Manganese(III) mediated synthesis of A2B Mn(III) corroles: A new general and green synthetic approach and characterization

Article abstract of DOI:10.1016/j.inoche.2017.10.018

A new general and green synthetic protocol for the synthesis of manganese(III) metallocorroles has been developed from substituted aryl aldehydes and 5-(4-nitrophenyl)dipyrromethane using manganese salt as template. This is the first report in the synthesis of corroles: the formation of direct C–C bond through metal initiation. This method allows higher working concentrations than those previously reported. The new A₂B manganese(III) metallocorroles were synthesized in good yield for different applications. The single crystal X-ray structure of 10-(3,4,5-fluorophenyl)-5,15-bis(4-nitrophenyl)manganese(III) corrole is also reported and shows that manganese atom is situating atop on macrocyclic plane.

Full text of DOI:10.1016/j.inoche.2017.10.018

Accepted Manuscript
Manganese(III) mediated synthesis of A2B Mn(III) corroles: A
new general and green synthetic approach and characterization
Omprakash Yadav, Atul Varshney, Anil Kumar
PII:
S1387-7003(17)30542-7
doi:10.1016/j.inoche.2017.10.018
INOCHE 6806
DOI:
Reference:
To appear in:
Inorganic Chemistry Communications
Received date:
Revised date:
Accepted date:
2 July 2017
16 October 2017
17 October 2017
Please cite this article as: Omprakash Yadav, Atul Varshney, Anil Kumar , Manganese(III)
mediated synthesis of A2B Mn(III) corroles: A new general and green synthetic approach
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ACCEPTED MANUSCRIPT
Manganese(III) mediated synthesis of A B Mn(III)corroles: A new general
2
and green synthetic approach and characterization
*
Omprakash Yadav, Atul Varshney and Anil Kumar
Department of Applied Chemistry, Delhi Technological University, Bawana Road, Delhi-42,
India.
E-mail: anil_kumar@dce.ac.in
Abstract: A new general and green synthetic protocol for the synthesis of manganese(III)
metallocorroles has been developed from substituted aryl aldehydes and 5-(4-
nitrophenyl)dipyrromethane using manganese salt as template. This is the first report in the
synthesis of corroles: the formation of direct C-C bond through metal initiation. This method
allows higher working concentrations than those previously reported. The new A B
2
manganese(III) metallocorroles were synthesized in good yield for different applications. The
single crystal X-ray structure of 10-(3,4,5-fluorophenyl)-5,15-bis(4-nitrophenyl)manganese(III)
corrole is also reported and shows that manganese atom is situating atop on macrocyclic plane.
Keywords: Corroles, Metallocorroles, Green Chemistry, dipyrromethane, one-pot method
1

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Graphical abstract
A new general and green protocol for metallocorroles using metal as template and report for
direct C-C bond formation in corroles synthesis.
Corrole chemistry increased exponentially after the discovery of facile, convenient and high
1
-6
yield synthetic methods developed by Paloesse, Gross, Gryko and their coworkers. In recent
years, metallocorroles are of great interest due to their exceptional properties that free base
7
corroles, an trianionic ligand, induces on metal chelated to it. The important property imparted
7
by free base ligand is the stability of metal in high oxidation states. Because of this utility of,
metallocorroles are responsible for important aspects related to energy, photochemistry,
8
-9
luminescence spectroscopy and other biological applications. The important are activation of
+
10-14
small molecules such as O , CO , H , H O , HOONO and more.
Manganese and iron
2
2
2
2
complexes have already been introduced as robust catalyst for such type of applications: oxygen
atom transfer reactions, oxygen, carbon dioxide and protons reduction reactions and antioxidants
1
1,12,15-30
in biological systems.
It has been clearly seen that manganese corroles have performed
9
,31
excellently in advanced applications.
Therefore, corroles and metallocorroles synthesis have
3
1
attracted great attention in recent years. Looking back into the synthesis of corroles, the first
corrole was synthesized by Johnson and Kay by cyclisation of 5,5'-bi-(5'-bromodipyrromethenes)
2

