Axial base-controlled catalytic activity, oxidative stability and product selectivity of water-insoluble manganese and iron porphyrins for oxidation of styrenes in water under green conditions

Article abstract of DOI:10.1002/aoc.4117

A series of water-insoluble iron(III) and manganese(III) porphyrins, FeT(2-CH₃)PPCl, FeT(4-OCH₃)PPCl, FeT(2-Cl)PPCl, FeTPPCl, MnT(2-CH₃)PPOAc, MnT(4-OCH₃)PPOAc, MnT(2-Cl)PPOAc and MnTPPOAc, in the presence of imidazole (ImH), F^?, Cl^?, Br^? and acetate were used as catalysts for the aqueous-phase heterogeneous oxidation of styrenes to the corresponding epoxides and aldehydes with sodium periodate. Also, the effect of various reaction parameters such as reaction time, molar ratio of catalyst to axial base, type of axial base, molar ratio of olefin to oxidant and nature of metal centre on the activity and oxidative stability of the catalysts and the product selectivity was investigated. Higher catalytic activities were found for the iron complexes. Interestingly, the selectivity towards the formation of epoxide and aldehyde (or acetophenone) was significantly influenced by the type of axial base. Furthermore, Br^? and ImH were found to be the most efficient co-catalysts for the oxidation of olefins performed in the presence of the manganese and iron porphyrins, respectively. The optimized molar ratio of catalyst to axial base was different for various axial bases. Also, the order of co-catalyst activity of the axial bases obtained in aqueous medium was different from that reported for organic solvents. The use of a convenient axial base under optimum reaction catalyst to co-catalyst molar ratio in the presence of the manganese porphyrin gave the oxidative products with a conversion of ca 100% in a reaction time of less than 3?h. However, the catalytic activity of the iron porphyrins could not be effectively improved by increasing the catalyst to co-catalyst molar ratio.

Full text of DOI:10.1002/aoc.4117

Received: 24 July 2017
DOI: 10.1002/aoc.4117
Revised: 28 August 2017
Accepted: 30 August 2017
F U L L P A P E R
Axial base‐controlled catalytic activity, oxidative stability
and product selectivity of water‐insoluble manganese and
iron porphyrins for oxidation of styrenes in water under
green conditions
Saeed Zakavi
| Akbar Hashemi‐Amiri | Fatemeh Asadi
Department of Chemistry, Institute for
Advanced Studies in Basic Sciences
(IASBS), Zanjan, Iran
A series of water‐insoluble iron(III) and manganese(III) porphyrins, FeT(2‐
CH3)PPCl, FeT(4‐OCH3)PPCl, FeT(2‐Cl)PPCl, FeTPPCl, MnT(2‐CH3)PPOAc,
MnT(4‐OCH3)PPOAc, MnT(2‐Cl)PPOAc and MnTPPOAc, in the presence of
imidazole (ImH), F−, Cl−, Br− and acetate were used as catalysts for the aque-
ous‐phase heterogeneous oxidation of styrenes to the corresponding epoxides
and aldehydes with sodium periodate. Also, the effect of various reaction
parameters such as reaction time, molar ratio of catalyst to axial base, type of
axial base, molar ratio of olefin to oxidant and nature of metal centre on the
activity and oxidative stability of the catalysts and the product selectivity was
investigated. Higher catalytic activities were found for the iron complexes.
Interestingly, the selectivity towards the formation of epoxide and aldehyde
(or acetophenone) was significantly influenced by the type of axial base.
Furthermore, Br− and ImH were found to be the most efficient co‐catalysts
for the oxidation of olefins performed in the presence of the manganese and
iron porphyrins, respectively. The optimized molar ratio of catalyst to axial base
was different for various axial bases. Also, the order of co‐catalyst activity of
the axial bases obtained in aqueous medium was different from that reported
for organic solvents. The use of a convenient axial base under optimum reaction
catalyst to co‐catalyst molar ratio in the presence of the manganese porphyrin
gave the oxidative products with a conversion of ca 100% in a reaction time of
less than 3 h. However, the catalytic activity of the iron porphyrins could not
be effectively improved by increasing the catalyst to co‐catalyst molar ratio.
Correspondence
Saeed Zakavi, Department of Chemistry
Institute for Advanced Studies in Basic
Sciences (IASBS), Zanjan 45137‐66731,
Iran.
Email: zakavi@iasbs.ac.ir
Funding information
Iran National Science Foundation (INSF),
Grant/Award Number: 95816928; Institute
for Advanced Studies in Basic Sciences
(IASBS)
KEYWORDS
heterogeneous catalysis, oxidation in water, periodate, styrenes, water‐insoluble metalloporphyrins
1 | INTRODUCTION
catalysts is among the main strategies employed to over-
come the problems associated with the oxidative degrada-
Biomimetic oxidation of organic compounds catalysed by
metalloporphyrins under homogeneous and heteroge-
neous conditions has been extensively studied in the past
four decades.[1] The heterogenization of homogeneous
tion of metalloporphyrins. Also, the catalyst may be easily
separated from the reaction mixture and reused in the
case of heterogeneous catalysts.[1a,b,2] In this regard,
different bulk and nanosized supports have been used to
Appl Organometal Chem. 2017;e4117.
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Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4117

