Synthesis of a Novel Manganese(III) Porphyrin and Its Catalytic Role in Selective Oxidation of Aromatic Alcohols

Article abstract of DOI:10.1134/S003602361909002X

Abstract: A novel azido complex of manganese(III) porphyrin with 1-methylimidazole has been synthesized. This complex can be abbreviated as [Mn^III(THMPP)N₃(1-MeIm)], where THMPP is 5,10,15,20-tetrakis(4-hydroxy-3-methoxyphenyl)porphi

Full text of DOI:10.1134/S003602361909002X

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2019, Vol. 64, No. 9, pp. 1101–1104. © Pleiades Publishing, Ltd., 2019.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Synthesis of a Novel Manganese(III) Porphyrin and Its Catalytic Role
in Selective Oxidation of Aromatic Alcohols
a
a
b,
c,
Niharika Anand , Sudha Yadava , Pankaj Kumar Chaurasia *, and Shashi Lata Bharati **
a
Niharika Anand and Sudha Yadava, Department of Chemistry, DDU Gorakhpur University, Gorakhpur, 273009 India
b
Department of Chemistry, LS College, Muzaffarpur, Bihar, 842001 India
c
Department of Chemistry, North Eastern Regional Institute of Science and Technology,
Nirjuli, Arunachal Pradesh, 791109 India
*
e-mail: pankaj.chaurasia31@gmail.com
*e-mail: shashilatachem@gmail.com
*
Received September 19, 2018; revised December 17, 2018; accepted March 20, 2019
Abstract—A novel azido complex of manganese(III) porphyrin with 1-methylimidazole has been synthe-
III
sized. This complex can be abbreviated as [Mn (THMPP)N (1-MeIm)], where THMPP is 5,10,15,20-
3
tetrakis(4-hydroxy-3-methoxyphenyl)porphine and 1-MeIm is1-methylimidazole. The complex has been
characterized by UV-visible, FT-IR, ESI-MS spectra, elemental analysis, and magnetic susceptibility. The
tentative structure has been proposed to be octahedral. The catalytic activity of the complex synthesized has
been studied using different oxidants in the selective oxidation of aromatic alcohols to aldehydes. The selec-
tively transformed products have been obtained under room conditions and short time period in high yields.
Keywords: manganese(III) porphyrin, 1-methylimidazole, 5,10,15,20-tetrakis(4-hydroxy-3-methoxyphe-
nyl)porphine, alcohol, catalyst, oxidation
DOI: 10.1134/S003602361909002X
In recent years, interest for the synthesis of manga- catalytic properties have also been tested in the oxida-
nese porphyrins due to their applications in biomi- tion of aromatic alcohols to their corresponding alde-
metic chemistry and oxidation catalysis is rapidly hydes using different oxidants.
increased. Synthetic manganese porphyrins can
mimic the actions of superoxide dismutase (SOD) [1–
EXPERIMENTAL
3
] and catalase enzymes [4–7]. These are extensively
used as structural and functional models of the cyto-
chrome P-450, a well known monooxygenase enzyme
Materials
4
-Hydroxy-3-methoxybenzaldehyde (Vanillin),
benzyl alcohol, sodium periodate and hydrogen per-
[
8, 9].
Transformation of organic substrates into their use- oxide were purchased from S.D. Fine-Chem Limited
ful forms is extremely beneficial for the large scale pro- (Mumbai). 1-Methylimidazole and 4-methoxybenzyl
duction. The classical oxidation methods generally alcohol were purchased from Chemical Centre
take long time for completion of reactions with low (Mumbai). Sodium hypochlorite was purchased from
selectivity and produce immense amounts of hazard- Merck (Mumbai). Chemicals were of A.R. grade. Pyr-
ous wastes. To overcome these drawbacks, various role (Merck, Germany) and acetylacetone (S.D. Fine-
transition metal based catalysts are being used. Metal- Chem Limited, Mumbai) were freshly distilled before
loporphyrin is the most important class of catalysts use. Milli-Q water has been used during the experi-
which is being used in such types of oxidation reac- ment from our laboratory (Waters Millipore).
tions. Meso-tetraarylporphyrin derivatives generally
show better catalytic activities among all the synthetic
Physical Measurements
Electronic spectra were recorded in methanol on a
porphyrins. The first use of synthetic metalloporphy-
rin as a catalyst in the oxidation reactions was reported
by Groves and coworkers in 1979 [10]. After then, Hitachi (Japan) spectrophotometer model U-2900
many researchers have attempted to use metallopor- from 190–900 nm in our laboratory. FT-IR spectra
phyrins as catalysts in various organic syntheses [11–29]. were recorded on a Perkin Elmer spectrum II spectro-
In this work, a novel manganese(III) porphyrin photometer using potassium bromide pellets (4000–
–1
complex has been synthesized and characterized. The 400 cm ). ESI-Mass spectra were recorded on a
1101

