Solvent effects on catalytic activity of manganese porphyrins with cationic, anionic and uncharged meso substituents: Indirect evidence on the nature of active oxidant species

Article abstract of DOI:10.1002/aoc.4678

Oxidation of cyclohexene and styrene with sodium periodate and tetra-n-butylammonium periodate (TBAP) catalyzed by MnT(3-MePy)P(OAc), MnT(4-SO₃)PP(OAc) and MnTPP(OAc) has been studied in water, methanol, acetonitrile and dichloromethane as solvents. The results show significant dependence of the product distribution on the type of solvent and the electronic nature of the aryl substituents introduced at the porphyrin periphery. While the oxidation of cyclohexene and styrene in the presence of MnT(3-MePy)P(OAc) and MnTPP(OAc) in water (also in methanol) gave the corresponding epoxides as nearly the sole product, performing the reactions in the presence of MnT(4-SO₃)PP(OAc) yielded the products of allylic oxidation, cyclohexene-2-ol and cyclohexene-2-one and acetophenone as the major products. In the case of styrene, performing the reaction in the presence of MnT(4-SO₃)PP(OAc), MnT(3-MePy)P(OAc) and MnTPP(OAc) in acetonitrile gave a mixture of styrene oxide and acetophenone as the products. Under the same conditions, the oxidation of cyclohexene afforded cyclohexene oxide as approximately the exclusive product. Furthermore, the oxidation of olefins in dichloromethane gave the corresponding epoxide as the exclusive products. The product distributions observed in the protic and aprotic solvents were used to provide indirect evidence on the relative contribution and reactivity of high valent manganese oxo and periodato Mn(III) porphyrin species to the oxidation reactions.

Full text of DOI:10.1002/aoc.4678

Received: 24 August 2018
DOI: 10.1002/aoc.4678
Revised: 5 October 2018
Accepted: 10 October 2018
F U L L P A P E R
Solvent effects on catalytic activity of manganese
porphyrins with cationic, anionic and uncharged meso
substituents: Indirect evidence on the nature of active
oxidant species
Zahra Esfandiari bayat1 | Hajar Rahiminezhad2 | Saeed Zakavi1
1 Institute for Advanced Studies in Basic
Oxidation of cyclohexene and styrene with sodium periodate and tetra‐n‐
butylammonium periodate (TBAP) catalyzed by MnT(3‐MePy)P(OAc), MnT(4‐
SO3)PP(OAc) and MnTPP(OAc) has been studied in water, methanol,
acetonitrile and dichloromethane as solvents. The results show significant
dependence of the product distribution on the type of solvent and the electronic
nature of the aryl substituents introduced at the porphyrin periphery. While the
oxidation of cyclohexene and styrene in the presence of MnT(3‐MePy)P(OAc)
and MnTPP(OAc) in water (also in methanol) gave the corresponding epoxides
as nearly the sole product, performing the reactions in the presence of MnT(4‐
SO3)PP(OAc) yielded the products of allylic oxidation, cyclohexene‐2‐ol and
cyclohexene‐2‐one and acetophenone as the major products. In the case of
styrene, performing the reaction in the presence of MnT(4‐SO3)PP(OAc),
MnT(3‐MePy)P(OAc) and MnTPP(OAc) in acetonitrile gave a mixture of styrene
oxide and acetophenone as the products. Under the same conditions, the oxida-
tion of cyclohexene afforded cyclohexene oxide as approximately the exclusive
product. Furthermore, the oxidation of olefins in dichloromethane gave the
corresponding epoxide as the exclusive products. The product distributions
observed in the protic and aprotic solvents were used to provide indirect
evidence on the relative contribution and reactivity of high valent manganese
oxo and periodato Mn(III) porphyrin species to the oxidation reactions.