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ZAKAVI ET AL.
immobilize metalloporphyrins. Water is the best solvent
for such oxidation reactions from the green chemistry
point of view.[3] Cationic and anionic metalloporphyrins
may be used for the catalysis of oxidation reactions under
aqueous conditions. However, relatively elaborate syn-
thetic and purification procedures are required to intro-
duce water‐soluble groups at the periphery of porphyrin
macrocycles.[4] Furthermore, the stereoelectronic proper-
ties of the substituents introduced at the periphery of
porphyrin ligand for increasing the solubility in water
may have significant effects on the catalytic activity and
oxidative stability of metalloporphyrins.[5] Oxidation of
olefins to epoxides with tetra‐n‐butylammonium
periodate catalysed by cationic, anionic and neutral
manganese5b,6] and iron[5a,6f,g] porphyrins has been exten-
sively studied in dichloromethane. Also, the oxidation of
olefins with sodium periodate in a two‐phase CH2Cl2–
H2O solvent system was reported.[7] In these studies,
imidazole (ImH) was used as the co‐catalyst and the oxi-
dation of olefins afforded the corresponding epoxides as
the exclusive or major product.
FIGURE 2 Catalytic oxidation of styrenes with periodate in water
reaction conditions for the oxidation of styrenes catalysed
by MnT(4‐OCH3)PPOAc were investigated.
2.1 | Oxidation of olefins catalysed by
MnT(4‐OCH3)PPOAc
2.1.1 | Effect of reaction time
In the work presented here, a series of water‐insoluble
manganese and iron porphyrins (Figure 1) with different
groups at the meso positions and various anionic and neu-
tral co‐catalysts were used for the catalytic oxidation of
styrenes (Figure 2) with sodium periodate in water. Under
these conditions, the metalloporphyrin acts as a non‐
immobilized heterogeneous catalyst[5c,d] for the oxidation
of olefins in water, and consequently a decrease in the oxi-
dative degradation of the catalyst is expected. Also, the
catalyst may be separated using simple methods such as
filtration or centrifugation.
The results of oxidation of olefins with sodium periodate
(Figure 2) in the presence of MnT(4‐OCH3)PPOAc and
various co‐catalysts (Br−, Cl−, F−, OAc− and ImH) are
summarized in Table 1 and Tables S1–S4. As shown in
Figure 2, the corresponding aldehydes (or acetophenone
in the case of α‐methystyrene) and epoxides were
obtained as the major and minor products, respectively.
Due to incomplete degradation of catalyst after 3 h, the
effect of longer reaction times on the conversions was
studied. According to the data of Table 1, in the reaction
catalysed by MnT(4‐OCH3)PPOAc and Br−, with the
exception of 4‐methylstyrene, the oxidation of other ole-
fins was nearly completed after ca 9 h. When Cl− was
used as co‐catalyst (Table S1), nearly complete oxidation
of the olefins was observed after a reaction time of ca
19 h. In other words, longer times were needed for the
completion of reaction compared to those in the pres-
ence of Br− (Table 1). As was observed in the presence
of Br−, in the case of F− (Table S2), OAc− (Table S3)
and ImH (Table S4), the oxidation of 4‐methylstyrene is
inefficient and cannot be improved by an increase of
the reaction time. A comparison of Table 1 and
Tables S1–S4 shows that (i) the use of Br− as the axial
base and a reaction time of 5 h were the best conditions
for the oxidation of 4‐methoxystyrene; (ii) ImH was the
best co‐catalyst for the oxidation of α‐methylstyrene in
5 h; (iii) styrene was oxidized efficiently in the presence
of Br− after a time of 9 h; and (iv) for the oxidation of
4‐methylstyrene, Cl− was the best axial base for a
reaction time of 19 h.
2 | RESULTS AND DISCUSSION
The oxidation of styrenes with periodate in the presence
of various manganese and iron porphyrins in water has
been studied. With respect to the influence of various
parameters on the catalytic activity of metalloporphyrins
in polar and nonpolar solvents,[1a,5–8] the optimum
X
Ar
N
N
M
Ar
Ar
N
N
2
3
Ar
1
4
M = Fe(III) or Mn(III)
X = F, Cl, Br, Acetate
Ar
Porphyrin
Metalloporphyrin
FeTPPX
MnTPPX
Phenyl,
H2TPP
FeT(2-Cl)PPX
MnT(2-Cl)PPX
FeT(2-CH3)PPX
MnT(2-CH3)PPX
FeT(4-OCH3)PPX
MnT(4-OCH3)PPX
2-chlorophenyl,
H2T(2-Cl)PP
2-methylphenyl, H2T(2-CH3)PP
4-methoxyphenyl, H2T(4-OCH3)PP
Also, the following order of co‐catalytic activity was
observed for the oxidation of various styrenes:
FIGURE 1 Porphyrins and metalloporphyrins used in this study

