst, but conversion was lower
over the former than over the latter
52 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 6 h 100 [114] Catalyst efficiency and product yield depend on the
53 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 24 h 12 [114] preparation method and lipophilicity of the support
54 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 24 h 49 [114]
55 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 24 h 66 [114]
56 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 5 h 100 [114]
57 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 24 h 60 [114]
58 Cyclooctene H2 O2 /t-BuOH, 70 ◦ C, 24 h 37 [114]
59 Cyclooctene H2 O2 /t-BuOH, 22 ◦ C, 24 h 24 [114]
54 (R)-Limonene H2 O2 /t-BuOH, 22 ◦ C, 24 h Trace [114]
56 (R)-Limonene H2 O2 /t-BuOH, 22 ◦ C, 24 h 70 [114]
60 (R)-Limonene H2 O2 /t-BuOH, 22 ◦ C, 0.3 h 1 [114]
61a Cyclooctene H2 O2 /CH3 CN, 55 ◦ C, 10 h 76 [115] Only 61a showed good recoverability and high stability
61b Cyclooctene H2 O2 /CH3 CN, 55 ◦ C, 3 h 83 [115] against leaching
61c Cyclooctene H2 O2 /CH3 CN, 55 ◦ C, 6 h 84 [115]
61d Cyclooctene H2 O2 /CH3 CN, 55 ◦ C, 10 h 65 [115]
62 Cyclooctene H2 O2 /CH3 CN, 55 ◦ C, 1 h 99 [119] Excellent epoxide yields, short reaction time, green approach
63a Cyclooctene H2 O2 /CH3 OH:H2 O, 60 ◦ C, 3 h 99 [121] Catalysts can be recycled 10 times with no loss of catalytic
63b Cyclooctene H2 O2 /CH3 OH:H2 O, 60 ◦ C, 3 h 99 [121] properties by simple magnetic decantation
64 Cyclooctene H2 O2 /CH3 CN, 40 ◦ C, 12 h 86 [123] For equimolar olefin:alcohol, the olefin was the first to be
oxidized

4. Conclusions and outlook
The chemistry of Mo(VI) and W(VI) is quite similar in many
cases [30]. However, some deviations in physicochemical prop-
erties (such as Pauling electronegativity, ionic radius, and Lewis
acid strength of the cations) exist between these two species
[124]. These differences may in turn result in different cat-
alytic activity of Mo and W complexes. Mo(VI) oxido–peroxido
complexes have been known as among the most efficient cata-
lysts for epoxidation [29]. W(VI) oxido–peroxido complexes are
even more efficient catalysts than the corresponding Mo(VI)
species, and the ability of these complexes to catalyze epox-
idation has attracted major research interest during the last
20 years.
We have described progress made in the area of W(VI)-catalyzed
epoxidation. Comparison of the activity of the various catalysts
considered in this review suggests the following conclusions:
(a) W(VI) oxido–bisperoxido complexes act not only as epoxidation
catalysts but also as stoichiometric reagents in the epoxidation
of olefins. Oxygen transfer rates are much greater from W(VI)
bisperoxido complexes to alkenes than from the corresponding
Mo(VI) species [32,61].
(b) In the presence of W(VI) peroxido complexes, oxidation of allylic
alcohols is several orders of magnitude faster than for sim-
ple olefins. The mechanism of this epoxidation depends on the
existence (or absence) of an easily replaceable ligand on W.
 M. Amini et al. / Coordination Chemistry Reviews 268 (2014) 83–100 99

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