Novel complexes of Mn(III) with macrocylic porphine ligand and ethylenediamine

Article abstract of DOI:10.1080/00958972.2011.632412

The present work describes the synthesis and characterization of a few Mn(III) porphyrins with ethylenediamine. A new series of high-spin Mn(III) porphyrins having general formula [Mn(TMPP)X] and [Mn(TMPP)X(en)], where TMPP=tetra-p-methoxyphenylporphinato

Full text of DOI:10.1080/00958972.2011.632412

This article was downloaded by: [Cambridge University Library]
On: 06 April 2015, At: 03:04
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Coordination Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gcoo20
Novel complexes of Mn(III) with
macrocylic porphine ligand and
ethylenediamine
Sudha Yadava a & Shashi Lata Bharati a
a Department of Chemistry , DDU Gorakhpur University ,
Gorakhpur-273009, India
Published online: 14 Nov 2011.
To cite this article: Sudha Yadava & Shashi Lata Bharati (2011) Novel complexes of Mn(III) with
macrocylic porphine ligand and ethylenediamine, Journal of Coordination Chemistry, 64:22,
3950-3959, DOI: 10.1080/00958972.2011.632412
To link to this article: http://dx.doi.org/10.1080/00958972.2011.632412
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Journal of Coordination Chemistry
Vol. 64, No. 22, 20 November 2011, 3950–3959
Novel complexes of Mn(III) with macrocylic porphine ligand
and ethylenediamine
SUDHA YADAVA* and SHASHI LATA BHARATI
Department of Chemistry, DDU Gorakhpur University, Gorakhpur-273009, India
(Received 26 October 2010; in final form 29 September 2011)
The present work describes the synthesis and characterization of a few Mn(III) porphyrins with
ethylenediamine. A new series of high-spin Mn(III) porphyrins having general formula
[Mn(TMPP)X] and [Mn(TMPP)X(en)], where TMPP ¼ tetra-p-methoxyphenylporphinato
ligand, X ¼ Clꢀ, Brꢀ, Nꢀ3 or NCSꢀ and en ¼ ethylenediamine. Molar conductance values of
these complexes show their non-electrolytes in ethyl alcohol. These complexes have been
characterized by U.V., I.R., ESI-mass spectra, elemental analyses and magnetic susceptibility
measurements. The tentative structures have also been proposed.
Keywords: Tetra-p-methoxyphenylporphine;
Spectroscopic studies
Ethylenediamine;
Mn(III)
porphyrins;
1. Introduction
Macrocyclic complexes have received much attention [1] because they are involved in
important biological processes, such as photosynthesis and dioxygen transport, in
addition to catalytic properties [2] with important industrial applications. Their
enhanced kinetic and thermodynamic stabilities led to potential applications as metal
extrants [3], radiotherapeutic [4] and medical imaging agents [5]. The occurrence of the
porphyrin rings in nature in such crucial and multiple roles as those spanned by the
heme-proteins, chlorophyll and vitamin B12 suggest that advantages are associated with
this macrocyclic structure [6]. The coordination of anions and small or large molecules
to metalloporphyrins determines their role in enzymatic and catalytic reactions [7, 8].
In metalloporphyrins, electron transfer reactions can be finely tuned by the metal, the
porphyrin macrocycle and the electronic properties of the axial ligands [9]. There has
been growing interest [9, 10] in manganese porphyrins because of their reactivity and
accessibility of several oxidation states that can be used for redox cycles useful for
biochemical applications.
Mn(III) porphyrins have been used as catalysts in oxidative degradation of plasmid
bluescript [11] and as ionophores in potentiometric, piezoelectric or fluorimetric sensor
devices for detection of hydrazine [12], thiocyanate [13], dioxins [14] and salicylate [15].
Mn(III) porphyrins using tetraphenylporphines have been studied extensively [16–19].
