Novel Mn(III) Porphyrins and Prospects of Their Application in Catalysis

Article abstract of DOI:10.1134/S0036023619030045

Four novel Mn(III) porphyrins have been synthesized and characterized by UV-Vis, IR, ESI-mass spectroscopy, elemental analysis, magnetic susceptibility studies, TLC, and conductivity measurements. The tentative structure has been proposed. Depolymerization of coal using the synthesized Mn(III) porphyrins have been demonstrated by the optical density method using humic acid as a model of coal. The synthesized complexes have shown excellent depolymerization activity based on comparative studies. Complexes have been successfully applied for the catalytic oxidation of benzyl alcohol, aniline, benzoin, and benzaldehyde into benzaldehyde, nitrobenzene, benzil, and benzoic acid, respectively, at room temperature and pressure.

Full text of DOI:10.1134/S0036023619030045

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2019, Vol. 64, No. 3, pp. 335–341. © Pleiades Publishing, Ltd., 2019.
COORDINATION
COMPOUNDS
Novel Mn(III) Porphyrins and Prospects
of Their Application in Catalysis1
S. L. Bharatia, *, C. Sarmaa, P. J. Hazarikaa, P. K. Chaurasiab, **, N. Anandc, and S. Yadavac
aDepartment of Chemistry, North Eastern Regional Institute of Science and Technology,
Nirjuli, Arunachal Pradesh, 791109 India
bPG Department of Chemistry, LS College Muzaffarpur, (Under B.R.A. Bihar University, Bihar), Muzaffarpur, 842001 India
cDepartment of Chemistry, D.D.U. Gorakhpur University, Gorakhpur, UP, 273009 India
*e-mail: shashilatachem@gmail.com
**e-mail: pankaj.chaurasia31@gmail.com
Received October 25, 2017; revised March 23, 2018; accepted August 15, 2018
Abstract⎯Four novel Mn(III) porphyrins have been synthesized and characterized by UV-Vis, IR, ESI-mass
spectroscopy, elemental analysis, magnetic susceptibility studies, TLC, and conductivity measurements. The
tentative structure has been proposed. Depolymerization of coal using the synthesized Mn(III) porphyrins
have been demonstrated by the optical density method using humic acid as a model of coal. The synthesized
complexes have shown excellent depolymerization activity based on comparative studies. Complexes have
been successfully applied for the catalytic oxidation of benzyl alcohol, aniline, benzoin, and benzaldehyde
into benzaldehyde, nitrobenzene, benzil, and benzoic acid, respectively, at room temperature and pressure.
Keywords: Mn(III) porphyrins, humic acid, biomimetic catalyst, coal depolymerization, oxidation reaction
DOI: 10.1134/S0036023619030045
INTRODUCTION
peroxidase depolymerizes humic acid [16] and this
depolymerization activity is due to the Mn(III) che-
lated complexes.
Macrocyclic complexes have received much atten-
tion because they are involved in important biological
processes, such as photosynthesis, dioxygen transport,
in addition to catalytic properties [1, 2] with important
industrial applications. The increasing demand for
catalyst in oxidation reactions under mild conditions
has provided the impulse for research into new effi-
cient systems based on metalloporphyrin catalysts that
mimic natural enzymatic systems [3–7]. Due to strong
complexing properties and catalytic behavior of metal-
loporphyrins, these complexes have found numerous
applications in chemical analysis [8]. Due to their sig-
nificant properties, manganese porphyrins are highly
useful in biochemical applications [9, 10]. The metal-
loporphyrins generally mimic the functions of lignin
peroxidase in degrading lignin model compounds and
shown to be an effective catalyst for pulp bleaching and
pulp mill effluent decolourization [11]. Lignin perox-
idase, a heme containing enzyme secreted by fungal
strains [12–14] which oxidizes Mn(II) to Mn(III) in
the presence of H2O2. It depolymerizes lignin which is
a natural polymer of varying composition containing
aryl-propyl unit [15]. Humic acid has structural simi-
larity with lignin and considered as coal model. Lignin
Water solubility is another required property for the
porphyrins to be utilized in different medicinal pur-
poses, biological and other applications. The study on
artificial water soluble porphyrins is currently under
active research regarding to design, synthesize and
biological assay [17, 18]. In biomimetic work, the pre-
ferred system should contain aqueous medium. How-
ever, the main drawback of the most of Mn(III) por-
phyrins are the inadequate solubility in aqueous
media. To overcome this limitation, the authors were
tried to work on this drawback. On other hand, the
effective biomimetic catalytic activity of Mn(III) por-
phyrins prompted us to explore their depolymerization
activity towards humic acid, so that low molecular
weight coal fractions can be used as a feed stock for
commodity and rare chemicals as an alternative to
depleting oil reserves which are at present the basis of
our chemical industries. The use of Mn(III) porphy-
rins as effective catalysts in the oxidation of various
organic substrates like benzyl alcohol, aniline, ben-
zoin and benzaldehyde was another significant objec-
tive of this work.