ZAKAVI ET AL.
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TABLE 1 Effect of reaction time on MnT(4‐OCH3)PPOAc‐catalysed oxidation of styrenes with periodate in the presence of Br− in watera,b
Conversion (%)
time (3 h)
Conversion (%)
time (5 h)
Conversion (%)
time (7 h)
Conversion (%) time (9 h)
{epoxide selectivity, %}c
Conversion (%)
(time, h)
Alkene
35d
66
84
95 {65}
—
64e
89
94
96 {94}
—
94d
97 {60}
9
—
—
—
7d
12
14
23 (17 h) {75}
aMnT(4‐OCH3)PPOAc, co‐catalyst (Br−), olefin and periodate were used in 1:10:85:170 molar ratio.
bAll reactions were repeated at least three times and the average of them with an error of ca 5–10% are reported.
c,dCorresponding epoxide and para‐substituted benzaldehyde were obtained.
c,eα‐Methystyrene oxide and acetophenone formed as the major and minor products, respectively.
should participate in a substitution reaction with the coor-
dinated water molecule to show its co‐catalytic activity.
Therefore, the observed order of co‐catalytic activity for
ImH and the anionic co‐catalysts depends to some extent
on the rate of substitution of MnT(4‐OCH3)PP(IO4)(H2O)
by the used co‐catalysts.
The catalytic performance of metalloporphyrins
depends closely on the degree of oxidative degradation
of the catalyst under reaction conditions.[1a,b] The extent
of oxidative degradation of MnT(4‐OCH3)PPOAc in the
presence of the various co‐catalysts (Table 2) for the same
reaction time shows the following orders:
Styrene
ImH (92%) > OAc− (83%) > F−
(76%) > Cl− (70%) > Br− (63%).
ImH (86%) > Br− (76%) > Cl−
(65%) ≈ F− (63%) ≈ OAc− (62%).
α‐Methylstyrene
4‐Methoxystyrene Br− (80%) ≈ Cl− (78%) > OAc−
(72%) > ImH (63%) > F− (58%).
4‐Methylstyrene
OAc− (93%) ≈ ImH (92%) > Cl−
(70%) ≈ F− (67%) > Br− (44%).
It is observed that the better co‐catalytic activity of
ImH for the oxidation of styrene and α‐methylstyrene
cannot be generalized for the other styrenes.
The basic strength of ImH (pKa = 6.95[6c]), F−
(pKa = 3.18[9]) and acetate (pKa = 4.76[9]) leads to the
increasing of the pH value and the formation of a signifi-
cant amount of OH− anions which in turn may act as the
axial base. Also, F−, Cl− and acetate are strong hydrogen
bond acceptor species and accordingly are effectively
hydrated in aqueous solutions; the free energies of ionic
hydration for F−, Cl−, Br− and OAc− are −370.3, −340.4,
Styrene
Br− (95%) > ImH (67%) > OAc−
(54%) ≥ Cl− (50%) > F− (29%).
α‐Methylstyrene
ImH (94%) > Br (89%) ≈ F
−(88%) > Cl− (74%) > OAc− (60%).
4‐Methoxystyrene Br− (97%) > ImH (89%) > OAc−
(82%) ≈ F− (80%) > Cl− (69%).
4‐Methylstyrene
Cl− (20%) ≥ F− (18%) ≥ OAc−
(15%) = ImH (15%) ≈ Br− (14%).
−334.2[10a] and −231.6 kcal mol−1 [10b]
respectively. In
,
the case of ImH, the molecule is able to act as a strong
hydrogen bond donor and acceptor. Therefore, the order
of co‐catalytic activity of the other species is significantly
influenced by their hydration energy and consequently
does not correlate with that observed in aprotic solvents
such as dichloromethane.[11] On the other hand, the water
molecule easily occupies the vacant coordination site of the
five‐coordinate MnT(4‐OCH3)PPOAc. The co‐catalytic
activity of a given species requires the coordination of the
species to the metal centre.[6c] Accordingly, the species
It should be noted that the observed oxidative
degradation of MnT(4‐OCH3)PPOAc is much less than
that previously observed for the oxidation of olefins with
tetra‐n‐butylammonium periodate under homogeneous
conditions.[5b]
As is evident from Table 2, the selectivity of reaction
towards the formation of epoxide or carbonyl compounds
is markedly influenced by the type of co‐catalyst; the
presence of Cl− and Br− led to a decrease in the yield of
the epoxides.

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ZAKAVI ET AL.
TABLE 2 Effect of type of co‐catalyst (X) on MnT(4‐OCH3)PPOAc‐catalysed oxidation of styrenes with periodate in water at optimized
reaction timesa,b,c,d
Conversion (%) time Conversion (%) time Conversion (%) time Conversion (%) time Conversion (%) (time,
Alkene
(3 h) X = Br−
(5 h) X = F−
(7 h) X = Cl−
(9 h) X = OAc−
h) X = ImH
95 (9 h)
[63%]
{65}e
93 (23 h)
[76%]
{90}e
98 (19 h)
[70%]
{70}e
96 (15 h)
[83%]
{92}e
97 (17 h)
[92%]
{96}e
96 (9 h)
[76%]
{94}
97 (21 h)
[63%]
{100}
100 (17 h)
[65%]
{97}
98 (11 h)
[62%]
{100}
94 (5 h)
[86%]
{100}
97 (5 h)
[80%]
{60}
97 (17 h)
[58%]
{85}
97 (19 h)
[78%]
{68}
94 (21 h)
[72%]
{84}
98 (9 h)
[63%]
{93}
23 (17 h)
[44%]
{75}
31 (17 h)
[67%]
{87}
84 (19 h)
[70%]
{80}
31 (19 h)
[93%]
{89}
31 (19 h)
[92%]
{95}
aMnT(4‐OCH3)PPOAc, co‐catalyst, olefin and periodate were used in a ratio of 1:10:85:170.
bSee footnotes of Table 1.
cValues in parentheses show the best reaction times.
dValues in brackets represent catalyst oxidative degradation.
eValues show the epoxide selectivity (see also footnotes of Table 1).
100
100
80
80
60
60
40
40
20
0
20
0
0
50
100
150
0
50
100
150
(b) F- / Cat.
(a) Br- / Cat.
100
80
60
40
20
0
100
80
60
40
20
0
0
50
100
150
0
50
100
150
(d) OAc- / Cat.
(c) Cl- / Cat.
100
80
60
40
20
0
FIGURE 3 Effect of molar ratio of (a)
MnT(4‐OCH3)PPBr:Br−, (b) MnT(4‐OCH3)
PPF:F−, (c) MnT(4‐OCH3)PPCl:Cl−, (d)
MnT(4‐OCH3)PPOAc:OAc− and (e)
MnT(4‐OCH3)PPOAc:ImH on catalytic
activity of manganese porphyrin for
oxidation of styrene (solid curve), 4‐
methoxystyrene (dotted curve), α‐
0
50
100
150
methylstyrene (dashed curve) and 4‐
methylstyrene (dash‐dotted curve)
(e) ImH / Cat.