*Corresponding author. Email: dr_sudhayadava@yahoo.co.in
Journal of Coordination Chemistry
ISSN 0095-8972 print/ISSN 1029-0389 online ß 2011 Taylor & Francis
http://dx.doi.org/10.1080/00958972.2011.632412

Mn(III) porphine
3951
We have chosen tetra-p-methoxyphenylporphine to see changes in the properties of
Mn(III) porphyrin complexes with the objective of finding better Mn(III) porphyrin
complexes for the applications mentioned above.
2. Experimental
2.1. Materials
All chemicals were of A.R. grade and have been purified and dried whenever necessary
by the standard methods as given in literature [20–22]. Pyrrole (Merck, Germany) and
acetylacetone (S.D.-fine chemicals, Mumbai), have been freshly distilled prior to use.
Milli-Q water has been used throughout the experimental procedures.
2.2. Physical measurements
The complexes were analyzed using standard procedures [23]. C, H, and N contents
were analyzed from Cochin University of Science and Technology, Cochin.
Conductivity measurements were carried out on a Century digital conductivity meter,
model CC-601, with 10ꢀ3 mol Lꢀ1 concentration in ethanol at room temperature. Purity
of the complexes was checked by TLC plates using silica gel adsorbent and CH2Cl2/
CH3OH in 8/2 ratio. Electronic spectra were recorded on a Hitachi (Japan) model U-
2000 from 200–1100 nm in methanol. IR spectra were recorded using KBr discs on a
Perkin-Elmer (model-557) Beckman Acculab-10. Magnetic susceptibility measurements
were carried out at room temperature using a EV7VSM (ADE-DMS, USA) Vibrating
Sample Magnetometer, from IIT, Kanpur. ESI-mass spectra were recorded on a
WATERS-Q-T of Premier-HAB213 using ethanol as solvent, from IIT, Kanpur.
2.3. Syntheses
2.3.1. Preparation of ligand. Tetra-p-methoxyphenylporphine has been synthesized by
literature method [24]. Freshly distilled pyrrole 5.6 mL (0.08 mol) and 9.7 mL (0.08 mol)
of anisaldehyde were refluxed with 300 mL of propionic acid for 30 min. The solution
was cooled at room temperature and filtered. Dark shining purple crystals were
obtained, washed with methanol, followed by hot water and finally dried in vaccum.
Recrystallization was done with 1 : 1 ratio of dichloromethane and chloroform.
2.3.2. Preparation of Mn(III) porphyrins, [MnIII(TMPP)X]. All Mn(III) porphyrin
syntheses were based on an adaptation of combined literature methods [25, 26]. The
bis(acetꢀylacetonato) Mn(III) complexes with axial halo- or pseudo-halo groups, i.e.
Clꢀ, Br , Nꢀ3 or NCSꢀ, serve as useful intermediates for Mn(III) porphyrins [27].
For preparation of chloro-complex, 0.979 g (0.003 mol) of [MnIII(acac)2Cl] and 2.5 g
(0.003 mol) of H2TMPP were dissolved in 150 mL of glacial acetic acid containing
45 mL of acetic anhydride and refluxed for 4 h on a hot plate. After refluxing, volatile
materials were removed on a steam-bath and resulting bright green complex was dried

3952
S. Yadava and S.L. Bharati
under vaccum over P2O5. Recrystallization was done with 1 : 1 ratio of chloroform and
methanol, and then air dried. The yield was 3.19 g (91%). The Brꢀ, N3ꢀ and NCSꢀ
complexes were prepared analogously. All these complexes are non-hygroscopic. This
method gives higher yield and takes less time in comparison to previous reported
literature methods for the synthesis of other Mn(III) porphyrins.
2.3.3. Preparation of ethylenediamine complexes, [MnIII(TMPP)X(en)]. For prepara-
tion of the chloro complex, 0.822 g (0.001 mol) of [MnIII(TMPP)Cl] was dissolved in
4.0 mL of ethanol and then added to it 2.0 mL (0.030 mol) ethylenediamine. The whole
content was stirred for 25 min at room temperature then refluxed for 24 h. The reaction
mixture was cooled at room temperature for 1 h and dried under vaccum over P2O5.