1
The article is published in the original.
335

336
BHARATI et al.
thiocyanato(tetraphenylporphinato)MnIII
EXPERIMENTAL
Chemicals
(1,2-
diaminoethane) [Mn(TPP)NCS(dae)], 0.725
g
(0.001 mole) of [Mn(TPP)NCS], along with 4 mL of
1,2-diaminoethane was stirred for 25 minutes and
then refluxed for 36 h. After refluxing the whole con-
tent was cooled at room temperature for 1 h then dried
under vacuum over P2O5. Thus, obtained black crys-
tals were re-crystallized with ethanol. The obtained
yield was 0.640 g (81%). The other complexes were
prepared in the same way. All these complexes were
hygroscopic in nature.
All the chemicals which have been used were of
A.R. grade and have been purified and dried whenever
necessary by the standard methods [19–21]. Pyrrole
was purchased from Merck (Germany) and acetylace-
tone from S.D.-fine chemicals (Mumbai). Pyrrole
and acetyleacetone havebeen used freshly distilled.
Humic acid was in the form of its sodium salt and
purchased from Aldrich. Milli-Q water has been used
throughout the experimental procedure. The stock
solution of humic acid has been prepared in Milli-Q
water 1 mg/mL while the complexes have been used in
10–3 M concentration.
All the chemicals used in the study of catalytic oxi-
dation reaction were obtained from pure grade of SRL
MERCK and OTTO. A mild oxidant H2O2 was used in
all the catalytic oxidation-reactions. The characteriza-
tions of products were done by IR spectra (Model) by
using KBr disc. The progresses of reactions were mon-
itored by UV-Visible spectroscopy.
Catalytic Applications
Coal depolymerization activity. The coal depolym-
erization activity of the Mn(III) porphyrins was
recorded on the same spectrophotometer as men-
tioned above using 1 mL capacity cuvettes at room
temperature. The depolymerization activity has been
assessed by measuring the decrease in absorbance at
450 nm and increase in absorbance at 360 nm [15, 16,
24]. The reaction solution consisted of 20 μL of humic
acid solution and 892 μL of milli-Q water. The reac-
tion was initiated by addition of 88 μL of Mn(III) por-
phyrin solution. Absorbance was observed at the inter-
val of 30 s at 450 nm and 360 nm respectively.
In other catalytic applications of manganese por-
phyrins, oxidation of different substrates like benzyl
alcohol, aniline, benzoin and benzaldehyde was per-
formed based on literature study [29, 30] and similar
methodology was applied successfully to all aforemen-
tioned substrates.