Sciences (IASBS), 45137‐66731 Zanjan,
Iran
2 School of Chemistry, Damghan
University of Basic Sciences, 36716‐41167
Damghan, Iran
Correspondence
Saeed Zakavi, Institute for Advanced
Studies in Basic Sciences (IASBS), 45137–
66731, Zanjan, Iran.
Email: zakavi@iasbs.ac.ir
KEYWORDS
allylic oxidation of cyclohexene, oxidation of alkenes, manganese(III)porphyrins, solvent effects,
Substituent effects
1 | INTRODUCTION
catalytic oxidation of organic compounds with different
terminal oxidants in the presence of metalloporphyrins
Biological oxidations including oxygenations of organic
substrates catalyzed by cytochrome P‐450, oxidations by
peroxidases, oxidative halogenations by chloroperoxidases
and hydrogen peroxide dismutation by catalase are the
main reactions catalyzed by heme enzymes.[1] The
has been the subject of extensive experimental and
theoretical investigations since the late 1980,s.[1,2] The cat-
alytic performance of metalloporphyrins is influenced by
parameters such as the stereoelectronic properties of sub-
stituents at the porphyrin periphery and the type of metal
Appl Organometal Chem. 2018;e4678.
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ESFANDIARI BAYAT ET AL.
center, axial base, solvent and terminal oxidant.[1e, 3] It is
generally accepted[4] that electron‐deficient metalloporph-
yrins are more efficient catalysts than the electron‐rich
ones in the oxidation of organic compounds with different
terminal oxidants. However, there are many reports
showing that electron‐rich metalloporphyrins can have
comparable or higher catalytic activity than the electron‐
deficient ones.[5] We have previously reported the oxida-
tion of alkenes with tetra‐n‐butylammonium periodate
(TBAP) in dichloromethane catalyzed by a series of
manganese(III) and iron(III) porphyrins.[5d, e] According
to the previous studies[3d, 5d, e] the catalytic performance
of Mn(III) meso‐tetra(aryl)porphyrins only weakly corre-
lates with the electronic properties of the meso substitu-
ents. It is noteworthy that in manganese and iron
porphyrin catalyzed oxidation of olefins with TBAP in
dichloromethane, low valent periodato manganese(III)
and iron(III) porphyrin species were found as the domi-
nant active oxidant species. Furthermore, the formation
of multiple active oxidants was evident for both heme
and non‐heme manganese catalysts in reaction with vari-
ous terminal oxidants.[3e, f, 5b–f, 6] In a recent work,[1e] we
have reported the catalytic activity of a series of water sol-
uble and insoluble iron(III) and Mn(III) meso‐tetra(aryl)
porphyrins in the oxidation of alkenes with sodium
periodate in water. The results were in good agreement
with the higher catalytic activity of the electron‐deficient
iron and manganese porphyrins. As shown by Mohajer
et al., using water‐saturated dichloromethane as the sol-
vent, significantly increases the catalytic activity of
electron‐deficient manganese porphyrins with little or no
effect on that of the electron‐rich ones.[5f] In the present
work, the catalytic activity of two water soluble cationic
and anionic manganese porphyrins and MnTPP(OAc) in
the oxidation of alkenes with sodium periodate or TBAP
was studied in water, methanol, acetonitrile and dichloro-
methane (Figure 1). In this study, the effects of solvent on
the product distribution and total conversion were used to
provide indirect evidence on the nature of the active oxi-
dant involved in the oxidation reactions. It is noteworthy
that due to the high reactivity of high valent manganese
oxo porphyrin intermediates at room temperature, most
of these species have been characterized by low tempera-
ture UV–vis spectroscopy or competitive oxidation of the
cis‐ and trans isomers of sterically hindered olefins such
as stilbene and octene.[3c–f, 5b–e, 6a] Furthermore, due to
the environmental problems associated with the use of
halogenated solvents,[7] oxidation of olefins in environ-
mentally preferable solvents[8] is of great interest in the
field of biomimetic catalysis.