Recrystallization was done with ethanol. Yield was 0.668 g (75%). The Brꢀ, N3ꢀ and
NCSꢀ complexes were prepared analogously. All these complexes are hygroscopic and
stored in a desiccator.
3. Results and discussion
The Mn(III) complexes with porphyrin were synthesized by the following reaction
scheme:
[MnIII(acac)2X] + H2TMPP
Gla. Acetic acid
containing acetic
anhydride
4 h
[MnIII(TMPP)X]
where acac = acetylacetonate
X = Cl–, Br–, N3– or NCS–
H2TMPP = tetra-p-methoxyphenylporphine
These [MnIII(TMPP)X] complexes were dissolved in ethanol and refluxed with ethylenediamine
to give final product. The proposed reaction scheme may be given as:
[MnIII(TMPP)X] + en
EtOH
↓
24 h
[MnIII(TMPP)X(en)]
These complexes were soluble in ethanol, methanol, pyridine, chloroform, DMSO
and partially in water. The molar conductance values in EtOH with 10ꢀ3 mol Lꢀ1
concentration are in the range 12–26 ꢀꢀ1 cm2 molꢀ1, indicating non-electrolytes [28].
The physical properties of these complexes have been given in table 1.

Mn(III) porphine
3953

3954
S. Yadava and S.L. Bharati
Table 2. Selected vibrational frequencies (cmꢀ1) in IR spectra of Mn(III) porphyrins.
Mn(TMPP)Cl
Mn(TMPP)Br
Mn(TMPP)N3
Mn(TMPP)NCS
Assignment
428
1623
1330
1517
3025
1174
–
425
1623
1325
1517
3023
1173
–
425
1620
1325
1512
3025
1173
–
426
1623
1323
1515
3026
1173
2074
–
ꢀ(Mn–N)
ꢀ(C¼C)py
ꢀ(C¼N)py
ꢀ(C¼C)ph
ꢀ(C–H)ph
ꢀ(OCH3)
ꢀ(NCS)
–
–
2023
ꢀ(N3)
3.1. Infrared spectra
Infrared spectra of these complexes show sharp bands at ꢁ1622 cmꢀ1 suggesting
ꢀ(C¼C)pyrrole. A medium band at ꢁ1324 cmꢀ1 for ꢀ(–C¼N–)pyrrole appears at 1350 cmꢀ1
in the free ligand. This band shows a downward shift of ꢁ25 cmꢀ1 indicating
coordination of porphine nitrogen. A medium band at ꢁ1512 cmꢀ1 indicates
ꢀ(C¼C)phenyl. Another weak absorption at ꢁ1173 cmꢀ1 indicates ꢀ(–OCH3) of
phenyl. A strong band at ꢁ840 cmꢀ1 is assigned to p-disubstituted benzene. A sharp
band at ꢁ956 cmꢀ1 indicates the presence of (C–H) rocking mode of pyrrole. All these
peaks are in agreement with previous literature values [29, 30]. The spectra show two
bands characteristics of coordinated NCSꢀ i.e. ꢀ(C–N) at ꢁ2074 cmꢀ1 and ꢀ(C–S) at
820 cmꢀ1 suggesting coordination of NCSꢀ [31] in the thiocyanate complex. Two
characteristic peaks of coordinated azide ꢀas(N–N) show the strong absorption at
1248 cmꢀ1 and another broad peak at ꢁ2030 cmꢀ1, indicating coordination of –Nꢀ3 [32].
The ꢀ(Mn–N) was characterized by the presence of an absorption at ꢁ425 cmꢀ1 for all
the complexes [30, 33] (table 2).