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and introduced a meso carbon atom, cyclisation of bilene and biladienes with the introduction of
link between two α-carbon atoms but resulted into the formation of a palladium(II)-10-
3
2
oxacorrole instead. Later on biladenedihydrobromide derivative was used for the synthesis of
corrole using different metal salts as template and rhodium metal complex was confirmed by X-
3
3
ray crystallographic method. The metallocorroles were obtained only in the case of manganese
3
3-34
and iron metal salts used.
Manganese as a template has been used to synthesize corrole with
3
4
the condensation of dipyrrins in DMF. Paolesse and co-workers reported first direct synthesis
of cobalt corrole using 3,4-Dimethyl-2-(a-hydroxybenzyl)- pyrrole-5-carboxylic acid as
3
5
monopyrrolic sourse. Superoxide induced cyclizations of metallo-2,2'-bidipyrrins was found to
3
6
be selective for the synthesis of corrole. Alternatively, the reaction of free base octaethylcorrole
3
7
with carbonyl complex of manganese in toluene also gave metallocorroles. Till now, the
3
8
3-4
6
methods developed by Murakami, Gross and Gryko, the oxidative cyclization of α, ω-
didesoxybiladienes-a,c are being used for the preparation of corroles. The most convenient
method to obtain manganese(III) corroles after the facile syntheses of free base corroles is the
2
-7
reaction of free base corroles with manganese(II) acetate dihydrate in polar solvents. To date,
there is no report available in the literature for the synthesis of A B manganese(III) corroles
2
directly by a reaction between bilane and metal salt to yield metallocorroles via difficult C-C
bond formations.
In this paper, we report first the direct C-C bond formation in the synthesis of manganese(III)
corroles with various substituents, which can be used with a large variety of substituted
benzaldehydes including sterically hindered, electron withdrawing, electron releasing group
substituted (Scheme 1). The idea of selecting 5-(4-nitrophenyl)dipyrromethane is that the large
number of applications were reported on such corroles and metallocorroles which contain C6F5
3

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3
-6
groups on their meso-carbon positions. Usually, these corroles have high stability and ease of
1
9
an excellent characterization tool: the F NMR spectroscopy. It is very important to develop
protocols for such types of corroles which do not contain the strong electron withdrawing and
very expensive C F groups on meso positions. The choice of 5-(4-nitrophenyl)dipyrromethane
6
5
3
seems to be practically interesting candidate to fulfill the desired requirement. Further, reduction
of nitro group will certainly enhance the corroles electron – richness and reduced product 4-
aminophenyl moieties may be used as synthetic models for further modifications.
All the manganese(III) corroles were characterized by UV–visible spectroscopy, elemental
analysis and mass spectrometry. Due to paramagnetic nature of manganese(III) corroles, NMR
spectroscopy was not performed to characterize the compounds. The electronic spectra of
manganese(III) corroles reported, herein, are similar to those of previously reported
1
6-17
manganese(III) porphyrins and corroles.
The UV-visible spectrum as shown in Fig. 1
confirms the formation of desired manganese corroles and calculated yield were found to be
1
6-17
comparable to available literature.
They display split Soret bands (λmax = 400-425 nm), a
ligand-sensitive absorbance at λmax = 480-490 nm and broad Q bands at 600 nm (Fig. 1).
The present reaction conditions were optimized with respect to solvent, temperature, time of the
reaction and use of reactants used. Initially, we planned to follow the procedure as reported for
3
9
metalloporphyrins. The 5-(4-nitrophenyl)dipyrromethane and pentafluorobenzaldehyde was
dissolved in DMF and HCl was added dropwise over a period of 10 min. and the resulting
reaction mixture was refluxed. The progress of the reaction was checked with TLC and UV-
visible spectroscopy. But we could not succeed to get desired metallocorroles. So we changed
our strategy and follow the path of first synthesizing bilane using 5-(4-
nitrophenyl)dipyrromethane and aryl aldeydes in methanol-water containing HCl mixture. The
4