ZAKAVI ET AL.
5 of 13
anion in ca 1:20 molar ratio gave the maximum
conversion for the oxidation of styrene and α‐
methylstyrene (Figure 3d), a molar ratio of 1:1 was the
best one for the oxidation of 4‐methoxystyrene. Also, for
the oxidation reaction performed in the presence of
MnT(4‐OCH3)PPOAc and ImH (Figure 3e), molar ratios
of 1:10 to 1:20 were optimal for the oxidation of styrenes.
In the case of ImH, the decreased catalytic performance of
metalloporphyrins at high molar ratios of ImH to catalyst
was found to be due to the formation of metal(porphyrin)
(ImH)2 species,[6c,f,12] although the possibility of oxidation
of imidazole by high‐valent oxo metal species as a side
reaction cannot be excluded. It should be noted that the
ratio of 1:0 in Figure 3(e) corresponds to the use of
MnT(4‐OCH3)PPOAc in the absence of any co‐catalyst.
In other words, in Figure 3(e) the co‐catalytic activity of
ImH is compared with that of acetate anion. In contrast
to the other co‐catalysts, the catalytic activity of MnT(4‐
OCH3)PPOAc in the oxidation of 4‐methylstyrene may
be significantly increased by the presence of ImH as
co‐catalyst.
2.1.2 | Effect of molar ratio of MnT(4‐
OCH3)PPX to co‐catalysts
The catalytic activity of manganese and iron porphyrins
has been shown to be influenced by different nitrogen
donors and anionic ligands as co‐catalysts.[5,6a,6c,11]
However, the presence of these species may have either
positive or negative effects on the catalytic performance
of metalloporphyrins depending on the concentration of
the co‐catalyst.[5,12]
The results for the oxidation of styrenes with sodium
periodate using different molar ratios of MnT(4‐OCH3)
PPX to co‐catalyst (X = Br−, F−, Cl−, OAc− and ImH)
are shown in Figure 3. While an increase of MnT(4‐
OCH3)PPBr:Br− molar ratio from 1:0 up to approximately
1:30 was accompanied by an increase of the catalytic
activity of the catalyst, a further increase in the molar
ratio led to decreased conversion of styrenes to the oxida-
tive products (Figure 3a). However, different dependences
on the catalyst to Br− molar ratio were observed for the
oxidation of different olefins. Interestingly, Br− (also Cl−,
OAc− and F−; Figure 3) has little or no effect on the
catalytic activity of MnT(4‐OCH3)PPBr for the oxidation
of 4‐methylstyrene.
It is observed (Figure 3b) that in spite of the significant
increase in the catalytic activity of the catalyst for the
oxidation of 4‐methoxystyrene, the presence of excess
amounts of F− beyond a 1:1 molar ratio with respect to
[MnT(4‐OCH3)PP]+ (or 1:0 relative to MnT(4‐OCH3)
PPF) has no or a negative effect on the conversion of the
other styrenes.
In the case of chloride anion (Figure 3c), much higher
molar ratios of MnT(4‐OCH3)PPCl:Cl (ca 1:50 to 1:75)
are needed to achieve maximum conversion of styrenes.
Although the use of MnT(4‐OCH3)PPOAc and acetate
The results for the oxidation of styrenes catalysed by
MnT(4‐OCH3)PPX under the optimized conditions are
summarized in Table 3. The order of co‐catalytic activity
of the co‐catalysts used for the oxidation of styrenes is as
follows:
Styrene
Cl− > Br− > F− ≥ OAc− ≥ ImH.
Br− ≥ Cl− > OAc− > ImH > F−.
α‐Methylstyrene
4‐Methoxystyrene Br− ≥ Cl− ≥ F− ≥ ImH > OAc−.
4‐Methylstyrene
ImH > OAc− ≥ Br− ≥ Cl− ≥ F−.
It is observed that the non‐basic anions, i.e. bromide
and chloride, are usually better than the other
TABLE 3 Oxidation of styrenes with periodate in water under optimized molar ratio of MnT(4‐OCH3)PPX to co‐catalyst (X)a,b
Alkene
X = Br− conversion (%)c F− conversion (%) Cl− conversion (%) OAc− conversion (%) ImH conversion (%)
1:30:85:170 (52)
1:1:85:170 (30)
1:40:85:170 (56)
1:20:85:170 (26)
1:10:85:170 (24)
1:30:85:170 (94)
1:10:85:170 (33)
1:75:85:170 (93)
1:20:85:170 (69)
1:10:85:170 (53)
1:30:85:170 (97)
1:30:85:170 (9)
1:50:85:170 (92)
1:20:85:170 (7)
1:75:85:170 (95)
1:1:85:170 (8)
1:1:85:170 (85)
1:1:85:170 (10)
1:10:85:170 (89)
1:20:85:170 (31)
aMnT(4‐OCH3)PPX, co‐catalyst, olefin and periodate were used in a ratio of 1:X:85:170.
bAll reactions were repeated at least three times.
cValues in parentheses.