Characterization
The complexes were analyzed using standard pro-
cedures [22, 23]. The elemental analyses have been
done from Cochin University of Science and Technol-
ogy, Cochin. Electronic spectra were recorded on
Hitachi (Japan) model U-2000. I.R. spectra were
recorded on Perkin-Elmer (model-557) Beckman-
Acculab-10. The magnetic susceptibility measure-
ments were carried out at room temperature using EV7
Oxidation of benzyl alcohol. In a 50 mL round bot-
VSM (ADE-DMS-USA) Vibrating Sample Magne- tom flask the substrate benzyl alcohol (20 mmol)
tometer from IIT, Kanpur. Conductivity measure- along with 30% H2O2 (2 mmol) was taken in 10 ml of
ments were carried out on century digital conductivity
acetonitrile and water in 1 : 1 ratio. The mixture was
meter; model CC-601 with 10–3 M concentration in stirred initially and then, 0.01 mmol of Mn(III) por-
ethanol. ESI-mass spectra were recorded on phyrin as catalyst was added. The whole content was
WATERS-Q-T of premier-HAB213 using ethanol as a stirred at room temperature for 30 minutes. The prog-
solvent, from IIT Kanpur. Purity of the complexes was ress of reaction was monitored by UV-visible spectros-
checked by TLC, using CH2Cl2/CH3OH in the vol- copy. Excellent yield of benzaldehyde was achieved for
each complex that was average 82%.
ume ratio of 1 : 4 as the solvent. Coal depolymerization
study was based on previous literature study [15, 16, 24].
Oxidation of aniline. In a 50 mL round bottom flask
the substrate, aniline (20 mmol) along with 30% H2O2
(2 mmol) was taken in 10 mL of acetonitrile solution.
The mixture was stirred initially and then 0.01 mmol
of Mn(III) porphyrin as catalyst was added. The whole
content was stirred at room temperature for 1 hour.
The progress of reaction was monitored by using UV-
visible spectroscopy. Yield: ~84%.
Oxidation of benzoin. In a 50 mL round bottom
flask the substrate benzoin (10 mmol) along with 30%
H2O2 (2 mmol) was taken in 10 mL of acetonitrile
solution. The mixture was stirred initially and then,
0.01 mmol of Mn(III) porphyrin as catalyst was added
along with 0.01 mmol of KOH. The whole content was
Synthesis
Н2TPP (meso-tetraphenylporphyrin) was synthe-
sized by known Adler method [25]. The synthesis of
Mn(III) porphyrins was carried out by adopting a
combined literature methods [26, 27]. The bis (acety-
lacetonato)Mn(III) complexes with axial halo- or
pseudohalo groups i.e. Cl–, Br–, − or NCS–, serve as
N3
useful synthetic intermediate for the synthesis of
Mn(III) porphyrins [28]. The Mn(III) porphyrins
were synthesized by our previous literature method
[24].
Synthesis of Mn(III) porphyrin with 1,2-diami- stirred at room temperature for 40 minutes. The prog-
noethane, [Mn(TPP)X(dae)]. For the synthesis of ress of reaction was monitored by using UV-visible
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 64
No. 3
2019

NOVEL Mn(III) PORPHYRINS AND PROSPECTS
Table 1. Physical properties of Mn(III) porphyrins, colour—black
337
Molar
conductance
(Ω–1 cm2 M–1)
Analysis found (calculated), %
μeff
(B.M.)
Yield,
%
Formula
weight
Complexes
C
H
N
S
Br
–
Cl
Mn
[Mn(TPP)Cl(dae)]
[Mn(TPP)Br(dae)]
[Mn(TPP)N3(dae)]
4.82
4.90
4.85
14
58
37
59
81
72.3
4.70
11.0
–
4.64
(4.29) (7.09)
7.20
762
807
769
785
(72.0) (4.69) (10.9)
68.3 4.49 10.4
(67.9) (4.25) (9.09)
71.7 4.71 16.3
(71.0) (4.69) (15.9)
72.7 5.27 11.6
26
15
18
–
–
9.89
(9.76)
–
–
–
6.80
(6.70)
7.14
(7.10)
–
[Mn(TPP)NCS(dae)] 4.89
3.81
–
6.52
(72.1) (5.15) (11.1) (3.75)
(6.13)
Table 2. Selected vibrational frequencies (cm–1) in IR spectra of Mn(III) porphyrins
[Mn(TPP)N3(dae)]
[Mn(TPP)Cl(dae)]
[Mn(TPP)Br(dae)]
[Mn(TPP)NCS(dae)]
Assignment
424
1615
1324
1176
1560
3021
–
425
1618
1325
1175
1560
3020
–
427
1616
1325
1178
1555
3022
–
2023
3312
3422
425
1618
1328
1175
1560
3020
2080
–
ν(Mn–N)
ν(C=C)py
ν(C=N)py
ν(CPN)py
ν(C=C)ph
ν(C–H)ph
ν(NCS)
ν(N3)
ν(NH2)coordinated
ν(NH2)uncoordinated
–
–
3310
3421
3315
3422
3310
3422
spectroscopy. A change in colour was observed during [Mn(TPP)X(dae)]. The proposed reaction scheme
may be given as below:
reaction progress. Formation of yellow colour precip-
itate of benzoin was started. After completion of reac-
tion, yellow precipitate was filtered and dried. Re-
crystallization was done with ethanol. Yield: ~90%;
mp 94–96°C.