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bilane was extracted and dissolved in DMF. This reaction was carried out with two different
routes. In Route-I as shown in Scheme 1 produced manganese(III) corroles after the continuous
stirring of reactants overnight and yielded desired product in low yield. Whereas in Route-II the
reaction mixture was refluxed and yielded desired product in 1 hr. The progress of the reaction
was checked with TLC and UV-visible spectroscopy which shows the formation of product after
the refluxing of 15 min. only but completion of the reaction was confirmed after 1 hr in the form
of high yield of product. The yield of the manganese(III) corroles also depend upon the nature of
substituents present on the aldehyde used in the reaction. In the case of synthesis of A B
2
corroles, pentafluorobenzaldehyde and 5-(4-nitrophenyl)dipyrromethane were used to optimize
the reaction conditions. The different arylaldeydes used are tabulated in Table 1. Using this
method, we have synthesized a variety of manganese (III) corroles including complexes with
sterically encumbered, electron withdrawing and electron releasing group substituted corroles in
good yields.
5

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Scheme 1
6

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1.2
1.0
0.8
0.6
0.4
0.2
0.0
1
2
3
4
5
6
7
8
9
1
0
400
500
600
700
800
Wavelength (nm)
Fig. 1: UV-visible spectra of synthesized manganese(III) corroles.
In a typical reaction freshly distilled pentafluorobenzaldehyde (130 μL, 0.5 mmol) and 5-(4-
4
0
nitrophenyl)dipyrromethane (566 mg, 1.0 mmol) was dissolved in methanol (200 mL) and
mixture and water (100 mL) containing HCl (36%, 10 mL) was added slowly. The reaction
mixture was kept on stirring for two hours at room temperature under air. After two hours of
stirring, the crude product was washed and extracted several times with chloroform and dried
over anhydrous sodium sulfate. The solvent was removed using a vacuum pump. The extracted
product was dissolved in 50 ml of argon-purged dimethylformamide. The mixture was stirred
and 2.5 equiv. of manganese (III)acetatetetrahydrate was added. The final reaction mixture was
refluxed for 1 h in air. The rate of the reaction was monitored with TLC. After 1 hr refluxing,
DMF was removed in vacuo. The dark colored product was dissolved in dichloromethane and
purified by flash chromatography over silica gel using ethyl acetate as eluent. The final product
7

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was purified over alumina using ethyl acetate-hexane (7:3) mixture as eluent. The purified
product was recrystallized using ethyl acetate and hexane and afforded dark green crystals, 185
mg, 24 % yield.
Fig. 2. Single crystal X-ray structure of 3.
8

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The single crystal X-ray structure of one of the manganese(III) corrole, 3, obtained is shown in
Fig. 2. Manganese atom is axially coordinated to oxygen atom of dimethylformamide.
Manganese atom is situated 0.257 Å above the mean plane of 4 pyrrolic nitrogens and 0.32 Å
above the mean plane of macrocyclic core atoms. These values are comparable to axial
coordination to the manganese atoms in corroles and values are comparable to the literature
1
7, 41
value reported earlier.
In conclusion, we first report that metal ion initiates the cyclisation of bilane through carbon-
carbon bond formation to yield manganese(III) corroles under aerobic conditions. The advantage
of our method is the general nature of the reaction which is valid for any type of substituted
aldehyde and aryldipyrromethane. This method also avoids the difficult steps to form firstly C-C
bond formation and then cyclization of dipyrrin using metal as reported in the literature. So,
methodology reported in this paper follow the principles of Green Chemistry so protocol is
Green in nature. The yield of the manganese(III) corroles was reasonably good and the reaction
time was shorter than in other methods reported. Also, higher concentration of reagents can be
employed.
9