The asymmetric NH2 stretching frequency for ethylenediamine is 3440–3250 cmꢀ1; in
Zn(en)Cl2 it is given at 3290–3230 cmꢀ1 showing the chelating en [34]. While in the case
of these Mn(III) porphyrins ꢀ(NH2) appears at ꢁ3422 cmꢀ1 showing the presence of
free amine group and at ꢁ3315 cmꢀ1 corresponding to the amine group that has
coordinated with the metal ion. Characteristic bands of diamines appear between
1400 cmꢀ1–700 cmꢀ1. A strong band at ꢁ1330 cmꢀ1 has been assigned to ! (NH2). The
CN stretching modes of all uncomplexed diamines appear at 1090–1070 cmꢀ1 [35]. In
these newly synthesized complexes, ꢀ(CN) band appears at 1055–1046 cmꢀ1, the
downward shift showing the coordination of nitrogen to manganese. The NH2 rocking
mode is a strong band at ꢁ637 cmꢀ1. Two medium peaks at ꢁ848 cmꢀ1 and ꢁ881 cmꢀ1
indicate CH2 rocking mode. The ꢀ(C–C) has been assigned as a strong band at
ꢁ1005 cmꢀ1 [36]. The data indicate ethylenediamine is coordinated to Mn(III) as a
unidentate ligand (table 3).
3.2. Electronic spectra
Depending on the type of donor acceptor bonds there are three classes of
metalloporphyrins electronic spectra, normal, hypso and hyper, with the hyper spectra
being further divided into p-type and d-type [37, 38]. The third type of spectra i.e.

Mn(III) porphine
3955
Table 3. Selected vibrational frequencies (cmꢀ1) in IR spectra of Mn(III) porphyrins.
Mn(TMPP)Cl(en)
Mn(TMPP)Br(en)
Mn(TMPP)N3(en)
Mn(TMPP)NCS(en)
Assignment
ꢀ(Mn–N)
ꢀ(C¼C)py
ꢀ(C¼N)py
ꢀ(C¼C)ph
ꢀ(C–H)ph
ꢀ(OCH3)
ꢀ(NCS)
426
1621
1323
1517
3023
1175
–
423
1623
1325
1514
3021
1173
–
428
1623
1330
1515
3025
1174
–
2030
3310
3420
425
1622
1324
1512
3023
1173
2080
–
–
–
ꢀ(N3)
ꢀ(NH2)coordinated
ꢀ(NH2)uncoordinated
3315
3422
3312
3421
3310
3422
Table 4. Location and intensity of bands in absorption spectra of solutions of Mn(III)
complexes with TMPP and ethylenediamine in methyl alcohol.
ꢂmax nm (log ")
Complex
I (Q)
II
III
IV (B)
[Mn(TMPP)Br]
[Mn(TMPP)NCS]
[Mn(TMPP)N3]
684 (5.82)
681 (5.83)
677 (5.83)
682 (5.83)
625 (5.79)
604 (5.78)
652 (5.81)
651 (5.81)
520 (5.71)
560 (5.74)
556 (5.74)
558 (5.74)
589 (5.77)
567 (5.75)
591 (5.77)
–
–
–
444 (5.64)
451 (5.65)
448 (5.65)
460 (5.66)
431 (5.63)
440 (5.64)
435 (5.63)
427 (5.63)
515 (5.71)
514 (5.71)
485 (5.68)
471 (5.67)
465 (5.66)
466 (5.66)
[M(TMPP)Cl]
[Mn(TMPP)Br(en)]a
[Mn(TMPP)NSC(en)]
[Mn(TMPP)N3(en)]
[Mn(TMPP)Cl(en)]
aSolution of the complex in toluene.
d-hyper type are observed for metalloporphyrins having unoccupied orbitals in metals
with symmetries eg(d(ꢁ)) – dyz and dxz. The intense band at 440–480 nm in spectra of the
complexes [39] is assigned to charge transfer from the a1u(ꢁ) and a2u(ꢁ) orbitals of
porphyrin to the eg(d(ꢁ)) orbitals of the metal, a charge-transfer band [40].