2 | RESULTS AND DISCUSSION
2.1 | Oxidation of alkenes catalyzed by
MnT(4‐SO3)PP(OAc)
Oxidation of cyclohexene with TBAP in the presence of
MnT(4‐SO3)PP(OAc) and imidazole (ImH) in water and
methanol gave products derived from allylic oxidation
as the major products and cyclohexene epoxide as the
minor one (Table 1). The presence of ImH was found to
play crucial roles in the stabilization and reactivity of
high valent manganese(IV and V)–oxo porphyrin inter-
mediates (Figure 2) as well as the low valent periodato
manganese(III) species. These roles were attributed to
the ability of ImH to form σ and π bonds with the manga-
nese center and hydrogen bonds with the leaving group
(here, IO3−) and the coordinated ImH. Also, the latter
can stabilize a high valent manganese(IV and V)–oxo
porphyrin intermediate by hydrogen bond formation with
its oxygen atom.[3d, 9c] As was found in previous studies,[3d,
5c–e]
performing the reaction in dichloromethane yields
cyclohexene oxide as the sole product. In manganese
porphyrin catalyzed oxidation of organic compounds, high
valent manganese(IV)‐oxo porphyrin π cation radical and
low valent (oxidant)Mn(III)‐porphyrin species are usually
9]
invoked as the active oxidants.[3a,
The use of protic
solvents such as water and different alcohols has been
found to facilitate the formation of high valent manganese
TABLE 1 Oxidation of olefins with periodate catalyzed by
MnT(4‐SO3)PP(OAc) in water, methanol and dichloromethane at
room temperature for a reaction time of 4 hr
Conversion (Yield of epoxide)
[Epoxide selectivity] (%)b
Olefins water
96c (trace)[0]d
CH3OH
CH2Cl2
75 (4)[5]d
20 (20)[100]
37(17)[45]e
45(<1)[0]
13(13)[100]
MnT(4‐SO3)PP(OAc):ImH:olefin:oxidant (TBAP and sodium periodate for
the reaction performed in organic solvents and water, respectively) were
used in a 1:20:85:170 molar ratio. [b] All reactions were repeated at least three
[c]
times and the average values with an error of ca 5–10% are reported. The
use of ImH in 1:30 molar ratio relative to the catalyst led to a conversion of
100%. [d]Cyclohexene‐2‐ol and cyclohexen‐2‐one were obtained as the major
FIGURE 1 Porphyrins and manganese porphyrins used in
this study
[e]
products.
Acetophenone was the major product.

ESFANDIARI BAYAT ET AL.
3 of 6
styrene towards oxidation with the active oxidants in
water. It is observed that the product selectivity of the
reaction catalyzed by MnT(4‐SO3)PP(OAc) depends
strongly on the type of solvent, so that the change of
solvent from dichloromethane to protic ones (water or
methanol) in the case of cyclohexene leads to formation
of the allylic oxidation products as exclusive product
and significant decrease in the epoxide selectivity in
the case of styrene.
FIGURE 2 The formation of active oxidants (I and II) and
competition between epoxidation and allylic oxidation of cyclohexene
oxo species[3d, 5f, 9, 10] which can oxidize alkenes to the cor-
responding epoxide or the allylic products. Hydrogen
bonds formed between the leaving group (IO3−) and
hydrogen bond donors such as water, methanol and ImH
facilitate departure of the leaving group and the formation
of high valent manganese(IV)‐oxo porphyrin π cation rad-
ical species (Figure 2, species II). Also, these hydrogen
bonds will stabilize species II and shift the equilibrium
towards the formation of this species. The observed prod-
uct distribution arises from the competition between the
allylic C‐H bond and the C=C double bond (Figure 2)
for the active oxidant that also depends on the structure
of the alkene.[11] While epoxidation of alkenes can proceed
with the involvement of either a low valent periodato
manganese(III) species (species I, Figure 2) or a high
valent manganese oxo one (species II), the latter is
necessary for the allylic oxidation (Figure 3) Accordingly,
the exclusive formation of the allylic products in the
oxidation of cyclohexene in water (Table 1), provides
strong indirect evidence for the intermediacy of species II
as the active oxidant in this reaction. Also, nearly the same
product distribution was observed for the reaction
performed in methanol. Oxidation of styrene in water gave
nearly equal amounts of styrene oxide and acetophenone.