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ZAKAVI ET AL.
co‐catalysts. Also, for the most reactive olefin, 4‐
methoxystyrene, there is little difference between the
activity of the five co‐catalysts.
According to Table 3, although the reactivity of
styrenes in the presence of different co‐catalysts generally
catalyst, and therefore the optimized molar ratio of olefin
to oxidant should be investigated. Molar ratios of 1:1 to
1:3 were used and a ratio of 1:2 was found to be the best
one (Table 4 and Tables S5–S8). Further increase in the
molar ratio, in most cases, led to a decrease in the conver-
sions probably due to the increased oxidative degradation
of the catalyst.
decreases in the order 4‐methoxystyrene
>
α‐
methylstyrene > styrene > 4‐methylstyrene, there are
large differences between the relative reactivity of sty-
renes; 4‐methoxystyrene and α‐methylstyrene exhibit
nearly the same reactivities in the presence of Br− and
Cl−, but significantly different ones in the case of F−,
OAc− and ImH. Also, in all cases α‐methylstyrene shows
higher reactivity than styrene, indicating that the elec-
tronic effect of methyl substituent dominates over the ste-
ric effect of the group. This observation, in combination
with the results obtained for the oxidation of the two sty-
renes in the presence of the other metalloporphyrins
(discussed later), seems to be in favour of the involvement
of a high‐valent oxo metal species as the main active
oxidant[6c] a high‐valent metal oxo species and a six‐coor-
dinate metalloporphyrin‐periodato one are usually con-
sidered as the active intermediates in oxidation reactions
with periodate catalysed by manganese and iron
porphyrins.[5,6c] However, the former has less steric hin-
drance around the reaction centre.[6c] On the other hand,
protic solvents have been found to facilitate the departure
of leaving group (IO3−) and formation of high‐valent oxo
metal species.[8]
2.2 | Relative catalytic activity and
oxidative stability of manganese Porphyrins
The stereoelectronic properties of the meso‐ and β‐substit-
uents are among the main factors influencing the catalytic
activity and oxidative stability of metalloporphyrins.[13]
Accordingly, the catalytic performance of the manganese
porphyrins in the presence of various co‐catalysts has
been studied and compared (Table 5 and Tables S9–S12).
According to Table 5, catalytic activity of the manganese
porphyrins for the oxidation of styrenes in the presence
of bromide shows the following orders:
Styrene
MnT(2‐Cl)PPBr ≈ MnT(2‐CH3)PPBr
≈ MnTPPBr >> MnT(4‐OCH3)PPBr.
MnT(2‐Cl)PPBr ≈ MnT(2‐CH3)PPBr
≈ MnTPPBr ≥ MnT(4‐OCH3)PPBr.
α‐Methylstyrene
4‐Methoxystyrene MnT(4‐OCH3)PPBr
PPBr MnT(2‐CH3)PPBr >>
MnTPPBr.
≥
MnT(2‐Cl)
≥
4‐Methylstyrene
MnT(2‐CH3)PPBr > MnT(2‐Cl)PPBr
> MnTPPBr >> MnT(4‐OCH3)PPBr.
2.1.3 | Effect of molar ratio of olefin to
periodate
Also, the extent of oxidative degradation of the cata-
lysts decreases in the following orders:
Styrene: MnTPPBr > MnT(2‐CH3)PPBr ≈ MnT(2‐Cl)
PPBr ≥ MnT(4‐OCH3)PPBr.
The rate of oxidation reactions can be increased by
increasing the molar ratio of olefin to periodate. However,
this change may increase the oxidative degradation of the
TABLE 4 Effect of molar ratio of olefin to periodate on oxidation of styrenes catalysed by MnT(4‐OCH3)PPOAc in watera,b,c
Alkene:Oxidant 1:1 conversion
(%) [deg]
Alkene:Oxidant 1:2 conversion
(%) [deg]
Alkene:Oxidant 1:3 conversion(%)
[deg]
Alkene
21
56
41
[21]
[44]
[62]
53
93
45
[32]
[52]
[84]
75
95
77
[15]
[51]
[60]
7
8
7
[46]
[50]
[45]
aValues in brackets show the extent of oxidative degradation of the catalyst.
bCl− is the co‐catalyst.
cSee Table 3 for molar ratios.

ZAKAVI ET AL.
7 of 13
TABLE 5 Oxidation of styrenes catalysed by manganese porphyrins and optimized molar ratios of catalyst to Br− in watera,b
Conversion (%)
MnT(4‐OCH3)PPOAc
Conversion (%)
MnT(2‐CH3)PPOAc
Conversion (%)
MnT(2‐Cl)PPOAc
Conversion (%)
MnTPPOAc
Alkene
50
[46]c
99
[52]
100
[50]
98
[67]
94
99
100
99
[38]
[78]
[70]
[67]
97
89
94
65
[67]
[32]
[57]
[58]
9
93
76
44
[64]
[21]
[55]
[61]
aMolar ratios of catalyst, Br−, olefin and periodate were 1:X:85:170 (see Table 3 for values of X).
bFor a reaction time of 3 h; the average of at least three runs are reported.
cValues in the brackets show the degree of oxidative degradation of the catalysts.
α‐Methylstyrene: MnT(2‐CH3)PPBr > MnT(2‐Cl)PPBr
≥ MnTPP(Br) > MnT(4‐OCH3)PPBr.
4‐Methoxystyrene: MnT(4‐OCH3)PPBr > MnTPPBr ≈
MnT(2‐Cl)PPBr > MnT(2‐CH3)PPBr.
4‐Methylstyrene: MnT(4‐OCH3)PPBr > MnTPPBr >
MnT(2‐Cl)PPBr >> MnT(2‐CH3)PPBr.
performed in the presence of different co‐catalysts. The
co‐catalytic activities of ImH and the anionic axial bases
decrease as ImH > Br− > OAc− ≥ Cl− ≥ F−. Also, the oxi-
dative degradation of FeT(4‐OCH3)PPX decreases in the
order ImH > OAc− > F− > Br− > Cl−.
These results in combination with those summarized
in Tables S9–S12 concerning the oxidation of styrenes in
the presence of the manganese porphyrins and the other
co‐catalysts show that: (i) for a given co‐catalyst, the man-
ganese porphyrins may show comparable catalytic activi-
ties (e.g. in the case of α‐methylstyrene, Table 5) or
significantly different ones (as in the case of 4‐
methylstyrene), depending on the nature of substituents
at the double bond as well as the phenyl ring of styrene;
(ii) the order of catalytic activity of the manganese por-
phyrins significantly depends on the type of co‐catalyst
and olefin; (iii) MnT(2‐Cl)PPX and MnT(2‐CH3)PPX usu-
ally show higher catalytic activity than the other manga-
nese porphyrins; and (iv) the oxidative stability of
electron‐rich MnT(4‐OCH3)PPX may be comparable to
or less than that observed for MnT(2‐Cl)PPX and
MnT(2‐CH3)PPX (e.g. Tables S9 and S10).
2.3.2 | Effect of molar ratio of FeT(4‐
OCH3)PPX to X
It was observed in the case of the manganese porphyrins
that the molar ratio of catalyst to co‐catalyst (X) may play
a crucial role in the catalytic performance of the
metalloporphyrins. The results for the oxidation of α‐
methylstyrene in the presence of FeT(4‐OCH3)PPX are
summarized in Figure 4(a). Also, the results were com-
pared with those obtained in the presence of MnT(4‐
OCH3)PPX (Figure 4b).
According to Figure 4(a), ImH showed the highest co‐
catalytic activity in the reaction catalysed by FeT(4‐
OCH3)PPX. Also, there are large differences between the
co‐catalytic activity of ImH and the anionic co‐catalysts.
A comparison of Figure 4(a) and (b) shows the greater
dependence of the catalytic performance of the manga-
nese porphyrin on the type and molar ratio of the co‐cat-
alyst compared to the iron porphyrin. Also, only ImH
shows a marked co‐catalytic activity in the reaction
catalysed by FeT(4‐OCH3)PPX.
2.3 | Catalytic activity of iron Porphyrins
2.3.1 | Effect of reaction time for reactions
catalysed by FeT(4‐OCH3)PPX
The results obtained under the optimized reaction
conditions for the oxidation of α‐methystyrene catalysed
by MnT(4‐OCH3)PPX and FeT(4‐OCH3)PPX are pre-
sented in Table 7. It is observed that with the exception
of F−, the optimized molar ratio of catalyst to co‐catalyst
is different for the iron and manganese porphyrins. Also,
Table 6 presents the effect of reaction time on the oxida-
tion of α‐methylstyrene catalysed by FeT(4‐OCH3)PPX.
It is observed that after a reaction time of ca 30 h, the
maximum conversions are achieved for the reactions