Electronic spectra of porphyrins exhibit an intense band at 400 nm that are assigned
as soret or B band. Several weaker absorptions also occur at higher wavelengths,
480–700 nm, that are known as Q bands. For [MnIII(TPP)X] complexes [30] these bands
are at ꢁ615, ꢁ580, ꢁ525, ꢁ481 and ꢁ400, where X ¼ Clꢀ, Brꢀ, Acꢀ or NCSꢀ, while in
manganese(III) 5,10,15,20-tetra(N-ethyl-3carbazolyl) porphyrin, [MnIII(TCEP)] [41],
these bands appear at 433, 523, 562, and 654 nm.
For [Mn(TMPP)X], where X ¼ Brꢀ, NCSꢀ, Nꢀ3 or Clꢀ, characteristic B bands (Soret
band) have ꢂmax at 444, 451, 448, and 460 nm while the Q bands appear at ꢂmax 684,
681, 677, and 682, respectively. The [Mn(TMPP)X] complexes with ethylenediamine
exhibit B bands at 431, 440, 435, and 427 nm and Q bands at 625, 604, 652, and 651,
respectively. The assignment of B band has been done on the basis of previous studies
[42, 43]. These B and Q bands exhibit small red shifts in the spectra, due to the effect of
axial ligand and solvent [44, 45] (table 4).
Thus all data for manganese complexes with H2TMPP and ethylenediamine follow
similar trends when compared with TPP and TCEP manganese(III) complexes.

3956
S. Yadava and S.L. Bharati
Table 5. Ligand field parameters calculated for Mn(III) porphyrins.
Complexes
10Dq (cmꢀ1
)
B (cmꢀ1
)
ꢃ
[Mn(TMPP)Br]
26,371
25,614
25,933
24,703
25,000
28,153
29,620
28,801
976
948
960
914
0.85
0.83
0.84
0.80
0.81
0.91
0.96
0.93
[Mn(TMPP)NCS]
[Mn(TMPP)N3]
[Mn(TMPP)Cl]
[Mn(TMPP)Br(en)]
[Mn(TMPP)NSC(en)]
[Mn(TMPP)N3(en)]
[Mn(TMPP)Cl(en)]
925
1042
1097
1066
Since all Mn(III) porphyrins have
a
high-spin d4 configuration, the
strongly antibonding b1g orbital remains empty. The energy of the a1g level is
somewhat depressed. Further the eg(dꢁ) metal level is also depressed as it is bonding
with respect to the back ꢁ bonding with the porphyrin. The relative position of the eg
and b2g levels may be reversed. The lowest energy allowed charge transfer bands are the
porphyrin to metal a2u,a1u ! eg(dꢁ) transitions [46]. Bands I, II, and IV can be assigned
to a2u, a1u ! eg(dꢁ) charge transfer transitons. The assignment of band IV to charge
transfer transition has been previously suggested [47]. Ligand field parameters such as
10Dq, B and ꢃ have also been calculated for these Mn(III) porphyrins; 10Dq have been
calculated from the energy of ꢂmax at maximum absorbance. The value of B has been
calculated by the formula Dq/B ¼ 2.7 using Tanabe-Sugano diagram while ꢃ values have
been calculated using formula
ꢃ ¼ Bin complex=Bfree ion
The values of Racah interelectronic repulsion parameter (B) are below the free ion
value for Mn(III) ion (1140 cmꢀ1) [48], which indicates covalent metal ligand bonds in
all the complexes, with the covalency factor ꢃ varying in the range 0.88 ꢂ 0.08 (table 5).
3.3. Magnetic susceptibility measurements
The magnetic momentum values of these complexes are in the range 4.65–4.87 B.M.
[25, 49], indicating the presence of four unpaired electrons confirming high spin 3d4
configuration in all the complexes.
3.4. ESI-mass spectra
Electrospray-ionization mass spectroscopy was used for identity and purity analysis of
the Mn(III) porphyrins [50–52]. The molecular weight of the complexes have also been
calculated. The spectra give m/z 845 for [C49H36N5O4SMn]þ, m/z 787 for
[C48H36N4O4Mn]þ and m/z 734 for [C48H36N4O4 þ 2 H]þ for [Mn(TMPP)NSC(en)].