It should be noted that the use of dichloromethane as
the solvent led to the formation of styrene oxide as the sole
product, consistent with the intermediacy of a periodato
Mn(III)porphyrin intermediate as the main active
oxidant.[3d–f]
2.2 | Oxidation of alkenes in the presence
of MnT(3‐MePy)P(OAc)
Oxidation of cyclohexene and styrene with sodium
periodate catalyzed by MnT(3‐MePy)P(OAc) led to the
formation of the corresponding epoxides as nearly the
sole product in water (Table 2). The use of methanol as
solvent, again afforded cyclohexene oxide as the domi-
nant product, but in the case of styrene, gave a mixture
of approximately equal amounts of styrene oxide and
acetophenone. In comparison with MnT(4‐SO3)PP(OAc),
the catalyst showed a high selectivity towards the forma-
tion of the epoxide products. The use of acetonitrile as the
solvent (Table 3) led to a higher selectivity for the epoxide
in the case of cyclohexene. As was mentioned above, the
presence of high valent metal oxo species is needed for
the formation of allylic products. The substitution of 4‐
sulfonatophenyl group with the weaker electron‐
releasing 3‐methylpyridyl substituent at the meso posi-
tions, can shift the equilibrium between species I and II
(Figure 2) toward the former. This in turn shifts the reac-
tion toward the formation of cyclohexe oxide.
TABLE 2 Oxidation of olefins with periodate catalyzed by
MnT(3‐MePy)P(OAc) in water, methanol and dichloromethane at
room temperature for a reaction time of 4 hr
Also, the higher reactivity of cyclohexene versus sty-
rene demonstrates higher reactivity of the allylic CH
bond of cyclohexene relative to the double bond of
Conversion (Yield of epoxide)
[Epoxide selectivity] (%)b
Olefins water
100c (93) [93]c
CH3OH
CH2Cl2
100 (95) [95]c
~10 (~10) [100]
100 (94) [94]d
95 (53) [56]d
~5 (~5) [100]
MnT(3‐MePy)P(OAc):ImH:olefin:oxidant (sodium periodate or TBAP were
used in water, methanol and dichloromethane, respectively) were used in a
[b]
1:30:85:170 molar ratio.
The average of three reactions. [c]Cyclohexene‐
[d]
FIGURE 3 Oxidation of cyclohexene at the allylic CH bond with
2‐ol and cyclohexen‐2‐one were obtained as the minor products.
the species II
Acetophenone was the other product.

4 of 6
ESFANDIARI BAYAT ET AL.
metal center.[2a, 3e, f] On the other hand, the presence of
the former led to the allylic oxidation of cyclohexene
(Figure 3). It should be noted that the Mn(IV)/Mn(III)
reduction potential of manganese porphyrins depends
on the stereoelectronic properties of the meso and β sub-
stituents.[12] Accordingly, the oxidizability of species II
formed from the manganese porphyrins is expected to
decrease in the order MnT(3‐MePy)P(OAc) > MnT(4‐
SO3)PP(OAc) > MnTPP(OAc). However, the direction of
equilibrium between species I and II (Figure 2) and con-
sequently the extent of contribution of the two species in
the catalytic cycle is determined by the nature of the meso
substituents. Therefore, the formation of the allylic prod-
ucts upon the oxidation of cyclohexene in different sol-
vents seems to be controlled by the relative oxidizability
of high valent manganese‐oxo species and the relative
contribution of species I and II under the reaction
conditions.