[Mn(TPP)X] + dae
EtOH 26−36 h
Oxidation of benzaldehyde. In a 50 mL round bot-
tom flask the substrate benzaldehyde (20 mmol) along
with 30% H2O2 (2 mmol) was taken in 10 mL of aceto-
nitrile solution and 0.01 g of ammonium acetate was
also added as co-catalyst. The mixture was stirred ini-
tially and then 0.01 mmol of Mn(III) porphyrin as cat-
alyst was added. The whole content was stirred at room
temperature for 3 hrs. The progress of reaction was
further monitored by UV-visible spectroscopy. After
completion of reaction, product was filtered, dried
and then re-crystallized with hot water. Yield: ~81%,
mp 120–123°C.
[Mn(TPP)X(dae)]
Where dae = 1,2-diaminoethane
−
X = Cl−, Br−, N3 or NCS−
.
All these complexes were soluble in ethanol, meth-
anol, pyridine, chloroform, DMSO, DMF and par-
tially soluble in water (~50%). The molar conductance
values of these complexes in ethanol with 10–3 M con-
centration are in the range of 14–26 Ω–1 cm2 mol–1, indi-
cating their non-electrolytic nature [31]. Physical prop-
erties of these complexes have been given in Table 1.
All complexes were characterized by IR, electronic,
and ESI-mass spectra and their spectral details con-
firmed the chemical structure of the complexes syn-
thesized. IR spectra details were in good agreement
with reported literature for specified bands [32–38].
RESULTS AND DISCUSSION
These [Mn(TPP)X] complexes were dissolved in
ethanol and refluxed with 1,2-diaminoethane to give Selected vibrational frequencies (cm–1) in IR spectra
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 3 2019

338
BHARATI et al.
2.7 using Tanabe–Sugano diagram while β has been
calculated using formula:
β = Bin complex Bfree ion
.
The values of B have been found below the free ion
value for MnIII ion (1140 cm–1) [44], which indicates
covalent metal ligand bonds in all these complexes,
with the covalency factor β varying in the range 0.74–
0.77 (Table 4).
ESI-mass spectra was used for identity and purity
of these Mn(III) porphyrins [7, 45–47]. Different
molecular ions obtained for the four Mn(III) porphy-
rins along with their m/z values fully justified the syn-
thesized complexes which are as follow.
[Mn(TPP)Cl(dae)] = m/z 763 for [C46H36N6MnCl]+,
X
N
N
N
III
Mn
N
dae
m/z 727 for [C46H36N6Mn]+, m/z 668 for
[C44H28N4Mn + H]+; m/z 614 for [C44H28N4 + 2H]+,
[Mn(TPP)Br(dae)] = m/z 748 calculated for
[C44H28N4BrMn + H]+; m/z 667 for [C44H28N4Mn ]+;
m/z 614 for [C44H28N4 + 2H]+, [Mn(TPP)N3(dae)] =
m/z 731 calculated for [C44H28N7Mn + Na]+; m/z 667
for [C44H28N4Mn ]+; m/z 614 for [C44H28N4 + 2H]+
and [Mn(TPP)NCS(dae)] = m/z 748 calculated for
[C45H28N5SMn + Na]+; m/z 668 for [C44H28N4Mn +
H]+; m/z 614 for [C44H28N4 + 2H]+.