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Table 1: Analytical data of manganese(III) corroles. (Elemental analysis given in ref. no. 42)
Compound
Bilane
Yield
%)
UV-visible
data
HRMS
(
Calculated
(Found)
(
in nm)
419,474,591,
39
1
24%
758.0534
(758.0521)
Ar =
6
2
3
4
5
6
7
8
9
14%
20%
22%
19%
11%
17%
07%
10%
20%
416,471,591,
56
423,470,590,
39
420,473,588,
44
419,474,590,
51
412,464,590,
60
418,474,590,
39
418,472,590,
60
419,472,589,
41
418,471,591,
41
746.0110
(746.0138)
722.0722
(722.0706)
726.1060
(727.1126)
722.0722
(722.0718)
736.0225
(737.2099)
758.1322
(758.1302)
736.0879
(736.0863)
698.1110
(698.1122)
704.0816
(705.0866)
Ar =
Ar =
Ar =
Ar =
Ar =
Ar =
Ar =
Ar =
Ar =
6
6
6
6
6
6
6
6
1
0
6
10

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Acknowledgment
OPY thanks to CSIR and AV thanks to UGC for fellowship and AK thanks to DTU for
infrastructural facilities.
Supporting Information
HRMS of the reported metallocorroles can be found in supporting information file.
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0. The pyrrole (3 equiv.) was added to the 100 mL of 0.18 M aqueous HCl (1.5:98.5), followed by
the addition of the 4-nitrobenzaldehyde (1 equiv., 2.0 g, 0.010–0.019 mol). The resulting reaction
mixture was stirred at room temperature and the progress of the reaction was monitored by TLC.
After 2 hr stirring, the precipitated yellow solid product was filtered off and washed with water
and dried yellow product was again washed with petroleum ether to afford 5-(4-
nitrophenyl)dipyrromethane in high yields (97%).
41. The chemical formula and ring labeling system is shown in Figure 2. Crystal data for compound
3
: C H F MnN O , Mw, 795.61; system, monoclinic; space group, P 21/c; unit cell dimensions,
40 25 3 7 5
a= 8.0405(6) Å; b = 23.987(3) Å; c = 18.1125(13) Å;  = 90⁰ꢅ β =9ꢁ.ꢁ93(ꢀ)⁰;  = 90⁰; V
3
3
=
3490.5(5)Å ; Z = 4; T = 150 K; R , 0.1239; R(all), 0.1979; Gof = 1.019ꢅ Δ
= 1.035 e Å ;
ρmax
int
3
Δρmin= -1.119 e Å . The resolution obtained for the structure of the compounds was limited by the
poor quality of the available crystals. Intensity data were collected at 150(2) K on Bruker
diffractometer (a single wavelength Enhance X-ray source with MoK radiation, λ = 0.71073 Å).
α
The selected suitable single crystals were mounted using paratone oil on the top of a glass fiber
fixed on a goniometer head and immediately transferred to the diffractometer. Pre-experiment,
data collection, data reduction and analytical absorption corrections were performed with the
Bruker SAINT program. The crystal structures were solved with SHELXS-97 using direct
2
methods. The structure refinements were performed by full-matrix least-squares on F with
SHELXL-97. All programs used during the crystal structure determination process are included
in the WINGX software. CCDC no. 1556509.
42. CHN data. Calculated (Found); 1: C 58.59 (59.60), H 2.13 (2.23), N 10.08 (11.11); 2: C 59.46
(
57.47), H 2.70 (3.57), N 11.24 (11.05); 3: C 61.51 (61.80), H 2.51 (2.65), N 11.63 (12.01); 4: C
4.47 (64.46), H 3.19 (3.39), N 11.57 (11.47); 5: C 61.51 (61.46), H 2.51 (2.36), N 11.63 (11.47);
6
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6
: C 60.26 (55.16), H 2.70 (3.57), N 11.40 (7.48); 7: C 63.33 (61.62), H 3.59 (3.30), N 11.08
(
11.04); 8: C 61.97 (61.46), H 2.74 (2.63), N 11.41 (11.24); 9: C 65.33 (65.75), H 3.32 (3.50), N
2.03 (11.74); 10: C 63.08 (63.24), H 2.72 (2.90), N 11.93 (12.66).
1
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Highlights




We report direct C-C bond through metal initiation in corrole.
It is a green synthetic protocol.
It is a synthesis of metallocorroles directly from bilane.
Manganese(III) as template has been used for the synthesis of metallocorroles.
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