TABLE 3 Oxidation of olefins with TBAP catalyzed by MnT(3‐
MePy)P(OAc), MnT(4‐SO3)PP(OAc) and MnTPP(OAc) in acetoni-
trile at room temperature for a reaction time of 4 hr
Conversion (Yield of epoxide)
[Epoxide selectivity] (%)
Mn(3‐MePy)
Olefins P(OAc)
MnT(4‐SO3)
PP(OAc)
MnTPP
(OAc)
90c (88) [98]b
85 (80) [91]b
78 (65) [83]b
67 (43) [64]c
57 (45) [79]c
60 (21) [35]c
Catalyst:ImH:olefin:oxidant were used in a 1:30:85:170 molar ratio. [b]Cyclo-
[c]
hexene‐2‐ol and cyclohexen‐2‐one were obtained as the minor products.
Acetophenone was the other product.
2.3 | Oxidation of alkenes catalyzed by
MnTPP(OAc)
Oxidation of cyclohexene and styrene with periodate by
using MnTPP(OAc) as the catalyst afforded the corre-
sponding epoxides as the major product (Table 4).
Although no allylic products were observed in the oxida-
tion of cyclohexene in methanol, performing the reaction
in water gave the allylic products with a yield of 10%. It is
noteworthy that an epoxide selectivity of 100% was
observed for the reaction performed in dichloromethane
3 | EXPERIMENTAL
3.1 | Instrumental
1H NMR spectra were obtained on a Bruker 250 MHz
spectrometer. The absorption spectra were recorded on
a GBC‐916 UV–Vis spectrophotometer. All reactions were
analyzed by a Varian CP‐3800 gas chromatograph
equipped with a HP‐5 capillary column (phenylmethyl
siloxane 30 m × 320 μm × 0.25 μm) and a flame‐
ionization detector.
in the presence of different electron‐rich and electron‐
5d, e]
deficient metalloporphyrins.[3d,
The total conver-
sions are also much higher than those obtained in dichlo-
romethane. This finding suggests that a high valent
manganese‐oxo porphyrin species rather than a low
valent periodato manganese(III) porphyrin is involved
in the oxidation reactions conducted in water or metha-
nol. The former has been considered as a stronger oxidant
than the latter, due to the higher oxidation state of the
3.2 | Preparation of porphyrins and
manganese porphyrins
Meso‐tetra(4‐sulfonatophenyl) porphyrin, H2T(4‐SO3)PP,
meso‐tetra(4‐sulfonatophenyl)porphyrinatomanganese(III)
acetate, MnT(4‐SO3)PP(OAc), meso‐tetra(3‐pyridyl)p,
H2T(3‐Py)P, N‐methylated meso‐tetra(pyridyl)porphyrin,
H2T(3‐MePy)P and meso‐tetra(3‐methylpyridyl)porphyrin-
atomanganese(III) acetate, MnT(3‐MePy)P(OAc) were pre-
pared and purified according to the literature.[13] More
experimental details can be found in our previous
works.[1f, g, 5d]
TABLE 4 Oxidation of olefins with periodate catalyzed by
MnTPP(OAc) in water, methanol and dichloromethane at room
temperature for a reaction time of 4 hr
Conversion (Yield of epoxide)
[Epoxide selectivity] (%)
1
Olefins water
100 (90) [90]b
CH3OH
CH2Cl2
H2TPP: H NMR (CDCl3, 400 MHz): −2.77 (2H, br, s,
NH), 7.75–7.77 (8Hm and 4Hp,m), 8.21–8.24 (8Ho, d), 8.84
(8Hβ, s); UV–Vis (λ/nm) in CH2Cl2: 417 (Soret), 512, 545,
586, 647. Meso‐tetraphenylporphyrin, H2TPP was synthe-
sized and purified by Adler et al. method.[13c] H2T(4‐SO3)
PP was synthesized according to the literature as follows:
5,10,15,20‐tetrakis(4‐chlorosulphonylphenyl)porphyrin
was prepared by dropwise addition of an excess
amount of chlorosulfonic acid (200 μl, 2.7 mmol) to
100 (100) [100]
45 (43) [96]b
85 (78) [92]c
100 (89) [89]c
54 (54) [100]
MnTPP(OAc):ImH:olefin:oxidant (sodium periodate and TBAP for the reac-
tions in water and methanol, respectively) were used in a 1:20:85:170 molar
ratio. [b] Cyclohexene‐2‐ol and cyclohexen‐2‐one were obtained as the major
[c]
products. Acetophenone was the other product.