The magnetic susceptibility measurements show
that these complexes have μeff values in the range of
4.82–4.90 B.M. [48]. The presence of four unpaired
electrons indicates the high spin Mn(III) complexes
with porphyrins.
Fig. 1. Proposed chemical structure of Mn(III) porphy-
−
–
–
–
rins, where X = Cl , Br ,
noethane.
or NCS ; dae = 1,2-diami-
N3
of Mn(III) porphyrins are given in Table 2. UV-Visible
−
spectroscopic data for Cl–, Br–,
and NCS– com-
N3
plexes of manganese(III) porphyrin has been given in
Table 3. The assignment of B band has been done on
the basis of previous studies [39, 40]. All the data
observed for the synthesized MnIII-complexes with
H2TPP and 1,2-diaminoethane were in good agree-
ment with previous literature values. The intense band
in the range 460–471 nm in the spectra of these com-
plexes assigned to the charge transfer from a1u and a2u
orbitals of porphyrin to eg(dπ) orbital of manganese.
This respective band in the spectrum is called charge-
transfer band [41–43]. The ligand field parameters i.e.
10Dq, B and β has also been calculated for these MnIII-
porphyrins. 10Dq have been calculated from the
energy of λmax at maximum absorbance. The value of
B has been calculated by using the formula Dq/B =
On the basis of aforementioned characterization
measurements, all the four complexes have been pro-
posed to be a hepta-coordination complex with axial
ligands in transposition (Fig. 1).
Catalytic Applications
All these newly synthesized Mn(III) porphyrins
were tested for their coal depolymerization activity
towards humic acid for their coal depolymerization
activity towards humic acid by measuring absorbance
decrease at 450 nm and absorbance increase at 360 nm
in solution containing humic acid and Mn(III) por-
phyrins. The results of the studies have been given in
Fig. 2. Figure 2a shows the depolymerization of dark
Table 3. UV-visible spectroscopic data of free base porphy-
rin and Mn(III) porphyrins
Table 4. Ligand field parameters calculated for Mn(III)
porphyrins
λ
max, nm
Ligand/Complexes
B(soret) band
Q band
10Dq,
cm–1
B, cm–1
Complexes
β
H2TPP
406
460
462
475
471
635
647
655
661
675
[Mn(TPP)Cl(dae)]
[Mn(TPP)Br(dae)]
[Mn(TPP)N3(dae)]
Mn(TPP)NCS(dae)
[Mn(TPP)Cl(dae)]
[Mn(TPP)Br(dae)]
[Mn(TPP)N3(dae)]
[Mn(TPP)NCS(dae)]
23764
23148
23062
22893
880
851
854
847
0.77
0.75
0.74
0.74
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 64
No. 3
2019

NOVEL Mn(III) PORPHYRINS AND PROSPECTS
(a) (b)
339
0.207
0.206
0.205
0.204
0.203
0.202
0.201
0.200
0.199
0.232
0.230
0.228
0.226
0.224
0.222
0.220
0.218
0
100
Time, s
200
300
0
100 200
Time, s
300
0.384
0.382
0.380
0.378
0.376
0.374
0.372
0.370
0.368
0.292
0.291
0.290
0.289
0.288
0.287
0.286
0.285
0.284
0
100
200
300
0
100
200
300
Time, s
Time, s
0.067
0.066
0.065
0.064
0.063
0.062
0.061
0.060
0.059
0.130
01.29
0.128
0.127
0.126
0.125
0.124
0.123
0.122
0
0
100
Time, s
200
300
100
200
300
Time, s
0.332
0.330
0.328
0.326
0.324
0.322
0.320
0.318
0.316
0.314
0.420
0.418
0.416
0.414
0.412
0.410
0.408
0.406
0.404
0.402
0.400
0
100
200
300
0
100
200
300
Time, s
Time, s
Fig. 2. (a) Depolymerization activity of [Mn(TPP)Cl(dae)], Mn(TPP)Br(dae)], [Mn (TPP)N (dae)] and [Mn(TPP)NCS(dae)],
3
respectively at 450 nm. (b) Depolymerization activity of [Mn(TPP)Cl(dae)], [Mn(TPP)Br(dae)], [Mn (TPP)N (dae)] and
3
[Mn(TPP)NCS(dae)] respectively at 360 nm.