1
102
NIHARIKA ANAND et al.
Found (%): C, 64.11; H, 4.37; N, 12.84; O, 13.08;
Waters UPLC-TQD device. FT-IR and ESI-Mass
data were provided by SAIF, CDRI (Central Drug Mn, 5.60.
Research Institute, Lucknow). Electrical conductivity
data were recorded on a TOSHCON Auto ranging
–3
Catalytic Applications
Conductivity Meter TCM 15+ by preparing 10
molar solution in ethanol at room temperature. Ele-
Oxidation of alcohol to aldehyde catalyzed by
mental analyses were carried out on an Elemental Mn(THMPP)N (1-MeIm). Catalytic application was
3
Vario EL III by SAIF, STIC (Cochin). Magnetic sus- based on the literature studies [35–38]. 2 mmol of
ceptibility measurements were obtained at room tem- aqueous oxidant sodium periodate was added to the
perature on a Vibrating Sample Magnetometer from solution of acetonitrile (5 mL), alcohol (0.5 mL), and
IIT (Kanpur).
complex (0.01 g). Now, solution was stirred using
magnetic stirrer at room temperature. 1 mL aliquots of
the reaction mixture were withdrawn at regular inter-
vals of 5 min and UV-visible spectra were recorded
using UV-visible spectrophotometer Hitachi (Japan)
model U-2900.
Synthesis of Complexes
Preparation of porphyrin [H THMPP]. The por-
2
phyrin ligand, i.e. 5,10,15,20-tetra(4-hydroxy-3-
methoxyphenyl) porphine [H THMPP], was synthe-
2
sized by using Adler’s method with some modifica-
tions [30]. In this method, 5.6 mL (0.08 mol) of freshly
distilled pyrrole and 12.16 g (0.08 mol) of vanillin were
added in 300 mL of boiling propionic acid and the
whole reaction mixture was refluxed for 2 h. After
cooling, the reaction mixture was kept in refrigerator
for 12 h. The reaction mixture was filtered and washed
thoroughly with methanol until the filtrate became
colorless. The purple color crystals of porphyrin were
recrystallized with 1 : 1 ratio of chloroform and
dichloromethane.
RESULTS AND DISCUSSION
Characterization of the Complex
The newly synthesized manganese(III) complex
was hygroscopic and blackish-green in colour. It was
soluble in methyl alcohol, ethyl alcohol, acetone, ace-
tonitrile and chloroform. The molar conductance
–
1
2
–1
(
11 Ω cm mol ) indicates its non-electrolytic char-
acter [39].
UV-visible spectral studies. The UV-visible spec-
III
trum of Mn (THMPP)N exhibits a strong B band at
3
4
15 nm and four Q bands at 510, 545, 585 and 640 nm
Preparation of azide complex of manganese(III)
III
III
[40–42]. In case of Mn (THMPP)N (1-MeIm), two
porphyrin [Mn (THMPP)N ]. First of all,
Mn (acac) N (where acac = acetylacetonate) has
3
3
III
Q bands disappeared in the spectrum due to the coor-
dination of sixth ligand. There was red shift in B band
2
3
been synthesized by using literature method [31]. This
acetylacetonate complex of manganese(III) act as
intermediate in the preparation of manganese(III)
(
470 nm) and blue shift in Q bands (570, 605 nm).
The calculated values of ligand field parameters i.e.
III
porphyrin complex [32–34]. Preparation of 10Dq, B, and β for Mn (THMPP)N
(1-MeIm) were
3
III
–1
–1
Mn (THMPP)N was done by taking 0.003 mol of 23585 cm , 873 cm , and 0.77 respectively. The crys-
3
III
tal field splitting energy (10Dq) has been calculated
with the help of λ value at maximum absorbance.
Mn (acac) N and H THMPP and dissolved it in
2
3
2
1
50 mL of glacial acetic acid containing 45 mL acetic
max
Tanabe-Sugano diagram has been used for calculating
Racah interelectronic repulsion parameter (B)
whereas covalency factor (β) has been calculated with
following formula:
anhydride. The whole reaction mixture was refluxed
for 4 h. After removing the solvent by evaporation on
steam-bath, bluish-green crystalline solid complex
was obtained. Recrystallization was done with 1 : 1
ratio of chloroform and methanol.
β = Bin complex Bfree ion
,
Preparation of manganese(III) porphyrin complex
3+
–1
where B
for Mn ion = 1140 cm [43]; β is less
than 1, which means that the B value of complex is
free ion
III
with 1-methylimidazole [Mn (THMPP)N (1-MeIm)].
0
3
III
1 mmol (0.90 g) of Mn (THMPP)(N ) was dis- below the free ion value and thus confirms that the
3
solved into 8 mL of methyl alcohol with further addi- metal-ligand bond in the newly synthesized complex
tion of 1-methylimidazole (10 mmol, 0.8 mL) to it fol- is covalent in nature.
lowed by stirring for about 10 minutes. It was refluxed
for 23 h and cooled at room temperature for 1 h. The
reaction mixture was filtered and filtrate has been
evaporated and dried under vacuum over P O After
FT-IR spectral studies. The significant peaks
observed
in
the
FT-IR
spectrum
of
Mn(THMPP)N (1-MeIm) are given in Table 1.
3
2
5.
These peaks indicate the formation of the novel com-
plex.
drying, complex was found as blackish-green coloured
sticky solid. Yield – 0.78 g (80.41%).
Magnetic susceptibility measurements. Magnetic
For C H N O Mn anal. calcd. (%): C, 64.00; H, moment is calculated with the help of magnetic sus-
.34; N, 12.92; O, 13.12; Mn, 5.63.
52
42
9
8
4
ceptibility [44]. The μeff value for the complex was 4.78
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 64
No. 9
2019