ESFANDIARI BAYAT ET AL.
5 of 6
H2TPP (50 mg, 0.08 mmol) in dichloromethane (4 ml). The
solution was magnetically stirred at room temperature for
4 hr. After the required time, the solution was cooled to
4 °C and 4 ml of cold distilled water was added to the mix-
ture. The precipitate was filtered and the solid residue was
washed with dichloromethane to remove the unreacted
H2TPP until the filtrate becomes colorless. The suspension
of 5,10,15,20‐tetrakis(4‐chlorosulphonylphenyl)porphyrin
in water was refluxed for 12 hr.[13e] Rotary evaporation of
the solvent gave H2T(4‐SO3)PP. The formation of
tetrasulfonated salt of H2T(4‐SO3)PP was confirmed by 1H
NMR; dichloromethane extraction of H2T(4‐SO3)PP with
tetra‐n‐butylammonium bromide from an alkaline aque-
ous solution led to the formation of (n‐Bu)4H2T(4‐SO3)PP
that was used to prepare the 1H NMR spectra in CDCl3.
H2T(4‐SO3)PP (tetra‐n‐butylammonium salt), 1H
NMR (CDCl3, 400 MHz): −2.85 (2H, br, s, NH), 8.15–
8.17 (8Hm, d), 8.32–8.33 (8Ho, d), 8.82 (8Hβ, s), the pro-
tons of tetra‐n‐butylammonium appear at δ 1.01, 1.42,
1.60 and 3.38 ppm; UV–Vis (λ/nm) in CH2Cl2: 418
(Soret), 512, 543, 582, 645.
catalysts.[3d] However, in this study, a 1:20 (or 1:30 in
water) molar ratio of metalloporphyrin to ImH was found
to be the optimized one. TBAP and sodium periodate
were used as oxidant for the oxidation reactions con-
ducted in the organic solvents and water, respectively.
Progress of the reactions was followed by GC. For the
reactions in water, the organic compounds were extracted
by dichloromethane. After drying the solution on anhy-
drous sodium sulfate, the mixture was passed through a
short silicagel column to remove the catalyst and then
analyzed by GC.
4 | CONCLUSION
Oxidation of cyclohexene and styrene with sodium
periodate and TBAP catalyzed by MnT(3‐MePy)P(OAc),
MnT(4‐SO3)PP(OAc) and MnTPP(OAc) was studied in
different protic and aprotic solvents and found that: (i)
oxidation of cyclohexene with sodium periodate catalyzed
by MnT(4‐SO3)PP(OAc) in water and methanol (using
TBAP as the oxidant) afforded the products of allylic oxi-
dation as nearly the sole product; (ii) performing the reac-
tion in the presence of MnT(3‐MePy)P(OAc) in methanol,
water or acetonitrile gave cyclohexene oxide as nearly the
exclusive product; (iii) the oxidation of styrene in water,
catalyzed by MnT(4‐SO3)PP(OAc) yielded styrene oxide
as nearly the sole product, but the use of methanol or ace-
tonitrile led to the formation of acetophenone in addition
to styrene oxide. Also, the use of MnT(4‐SO3)PP(OAc) as
the catalyst gave nearly equal amounts of styrene oxide
and acetophenone; (iv) oxidation of the alkenes in the
presence of MnTPP(OAc) in water or methanol produced
the corresponding epoxides as the major product. In other
word, the product distribution is similar to that observed
in dichloromethane as an aprotic solvent. The large dif-
ferences between the product distribtion observed in the
used solvents were attributed to the relative stability
and contribution of high valent manganse oxo and
periodato Mn(III) porphyrin species in the protic and
aprotic solvents. On the other hand, the observed product
distributions gave evidence on the nature of active oxi-
dant species. Also, the formation of high valent manga-
nese oxo porphyrin intermediates is probably governed
by the electronic properties of the meso substituents.