8 of 13
ZAKAVI ET AL.
TABLE 6 Effect of reaction time on oxidation of α‐methylstyrene and oxidative degradation of FeT(4‐OCH3)PPX in watera
Co‐catalyst
(X)
Conversion (%)b
(time = 3 h)
Conversion (%)
(time = 5 h)
Conversion (%)
(time = 9 h)
Conversion (%)
(time = 17 h)
Conversion (%)
(time, h)
Br−
5
[1]c
—
—
—
—
37
[34]
89 (30 h)
[43] {90}d
Cl−
2
[0]
8
[2]
16
[4]
—
—
80 (34 h)
[23] {87}
F−
4
[17]
8
[22]
—
—
29
[31]
79 (34 h)
[49] {100}
ImH
OAc−
6
[49]
—
—
24
[70]
48
[80]
93 (34 h)
[88] {84}
3
[24]
—
—
—
—
49
[58]
82 (34 h)
[72] {100}
aMolar ratios of catalyst, X, olefin and periodate were 1:10:85.
bAverages of at least three runs are reported.
cValues in brackets show the degree of oxidative degradation (%) of the catalysts.
dEpoxide selectivity (%); see also the footnotes of Table 1.
30
15
0
100
50
0
0
0
50
100
150
50
100
150
(a) X/FeT(4-OCH3)PPX
(b) X/MnT(4-OCH3)PPX
FIGURE 4 Effect of molar ratio of (a) FeT(4‐OCH3)PPX to X for ImH (bold solid curve), Cl− (solid curve), Br− (dashed curve), F− (dash‐
dotted curve) and OAc− (dotted curve) on the oxidation of α‐methylstyrene in comparison with (b) results obtained in the presence of MnT(4‐
OCH3)PPX
TABLE 7 Effect of ImH and anionic co‐catalysts on oxidation of α‐methylstyrene catalysed by FeT(4‐OCH3)PPX and MnT(4‐OCH3)PPX
Conversion (%)
Catalyst
Conversio (%)b X = Br− Conversion (%) F− Conversion (%) Cl− Conversion (%) OAc− ImH
FeT(4‐OCH3)PPX
1:5:85:170a
10
[20]c
1:10:85:170
3.4
[19]
1:20:85:170
2.1
[21]
1:10:85:170
3.8
[24]
1:75:85:170
25
[70]
MnT(4‐OCH3)
1:30:85:170
1:10:85:170
1:75:85:170
1:20:85:170
1:10:85:170
PP(OAc)
94
33
93
69
53
[38]
[58]
[52]
[79]
[62]
aOptimized molar ratios of catalyst, X, olefin and periodate are reported.
bFor a reaction time of 3 h.
cValues in brackets show the degree of oxidative degradation of the catalysts.
the oxidative degradation of the manganese porphyrin is
usually greater than that of the iron porphyrin.
oxidation of styrenes in the presence of the iron porphy-
rins and different co‐catalysts are summarized in Table 8
and Tables S13–S16. The results show the much higher
co‐catalytic activity of ImH relative to the anionic co‐cat-
alysts for the iron porphyrins. A catalyst to co‐catalyst
molar ratio of 1:75 was found to be the optimal molar
ratio for the oxidation reaction. According to our previous
work,[5a] a molar ratio of 1:5 was the best molar ratio for
2.3.3 | Comparison of iron porphyrins
The stereoelectronic properties of meso‐substituents often
have marked effects on the catalytic activity and oxidative
stability of iron porphyrins.[5a,6f] The results for the