For [Mn(TMPP)Cl(en)], m/z 847 for [C50H44N6O4Mn–Cl]þ, m/z 805 for
[C48H36N4O4Mn þ H2O]þ and m/z 773 for [C48H38N4O4 þ K]þ have been obtained.
For [Mn(TMPP)Br(en)], m/z at 868 for [C48H36N4O4BrMn þ H]þ, m/z at 805
for [C48H36N4O4Mn þ H2O]þ and m/z at 734 for [C48H36N4O4 þ 2 H]þ and for [Mn

Mn(III) porphine
3957
OMe
X
N
N
N
N
OMe
MeO
MnIII
OMe
OMe
X
N
N
N
N
OMe
MeO
MnIII
en
OMe
Figure 1. Proposed structure for Mn(III) porphyrins.
(TMPP)N3(en)], m/z at 830 for [C48H36N7O4Mn þ H]þ, m/z at 805 for
[C48H36N4O4Mn þ H2O]þ and m/z at 734 for [C48H36N4O4 þ 2 H]þ have been found.
3.5. Structure
On the basis of elemental analysis, U.V., I.R., conductivity measurements, magnetic
susceptibility measurements and ESI-mass spectra, the first four complexes have been

3958
S. Yadava and S.L. Bharati
proposed to be square pyramidal while the proposed geometry for Mn(III) porphyrins
with ethylenediamine is octahedral as reported earlier [18, 19]. These proposed
structures are shown in figure 1.
4. Conclusion
Tetra-p-methoxyphenylporphinato Mn(III) complexes have been prepared. ESI-mass
spectra indicate monomeric complexes. On the basis of the positions of NH2 stretching
frequency in I.R. spectra of tetra-p-methoxyphenylporphinato manganese(III) com-
plexes with ethylenediamine, it has been concluded that ethylenediamine is unidentate.
Generally, the metal porphyrins are insoluble in water but in the case of Mn(III)
porphyrins with ethylenediamine a significant feature is that these are moderately
soluble in water. Water solubility is required to use porphyrins for medicinal purposes
[53]. Sun et al. [54] have synthesized porphyrin-nicacid dyad Mn(III) complexes to see
the combined effect of porphyrin and nicacid on DNA cleavage. Here we report
Mn(III) complexes with tetra-p-methoxyphenylporphine and ethylenediamine. It will be
interesting to see in which way these new complexes will affect DNA cleavage, a
property which has been seen in Mn(III) porphyrin complexes as tumor targeting agents
in photodynamic therapy [55, 56].
Acknowledgements
The authors acknowledge UGC-DSA Fellowship (New Delhi) for financial support and
would like to thank Prof. V.K. Yadav and Prof. Sundar S. Manoharan from IIT,
Kanpur, for ESI-mass spectra and magnetic susceptibility measurements.
References
[1] P. Souza, M.A. Mandiola, A. Arquero, V. Fernandez, E. Gulicrrer-Puebla, C. Ruiz Valero. Naturforsch
Z., 49b, 263 (1994).
[2] N.R. Champness, C.S. Frampton, G. Geid, D.A. Toucher. J. Chem. Soc., Dalton Trans., 3031 (1994).
[3] A.R. Adam, M. Antolovich, D.S. Baldwin, P.A. Duckworth, A.J. Leong, L.F. Lindoy, M. McPartlin,
P.A. Tasker. J. Chem. Soc., Dalton Trans., 1013 (1993).
[4] J.P.L. Cox, K.J. Jankowaski, K. Ataky, D. Parker, M.A. Eaton, N.R. Beeley, A.J. Millican, A. Harrison,
C. Walker. J. Chem. Soc., Chem. Commun., 797 (1989).
[5] L.F. Lauffer. Chem. Rev., 87, 901 (1987).
[6] M. Ravikanth, T.K. Chandrashekhar. Structure-Bonding, 82, 105 (1995).