SYNTHESIS OF A NOVEL MANGANESE(III)
1103
–
1
Table 1. Selected vibrational frequencies (cm ) in FT-IR In these experiments, NaIO , H O and NaOCl have
4
2
2
spectrum of Mn(THMPP)N (1-MeIm)
3
been used as oxygen source. The product characteri-
zation has been done by UV-visible, TLC and qualita-
tive analysis. The percentage yields of the products
obtained have been given in Table 2. Blank experi-
ments have also been done which gave only trace
amount of products. There are some other papers of
manganese based catalytic application may be helpful
for readers [48–54].
ν, cm–1
Assignment
6
21
Ring torsion (1-MeIm)
OPP bend (1-MeIm)
C–Hbend (pyrrolic)
C–Hrock (pyrrolic)
OCH3
6
7
62
63
1
1
1
1
1
1
1
1
090
168
204
273
414
456
519
590
859
C–N str
N3
OH
OCH
3
C=N (pyrrolic)
C–H bend (OCH3)
In plane str (1-MeIm)
C=C (ph)
H
3
CO
N
3
N
N
N
III
HO
Mn
OH
OCH
2
C–Hstr
N
1
-Melm
3
3115
C–Hstr (aromatic ring of 1-MeIm)
O–H
3
437
H
3
CO
O
OH
OH
Oxidant, CH
3
CN/H
2
O
H
which indicate the presence of four unpaired electrons
and confirms the formation of high-spin manga-
nese(III) complex [45–47].
R
R
Aromatic alcohol
R = H, OCH3
Substituted benzaldehyde
ESI-Mass spectral studies. The ESI-MS spectrum
of Mn(THMPP)N (1-MeIm) shows m/z values at
3
8
11, 852, 853, 854, 934, 935, 936 and 950 which corre-
Scheme 1. Oxidation of alcohols to aldehydes catalyzed
+
+
spond to [C H N O ] , [C H N O Mn] , by Mn(THMPP)N (1-MeIm).
48
36
5
+
8
48 36
4
8
3
+
[
[
[
C H N O Mn + H] , [C H N O Mn + 2H] ,
48 36 4 8 48 36 4 8
C H N O Mn] , [C H N O Mn
C H N O Mn + 2H] and [C H N O Mn+ 2H]
+
+
+
H] ,
5
2
42
6
8
52 42
6
8
+
+
CONCLUSIONS
52
42
6
8
52 42
7
8
ions respectively. These ions indicate the constituent
fragments of the molecule and thus help in the struc-
ture elucidation.
A new manganese(III) porphyrin complex with 1-
methylimidazole has been synthesized and character-
ized. The catalytic activity of this complex has also
been tested in selective oxidative transformation of
alcohols to aldehydes. Benzyl alcohol and 4-methoxy-
benzyl alcohol for the oxidation reactions were
Catalytic Properties
The utility of the novel azido complex of manga-
nese(III) porphyrin with 1-methylimidazole as a cata-
selected as substrate while NaIO , H O and NaOCl
4
2
2
lyst in the oxidative conversion of benzyl alcohol to have been used as oxygen source. These reactions take
benzaldehyde and 4-methoxybenzyl alcohol to place at room temperature and complete in 20 min
4-methoxybenzaldehyde has been tested (Scheme 1). only.
Table 2. Product yields in oxidation of benzyl alcohol catalyzed by Mn(THMPP)N (1-MeIm) with different oxidants
3
Product yield (%)
Entry
Substrate
Oxidant
Solvent
after 20 min
1
2
3
4
5
6
Benzyl alcohol
Benzyl alcohol
Benzyl alcohol
4-Methoxybenzyl alcohol
4-Methoxybenzyl alcohol
4-Methoxybenzyl alcohol
NaIO4
H O
CH CN/H O
86
69
34
90
76
38
3
2
CH CN
2
2
3
NaOCl
NaIO4
H O
CH CN
3
CH CN/H O
3
2
2
2
CH CN
3
NaOCl
CH CN
3
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 64 No. 9 2019

1104
NIHARIKA ANAND et al.
FUNDING
This work was supported by UGC, New Delhi to
Niharika Anand in the form of Rajiv Gandhi National Fel-
lowship.
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Supplementary materials are available for this article at
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