ZAKAVI ET AL.
9 of 13
TABLE 8 Catalytic activity of iron porphyrins for oxidation of styrenes with periodate in watera,b,c
Conversion (%) [deg]
FeT(4‐OCH3)PP(Cl)
Conversion (%) [deg]
FeT(2‐CH3)PP(Cl)
Conversion (%) [deg]
FeT(2‐Cl)PP(Cl)
Conversion (%) [deg]
FeTPP(Cl)
Alkene
4
[16]
5.4
[0]
18
[2]
0
[20]
2.1
[21]
3.9
[0]
10.3
[2]
3
[23]
0
[25]
4.3
[4]
25
[7]
5.7
[17]
0
[16]
2.6
[5]
21
[8]
2
[16]
aSee Table 7 for molar ratios of catalyst, Cl−, olefin and periodate.
bFor a reaction time of 3 h; the average of at least three runs is reported.
cValues in brackets show the degree of oxidative degradation of the catalysts.
the oxidation of olefins with tetra‐n‐butylammonium
periodate in the presence of iron porphyrins and ImH in
dichloromethane. It is observed that a much higher molar
ratio is required for the reaction performed in water. This
observation may be due the occupation of the sixth
coordination site of Fe(III) by water molecules and the
extensive hydration of ImH as a good hydrogen bond
donor and acceptor.
According to Table 8 and Tables S13–S16, FeT(2‐
CH3)PPX and FeT(2‐Cl)PPX showed higher catalytic
activity for the oxidation of styrenes compared to the
other iron porphyrins. Indeed, there is a better correla-
tion between the electron‐deficient character of the iron
porphyrins and their catalytic activity in comparison
with the manganese porphyrins. However, FeT(4‐
OCH3)PPX may have a catalytic activity comparable to
that of FeT(2‐Cl)PPX (Tables S14 and S15, oxidation of
4‐methystyrene and α‐methylstyrene), but the oxidative
stability of the former is much less than the latter. It is
notable that while FeT(2‐Cl)PPX showed better catalytic
activity in comparison with FeT(2‐CH3)PPX in the case
of the anionic co‐catalysts, the latter was more efficient
for the oxidation of styrenes in the presence of ImH as
the best co‐catalyst.
On the other hand, although the oxidative stability of
FeT(2‐Cl)PPX was generally higher than the other cata-
lysts, no correlation was found between the stability of
the iron porphyrins and the stereoelectronic properties
of the meso‐substituents. Also, the nature of co‐catalyst
had a significant influence on the degree of oxidative
stability and the order of oxidative stability of the iron
porphyrins. An oxidative degradation of ca 20% was found
for the iron porphyrins in the case of the anionic co‐cata-
lysts, but the oxidative degradation of the catalysts was
significantly greater in the presence of ImH.
2.3.4 | Effect of reaction temperature
As is evident from Table 8 and Tables S15–S19,
conversions of less than 25% were achieved for the oxida-
tion of styrenes catalysed by the iron porphyrins in the
presence of the anionic co‐catalysts. An increase of
temperature from 25 to 50 °C led to a significant increase
in the conversion of α‐methystyrene (Table 9). However,
TABLE 9 Oxidation of α‐methylstyrene with periodate catalysed by FeT(4‐OCH3)PPX at room temperature and 50 °C (values in paren-
theses) in the presence of different co‐catalysts
Axial ligand
X = Br−
F−
Cl−
OAc−
ImH
Catalyst:X:Olefin:periodatea
1:20:85:170
1:20:85:170
1:40:85:170
1:20:85:170
1:40:85:170
Catalyst:X:Olefin:periodateb
(1:5:85:170)
95 (10)
(1:10:85:170)
35 (3.4)
(1:20:85:170)
48 (2.1)
(1:10:85:170)
44 (3.8)
(1:75:85:170)
97 (25)
Conversion
Degradation
22 (20)
8 (19)
7 (21)
36 (24)
83 (70)
aOptimized molar ratios of catalyst, co‐catalyst, olefin and periodate for reactions performed at room temperature and those performed at 50 °C for a reaction
time of 3 h.
bOptimized molar ratios of catalyst, co‐catalyst, olefin and periodate for reactions performed at room temperature and those performed at 50 °C for a reaction
time of 3 h.

10 of 13
ZAKAVI ET AL.
the increase in the oxidative degradation of the catalysts
was much less than that observed in the conversion. In
other words, the efficiency of oxidation reaction per-
formed in the presence of the anionic co‐catalysts may
be improved by using higher temperatures. Furthermore,
the co‐catalytic activity of ImH and the anionic co‐cata-
lysts was much more than that observed at room temper-
ature. Also, in comparison with the reaction performed at
room temperature (Figure 4a), the increase in the catalyst
to co‐catalyst molar ratio (Figure 5) had marked effects on
the catalytic activity of the iron porphyrins.
2.4 | Proposed mechanism
The catalytic oxidation of olefins with periodate in the
presence of metalloporphyrins (species SI, Scheme 1)
necessitates the coordination of the axial base (B = ImH
and anionic co‐catalysts) and periodate anion to the metal
centre (species SII and SIII, respectively).[5a,6a] The co‐cat-
alytic activity of ImH and the anionic co‐catalysts has
been attributed to their coordination to the metal centre
which weakens the O―I bond of the coordinated
periodate anion.[6a] Meanwhile, electron donation from
axial base to metal centre facilitates the oxidation of metal
centre, departure of IO3− and the formation of high‐valent
oxo metal species (species SVI). Also, the results of com-
petitive oxidation of cis‐ and trans‐stilbene gave evidence
for the involvement of a high‐valent metal oxo porphyrin
species (species SVI) and the six‐coordinate periodato
complex, i.e. M(porphyrin)(ImH)(IO4) (M = Fe or Mn)
(species SIII).[5a,b] Furthermore, the presence of water or
hydrogen bond forming molecules such as alcohols has
been shown to accelerate the formation of the high‐valent
species.[5e,8] It is noteworthy that due to strong solvation
100
50
0
0
50
100
150
−
−
of IO3 anion by water molecules, the departure of IO3
X/FeT(4-OCH3)PPX
anion as the leaving group which occurs prior to the for-
mation of high‐valent oxo metal species is significantly
facilitated in aqueous solutions. On the other hand, the
formation of carbonyl compounds has been found to
FIGURE 5 Effect of molar ratio of FeT(4‐OCH3)PPX to X for ImH
(bold solid curve), cl− (solid curve), Br− (dashed curve), F− (dash‐
dotted curve) and OAc− (dotted curve) on the oxidation of α‐
methylstyrene at 50 °C
SCHEME 1 Proposed mechanism