brown humic acid (decrease in absorbance at 450 nm)
In other catalytic applications; conversion of ben-
and Fig. 2b shows the formation of yellowish coloured zyl alcohol into benzaldehyde, aniline into nitroben-
zene, benzoin into benzyl and benzaldehyde into ben-
zoic acid have been performed by using manganese
porphyrin complexes (Table 5). In a case of conversion
of benzyl alcohol to benzaldehyde, the progress of
reaction was monitored by taking UV-visible spectra at
every 10 minutes of interval. In the spectra, from the
beginning and at the end of reaction, a hypochromic
shift of the Mn(III)porphyrin Soret bands with small
loss of intensity has been observed. A characteristic IR
band appeared at 1674 cm–1 for C=O stretching fre-
compounds (increase in absorbance at 360 nm). Thus,
it has been shown that all these Mn(III) porphyrins
depolymerize the high molecular mass coal fraction
into smaller ones. Our all the synthesized porphyrins
have good levels of water solubility in comparing to our
previously reported Mn(III) complexes and thus,
showed the excellent depoymerization activity in com-
pare to our previously reported porphyrin complexes
[24] which is clear from Fig. 2. The mechanism of
breakdown is still to be investigated.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 3 2019

340
BHARATI et al.
Table 5. Catalytic applications of synthesized manganese porphyrin complexes in conversion reactions
S. No.
Reactants
Products
Temperature
Room
Room
Room
Room
Reaction time, min
Yields, %
1
2
3
4
Benzyl alcohol
Aniline
Benzoin
Benzaldehyde
Nitrobenzene
Benzil
30
60
40
~82
~84
~90
~81
Benzaldehyde
Benzoic acid
180
quency. A small peak at 3075 cm–1 for aromatic C–H
group while a medium peak at 2730 cm–1 for aldehydic
C–H group was found. In a case of conversion of ani-
line to nitrobenzene, the progress of the reaction was
monitored by UV-visible spectra taken at every 15 min
interval. With the progress of reaction, the intensity of
Soret band of the manganese porphyrin catalyst was
increased and also shifted towards lower wavelength.
In IR spectra of product, the more prominent peak at
1516 cm–1 for asymmetric stretching and a medium
peak at 1360 cm–1 for symmetric stretching of N–O
bond of nitro group appeared. Similarly, spectral
results and usual laboratory tests were also complied
with benzil and benzoic acid formation from benzoin
and benzaldehyde respectively.
REFERENCES
1. P. Souza, M. A. Mandiola, A. Arquero, et al., Natur-
forsch. Z. B 49, 263 (1994).
2. N. R. Champness, C. S. Frampton, G. Reid, et al., J.
Chem. Soc. Dalton Trans., 3031 (1994). doi
10.1039/DT9940003031
3. J. T. Groves, J. Porphyrins Phthalocyanines, 4, 350
(2000). doi
4. S. Nimri and E. Keinan, J. Am. Chem. Soc. 121, 8978
(1999). doi 10.1021/ja990314q
5. M. V. Vinodu and M. Padmanabhan, Proc. Indian
Acad. Sci. (Chem. Sci.) 113, 1 (2001).
6. M. M. Q. Simos, M. G. P. M. S. Neves, and J. A. S. Cava-
leiro, Jord. J. Chem. 1, 1 (2006).