[7] O.A. Golubchikov, O.I. Koifman, G.V. Ponomarev. In Porphyrins: Spectroscopy, Electrochemistry and
Applications, N.S. Enikolopyan (Ed.), p. 214, Nauka, Moscow (1987).
[8] A.B. Solov’era, T.N. Rumyantseva. In Advances in Porphyrin Chemistry, O.A. Golubchikov (Ed.),
Vol. 3, p. 245, NII Khimii SpbGU, St. Petersberg (2001).
[9] A. Budimir, T. Smuc, T. Weitner, I. Batinic-Haberle, M. Birus. J. Coord. Chem., 63, 2750 (2010).
[10] I. Batinic-Haberle, J.S. Reboucas, I. Spasojevic. Antioxid. Redox Signaling, 13, 877 (2010).
[11] S. Banafi, E. Cassani, E. Caruso, M. Cazzaro. Bioorg. Med. Chem., 11, 3595 (2003).
[12] M.S.M. Quintino, K. Araki, H.E. Toma, L. Angnes. Talanta, 74, 730 (2008).
[13] J.H. Khorasani, M.K. Amini, H. Motaghi, S. Tangestaninejad, M. Moghadam. Sens. Actuators B:
Chem., 87, 448 (2002).
[14] M. Mascini, A. Macagnano, D. Monti, M.D. Carlo, R. Paolesse, B. Chen, P. Werner, A. D’Amico, C. Di
Natale, D. Conpagnone. Biosens. Bioelectron., 20, 1203 (2004).

Mn(III) porphine
3959
[15] N.A. Chaniotakis, A.M. Chasser, M.E. Meyerhoff, J.T. Grives. Anal. Chem., 60, 185 (1988).
[16] A. Tulinsky, B.M.L. Chen. J. Am. Chem. Soc., 99, 3647 (1977).
[17] V.W. Day, B.R. Stults, E.L. Tassett, R.S. Marianelli, L.J. Boucher. Inorg. Nucl. Chem. Lett., 11, 505
(1975).
[18] J.F. Kirner, W.R. Scheidt. Inorg. Chem., 14, 2081 (1975).
[19] V.W. Day, B.R. Stults, E.L. Tassett, R.S. Marianelli, L.J. Boucher. Inorg. Nucl. Chem. Lett., 11, 505
(1975).
[20] R.J. Errington. Advanced Practical Inorganic and Metalloorganic Chemistry, 1st Edn, Chapman and Hall,
London (1997).
[21] W.L.F. Armarego, D.D. Perrin. Purification of Laboratory Chemicals, 4th Edn, Butterworth-
Heinemann, Oxford (1997).
[22] B.S. Furniss, A.J. Hannaford, V. Rogers, P.W.G. Smith, A.R. Tatchell. Vogel’s Text Book of Practical
Organic Chemistry, 4th Edn, ELBS, London (1984).
[23] G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denny. Vogel’s Text Book of Quantitative Chemical
Analysis, 5th Edn, ELBS, London (1996).
[24] A.D. Adler, F.R. Longo, J.D. Finarelli, J. Goldmacher, J. Assour, L. Karsakoff. J. Org. Chem., 32, 476
(1967).
[25] E.B. Fleischer, J.M. Palmer, T.S. Srivastava, A. Chatterjee. J. Am. Chem. Soc., 93, 3163 (1971).
[26] B.R. Stults, V.W. Day, E.L. Tassett, R.S. Marianelli. Inorg. Nucl. Chem. Lett., 9, 1259 (1973).
[27] B.R. Stults, V.W. Day, R.S. Marianelli. Inorg. Chem., 14, 722 (1975).
[28] S.F.A. Kettle. Coordination Compounds, p. 168, Thomas Nelson and Sons, The Pitman Press, London
(1975).
[29] D.W. Thomas, A.E. Martell. J. Am. Chem. Soc., 78, 1338 (1956).
[30] T.N. Lomova, B.D. Berezin. Russ. J. Coord. Chem., 27, 85 (2001).
[31] R.J.H. Clark, C.S. Williams. Spectrochim. Acta, 22, 1081 (1966).