ZAKAVI ET AL.
11 of 13
proceed through a radical mechanism with participation
of high‐valent oxo manganese and iron porphyrin
species.[14] According to the above discussion, a mecha-
nism is proposed for the oxidation of olefins with
periodate in the presence of ImH and anionic axial bases
(Scheme 1) under aqueous conditions. Paths A and C
show the formation of epoxide with the involvement of
a M(porphyrin)(ImH)(IO4) (species SIII) species or a
high‐valent metal oxo porphyrin intermediate (species
SVI), respectively. Formation of aldehyde and ketone
may be explained by a radical mechanism initiated by
high‐valent iron or manganese oxo species[5a,14] through
hydrogen abstraction from olefins or water (Path B).
Formation of SV which leads to the occupation of the fifth
and sixth coordination sites of the M(III) atom causes
catalyst deactivation.[6a,15] High‐valent iron(V) oxo
porphyrin species (SVI) and water can form an •OH radi-
cal (Path B). However, the reduced form of this intermedi-
ate, i.e. (porphyrin)(ImH)iron(IV)–OH species, may also
information (Tables S20 and S21). The exchange of ace-
tate for the halides was confirmed using UV–visible spec-
troscopy; in a typical experiment, excess amounts of the
tetra‐n‐butylammonium (TBA) salt of fluoride, bromide
or chloride were added to a solution of MnTPPOAc in
dichloromethane with an absorbance (A) of about 1.0 at
476 nm. The solution was stirred with a magnetic stirrer
for 20 min. The wavelength of maximum absorbance
shifted from 476 nm to 457, 485 and 478 nm for TBAF,
TBABr and TBACl, respectively.
4.1 | General oxidation procedure
In a typical reaction, solid metalloporphyrin (0.003 mmol)
and styrene (0.25 mmol) were added to a solution of ImH
(0.03 mmol) in water (1 ml). Then, 0.5 mmol (0.107 g) of
sodium periodate was added and the mixture was stirred
thoroughly for 3 h at ambient temperature. After
the required time, the catalyst was separated from the
reaction mixture by filtration and centrifugation and
the reaction mixture was extracted with dichloromethane
(3 × 2 ml), dried over MgSO4 and analysed using GC. KBr,
KCl, KF and KOAc were used as the sources of anionic
axial bases. All reactions were repeated at least three
times, analysed using GC and averaged. Commercially
available aldehydes and acetophenone were used to iden-
tify the products using GC analysis. Also, the epoxides of
styrenes were prepared according to the literature.[18]
•
be considered as the source of OH radicals needed for
the formation of aldehyde and ketone products; homolytic
•
cleavage of the iron(IV)–OH bond gives OH radical and
the catalyst precursor (SIV).
3 | EXPERIMENTAL
3.1 | Instrumentation
A Varian 3800 gas chromatograph equipped with an HP‐5
capillary column (phenylmethylsiloxane, 30 m × 320
μm × 0.25 μm) or a packed column (Chromosorb WHP
80‐100 Mesh, 4 mm × ¼ × 2 m) and a flame‐ionization
detector was used to analyse the reactions. 1H NMR spec-
tra were obtained with a Bruker Avance DPX 400 MHz
spectrometer. The absorption spectra were recorded with
4.2 | Degradation of Metalloporphyrins
The extent of degradation of metalloporphyrins in the
presence of various olefins for a reaction time of 3 h was
measured on the basis of the absorbance changes (ΔA)
at λmax of the metalloporphyrins (ΔA/A)[5,13]; at the end
of reaction, 5 ml of dichloromethane was added to the
reaction mixture, and the mixture was shaken for 5 min.
Then, the organic phase was separated and dried over
sodium sulfate. The dichloromethane solution of
metalloporphyrin was adjusted to 10 ml with dichloro-
methane and aliquots of the solution were transferred to
a 1 cm quartz cell and the absorbance at λmax was
measured and compared with that of the same solution
of initial catalyst.
a
Pharmacia Biotech Ultrospec 4000 UV–visible
spectrophotometer.
4 | PREPARATION OF
PORPHYRINS AND
METALLOPORPHYRINS
H2TPP, H2T(4‐OCH3)PP, H2T(2‐Cl)PP, H2T(2‐CH3)PP[16]
and the corresponding manganese and iron
complexes[5a,b,17] were prepared and purified according
to the literature.[5a,b] The iron and manganese porphyrins
with different counter anions were prepared by stirring a
dichloromethane solution of the iron and manganese
porphyrins bearing acetate counter anion with a saturated
aqueous solution of the potassium salt of the
respective anion (Cl−, Br−, F−).[17d] Values of λmax of
the metalloporphyrins are summarized in the supporting
5 | CONCLUSIONS
Aqueous‐phase heterogeneous catalysis of the oxidation
of styrenes with periodate in the presence of a series of
water‐insoluble manganese and iron porphyrins bearing
various substituents (phenyl, 4‐methoxyphenyl, 2‐
methylphenyl and 2‐chlorophenyl) at the meso positions

12 of 13
ZAKAVI ET AL.
Chem. 2015, 29, 63. g) A. Talaeizadeh, M. Tofighi, S. Zakavi,
Appl. Organomet. Chem. 2017, https://doi.org/10.1002/
aoc.3967.
led to the formation of the corresponding aldehydes and
epoxides as products. In the case of α‐methylstyrene,
acetophenone and α‐methylstyrene oxide were obtained.
Different anionic co‐catalysts (chloride, acetate, bromide
and fluoride) and ImH were used to improve the catalytic
activity of the metalloporphyrins; ImH and Br− were
found to be the best co‐catalysts for the oxidation of
styrenes catalysed by the iron and manganese porphyrins,
respectively. Interestingly, the use of chloride and
bromide anions as co‐catalysts increased the selectivity
of the reaction towards the formation of carbonyl
compounds. For the reaction performed in the presence
of the manganese porphyrins, complete oxidation of
styrenes was achieved at a reaction time of 3 h by
optimization of the catalyst to co‐catalyst molar ratio
However, for the iron porphyrins the catalytic activity
could not be improved by an increase in this ratio. On
the other hand, increasing the reaction temperature from
25 to 50 °C led to a significant increase in the catalytic
activity of the iron porphyrins, with a small increase in
the catalyst degradation. Also, the increase in the molar
ratio of iron porphyrin to co‐catalyst at 50 °C was much
more effective for the catalytic activity of the iron porphy-
rins than that observed at room temperature. In spite of
the higher oxidative stability of the iron porphyrins, the
manganese porphyrins generally showed higher catalytic
activity for the oxidation of styrenes than the iron
porphyrins.
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ACKNOWLEDGEMENTS
Financial support of this work by the Institute for
Advanced Studies in Basic Sciences (IASBS) is acknowl-
edged. This work was supported in part by the Iran
National Science Foundation (INSF) under grant no.
95816928.
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1999, 1999, 168.
ORCID
[8] D. Mohajer, M. Abbasi, Eur. J. Inorg. Chem. 2008, 2008, 3218.
Saeed Zakavi http://orcid.org/0000-0002-2223-6108
[9] J. Lurie, Handbook of Analytical Chemistry, MIR Publishers,
Moscow 1975.
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