7. I. Batinic-Haberle, I. Spasojevic, R. D. Stevens et al.,
Dalton Trans., 617 (2006). doi 10.1039/B513761F
8. M. Biesaga, K. Pyrzynska, M. Trojanowicz, Talanta,
CONCLUSIONS
51, 209 (2000). doi 10.1016/S0039-9140(99)00291-X
9. L. F. Lauffer, Chem. Rev. 87, 901 (1987). doi
In present study, we have synthesized novel
Mn(III) porphyrins which show excellent coal depo-
lymerization performance for humic acid, a lignin
model compound. Thus, these complexes mimic the
activity of lignin peroxidase enzyme, which also shows
the de-polymerization activity but the notable and
important difference is that these complexes show
their activity at room temperature at any pH whereas
lignin peroxidase is pH and temperature sensitive.
Easy preparation, short reaction time, independent of
particular pH and temperature make this an effective
useful method for the de-polymerization of coal and
other lignin model compounds. Such complexes have
also been used to analyze their ability to catalyze the
oxidation reactions. The milder reaction condition,
room temperature and pressure, less time requirement
of reaction, high reactivity and selectivity make these
catalysts efficient for the oxidation reactions.
10.1021/cr00081a003
10. M. Ravikanth and T. K. Chandrashekhar, Structure-
Bond. 82, 105 (1995). doi 10.1007/BFb0036827
11. Biotechnology in Pulp and Paper Industry, Eds. by
P. S. Skerker, R. L. Farrell, D. Dolphin, F. Cui, and
T. Wijesekera (Butterworth-Heinemann, Boston,
1990), Ch. 18.
12. D. L. Crawfold and R. L. Crawfold, Enz. Microb.
Technol. 2, 11 (1980). doi 10.1016/0141-
0229(80)90003-4
13. S. B. Pointing, A. L. Pelling, G. J. D. Smith, et al.,
Mycol
Res.
109,
115
(2005).
doi
10.1017/S0953756204001376
14. V. Shanmugam and K. D. S. Yadav, Indian J. Exp. Biol.
34, 116 (1996).
15. M. Hofrichter, Enz. Microbiol. Technol. 30, 454
(2002). doi 10.1016/S0141-0229(01)00528-2
16. M. Yadav, P. Yadav, K. D. S. Yadav, Biochemistry
(Moscow)
74,
1125
(2009).
doi
10.1134/S0006297909100083
ACKNOWLEDGMENTS
17. T. Murashima, S. Tsujimoto, T. Yamada, et al., Tetra-
hed. Lett. 46, 113 (2005). doi 10.1016/j.tet-
let.2004.11.024
Dr. S.L. Bharati is grateful to Department of
Chemistry, DDU Gorakhpur University for providing
UGC-DSA fellowship during her PhD time. The aca-
demic support of Prof. V.K. Yadav and Prof. S.S. Mano-
haran, Department of Chemistry, IIT Kanpur is
thankfully acknowledged for ESI-MS and Magnetic
Susceptibility measurements. Department of Chemis-
try, NERIST, Nirjuli, Arunachal Pradesh is also
thankfully acknowledged for providing necessary
facilities during some part of the work.
18. J. M. Pedrosa, M. Perez, I. Prieto, Phys. Chem. Chem.
Phys. 4, 2329 (2002). doi 10.1039/B108360K
19. R. J. Errington, Advanced Practical Inorganic and
Metalloorganic Chemistry, 1st Ed. (Chapman and Hall,
London, 1997).
20. W. L. F. Armarego, D. D. Perrin, Purification of Labo-
ratory Chemicals, 4th Ed. (Butterworth-Heinemann,
Oxford, 1997).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 64
No. 3
2019

NOVEL Mn(III) PORPHYRINS AND PROSPECTS
341
21. B. S. Furniss, A. J. Hannaford, V. Rogers, et al., Vogel’s 35. T. N. Lomova and B. D. Berezin, Russ. J. Coord.
Text Book of Practical Organic Chemistry, 4th Ed.
Chem. 27, 85 (2001). doi 10.1023/A:1009523115380
(ELBS, London, 1984).
36. G. Wilkinson, R. D. Gillard, and J. A. McCleverty,
Comprehensive Coordination Chemistry (Pergamon,
Oxford, 1987).