H2T(3‐Py)P was synthesized and purified according to
the Adler method with some modifications have been
described in our previous work.[13g] H2T(3‐MePy) P was
prepared by refluxing H2T(3‐Py)P with excess amounts
of methyltosylate in dimethylformamide and purified
according to the literature.[13h, i]
H2T(3‐Py)P. 1H NMR (CDCl3, 400 MHz): −2.83 (2H, br,
s, NH), 7.77–7.80 (4Hm,dd), 9.46 (4Ho, br, s), 8.52–8.54
(4Ho, br, d), 9.07–9.08 (4Hp, dd), 8.87 (8Hβ, s); UV–Vis (λ/
nm) in CH2Cl2: 418 (Soret), 512, 547, 588, 646. H2T(3‐
1
MePy)P: H NMR (DMSO‐d6, 400 MHz): −3.124 (2H, br,
s, NH), 8.626–8.661 (4Hm, dd), 10.007 (4Ho, adjacent to het-
eroatom, s), 9.323 (4Ho, d), 9.579–9.594 (4Hp, d), 9.266
(8Hβ, s), 4.698 (12H, CH3). UV–vis (λ/nm) in water: 415
(Soret), 512, 540, 577, 628.
The manganese complexes of H2TPP, H2T(3‐MePy)P
and H2T(4‐SO3)PP were prepared by the method of Adler
et al.[13j] MnTPP(OAc):UV–Vis (λmax/nm) in CH2Cl2: 470
(Soret band), 575, 612; MnT(4‐SO3)PP(OAc): UV–Vis
(λmax/nm) in H2O: 465 (Soret band), 557, 592; MnT(3‐
MePy)P(OAc): UV–Vis (λmax/nm) in H2O: 459 (Soret
band), 551.
3.3 | General oxidation procedure
In a typical reaction, metalloporphyrin, alkene, imidazole
and oxidant were used in a molar ratio of 1:20 (or 30 in
the case of water):85:170 which, with the exception of
ImH, is the same as that previously optimized by Mohajer
et al. for the reactions performed in dichloromethane,
using water insoluble manganese porphyrins as the
ACKNOWLEDGMENTS
Financial support of this work by the Institute for
Advanced Studies in Basic Sciences (IASBS) and
Damghan University of Basic Sciences Research Councils
is acknowledged.

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ESFANDIARI BAYAT ET AL.
[7] F. M. Kerton, Alternative Solvents for Green Chemistry, RSC
Publishing, Cambridge 2009.
ORCID
Saeed Zakavi http://orcid.org/0000-0002-2223-6108
[8] C. Capello, U. Fischer, K. Hungerbühlera, Green Chem. 2007, 9,
927.
[9] a) W. J. Song, M. S. Seo, S. D. George, T. Ohta, R. Song, M. J.
Kang, T. Tosha, T. Kitagawa, E. I. Solomon, W. Nam, J. Am.
Chem. Soc. 2007, 129, 1268. b) D. Mohajer, M. Abbasi, Eur. J.
Inorg. Chem. 2008, 3218. c) S. Zakavi, A. Abasi, A. R. Pourali,
S. Talebzadeh, Bull. Korean Chem. Soc. 2012, 33, 35.
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How to cite this article: Esfandiari bayat Z,
Rahiminezhad H, Zakavi S. Solvent effects on
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