[32] J.R. Dyer. Applications of Absorption Spectroscopy of Organic Compounds, Prentice-Hall of India Private
Limited, New Delhi (1969).
[33] G. WilkinsonSir, R.D. Gillard, J.A. McCleverty. Comprehensive Co-ordination Chemistry, Vol. 2,
p. 816, Pergamon Press, Oxford (1987).
[34] B.H. Stuart. Infrared Spectroscopy: Fundamentals and Applications, p. 104, John Wiley & Sons,
Chichester, West Sussex, England (2004).
[35] I. Gamo. Bull. Chem. Soc. Jpn., 34, 760 (1961).
[36] A.D. Allen, C.V. Senoff. Can. J. Chem., 45, 888 (1965).
[37] C. Cretu, C. Bucovicean, I. Armeanu, A.M. Lacrama, E. Cosma-Fagadar. Rev. Chim. Bucharest, 59, 979
(2008).
[38] A.D. Adler, F.R. Longo, J.D. Finarelli, J. Goldmacher, J. Assour, L. Karsakoff. J. Org. Chem., 32, 477
(1967).
[39] E. Fagadar-Cosma, M.C. Mirica, I. Balcu, C. Bucovicean, C. Cretu, I. Armeanu, G. Fagadar-Cosma.
Molecules, 14, 1370 (2009).
[40] Y. Lamamoto, M.D. Assis, K.J. Ciuffi, C.M.C. Prado, B.Z. Prellwitz, M. Moraes, O.R. Nascimento,
H.C. Sacco. J. Mol. Catal. A: Chem., 116, 365 (1997).
[41] C.P. Tidewall, L.D. Fondren, D.E. Nikles. Molbank, M656 (2010).
[42] J.W. Buchler, W. Kokisch, P. Smith. Struct. Bonding (Berlin), 34, 79 (1978).
[43] H. Sckeno, H. Kobayashi. J. Chem. Phys., 75, 283 (1981).
[44] L.J. Boucher. J. Am. Chem. Soc., 90, 6640 (1968).
[45] L.J. Boucher. In Coordination Chemistry, S. Kirschner (Ed.), p. 126, Plenum Press, New York, NY
(1969).
[46] L.J. Boucher. J. Am. Chem. Soc., 92, 2727 (1970).
[47] H.A.O. Hill, A.J. MacFarlane, R.J.P. Williams. J. Chem. Soc., 1704 (1969).
[48] J.E. Huheey, E.A. Keiter, R.L. Keiter. Inorganic Chemistry, Principles of Structure and
Reactivity, 4th Edn, p. 445, Pearson Education, Singapore (2005).
[49] D.V. Behere, S. Mitra. Inorg. Chem., 19, 992 (1980).
[50] I. Batinic-Haberle, I. Spasojevic, R.D. Stevens, B. Bondurant, A. Okado-Matsumoto, I. Fridovich,
Z. Vujaskovic, M.W. Dewhirst. Dalton Trans., 617 (2006).
[51] I. Batinic-Haberle, I. Spasojevic, R.D. Stevens, I. Fridovich, P. Hambright. J. Chem. Soc., Dalton Trans.,
2689 (2002).
[52] I. Batinic-Haberle, I. Spasojevic, R.D. Stevens, A. Okado-Matsumoto, I. Fridovich, P. Hambright,
P. Neta. Dalton Trans., 1696 (2004).
[53] T. Murashima, S. Tsujimoto, T. Yamada, T. Miyazawa, H. Uno, N. Ono, N. Sugimoto. Tetrahedron
Lett., 46, 113 (2005).
[54] E. Sun, X. Cheng, D. Wang, C. Zhuang, A. Xia, T. Shi. J. Coord. Chem., 62, 1584 (2009).
[55] J. Stubbe, J.W. Kozarich. Chem. Rev., 87, 1107 (1987).
[56] R. Song, Y.S. Kim, Y.S. Sohn. J. Inorg. Biochem., 89, 83 (2002).