22. G. H. Jeffery, J. Bassett, J. Mendham, et al., Vogel’s
Text Book of Quantitative Chemical Analysis, 5th Ed.
(ELBS, London, 1996).
37. I. Gamo, Bull. Chem. Soc. Jpn. 34, 760 (1961). doi
23. S. Yadava and S. L. Bharati, J. Coord. Chem. 64, 3950
10.1246/bcsj.34.760
(2011). doi .10.1080/958972.2011.632412
38. A. D. Allen and C. V. Senoff, Canad. J. Chem. 43, 888
24. S. L. Bharati and S. Yadava, J. Coord. Chem. 65, 3492
(1965). doi 10.1139/v65-115
(2012). doi .10.1080/00958972.2012.718763
39. J. W. Buchler, W. Kokisch, and P. Smith, Struct. Bond.
25. A. D. Adler, F. R. Longo, J. D. Finarelli, et al., J. Org.
(Berlin) 34, 79 (1978).
Chem. 32, 476 (1967). doi 10.1021/jo01288a053
40. H. Sckeno and H. Kobayashi, J. Chem. Phys. 75, 283
26. E. B. Fleischer, J. M. Palmer, T. S. Srivastava, et al., J.
Am. Chem. Soc. 93, 3162 (1971). doi
10.1021/ja00742a012
27. B. R. Stults, V. W. Day, E. L. Tassett, et al., Inorg.
Nucl. Chem. Lett. 9, 1259 (1973). doi 10.1016/0020-
1650(73)80007-8
(1981).
41. E. Fagadar-Cosma, M. C. Mirica, I. Balcu, et al., Mol-
ecules 14, 1370 (2009). doi 10.3390/mole-
cules14041370
42. Y. Lamamoto, M. D. Assis, K. J. Ciuffi, et al., J. Mol.
Catal. A: Chem. 116, 365 (1997). doi 10.1016/S1381-
1169(96)00343-3
28. B. R. Stults, V. W. Day, R. S. Marianelli, and V. B. Day,
Inorg. Chem. 14, 722 (1975). doi 10.1021/ic50146a004
43. H. A. O. Hill, A. J. Macfarlane, and R. J. P. Williams,
29. B. Bahramian, V. Mirkhani, M. Moghadam, et al.,
Appl. Catal. A: Gen. 315, 52 (2006). doi
10.1016/j.apcata.2006.08.037
30. S. L. H. Rebelo, M. M. Q Simoes, M. G. P. M. S. Neves,
et al., J. Mol. Catal. A: Chem., 201, 9 (2003). doi
10.1016/S1381-1169(03)00149-3
J.
Chem.
Soc.
A,
1704
(1969).
doi
10.1039/J19690001704
44. J. E. Huheey, E. A. Keiter, and R. L. Keiter, Inorganic
Chemistry, Principles of Structure and Reactivity (Pear-
son, Singapore, 2005), p.445.
45. S. L. Bharati, P. K. Chaurasia, and S. Yadava, J. Coord.
31. S. F. A. Kettle, Coordination Compounds (Pitman Press,
Chem. 61, 232 (2016). doi 10.1134/S0036023616020212
London, 1975)
46. I. Batinic-Haberle, I. Spasojevic, R. D. Stevens, et al.,
J. Chem. Soc. Dalton Trans., 2689 (2002). doi
10.1039/B201057G
32. D. W. Thomas and A. E. Martell, J. Am. Chem. Soc.
78, 1338 (1956). doi 10.1021/ja01588a021
33. R. J. H. Clark and C. S. Williams, Spectrochim. Acta
47. I. Batinic-Haberle, I. Spasojevic, R. D. Stevens, et al.,
22, 1081 (1966). doi 10.1016/0371-1951(66)80198-4
Dalton Trans., 1696 (2004). doi 10.1039/B400818A
34. R. J. Dyer, Applications of Absorption Spectroscopy of
Organic Compounds (Prentice-Hall of India, New 48. D. V. Behere and S. Mitra, Inorg. Chem. 19, 992
Delhi, 1969).
(1980). doi 10.1021/ic50206a039
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 3 2019