Effect of peripheral modification of manganese(III) porphyrazine on its reactivity in the coordination of imidazole

Article abstract of DOI:10.1134/S107042801110023X

Coordination of imidazole to manganese(III) porphyrazine and phthalocyanine modified by multiple peripheral substitution by trifluoromethylphenyl, trifluoromethylphenoxy, tert-butylphenyl, and 3,5-ditert- butylphenoxy groups was studied by spectrophotometric titration, and UV, visible, and IR spectroscopy. Manganese(III) complexes were found to react with imidazole with formation of 1 : 1 complexes in one-step reversible process. Specificity of the effect of multiple substitution of the macroring on quantitative parameters of reactions with the organic base is related to structural features of the organic complexes. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S107042801110023X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 10, pp. 1581–1587. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.N. Ovchenkova, T.N. Lomova, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 10, pp. 1551–1557.
Effect of Peripheral Modification of Manganese(III)
Porphyrazine on Its Reactivity in the Coordination of Imidazole
E. N. Ovchenkova and T. N. Lomova
Institute of Solution Chemistry, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: tnl@isc-ras.ru
Received March 10, 2011
Abstract—Coordination of imidazole to manganese(III) porphyrazine and phthalocyanine modified by
multiple peripheral substitution by trifluoromethylphenyl, trifluoromethylphenoxy, tert-butylphenyl, and 3,5-di-
tert-butylphenoxy groups was studied by spectrophotometric titration, and UV, visible, and IR spectroscopy.
Manganese(III) complexes were found to react with imidazole with formation of 1:1 complexes in one-step
reversible process. Specificity of the effect of multiple substitution of the macroring on quantitative parameters
of reactions with the organic base is related to structural features of the organic complexes.
DOI: 10.1134/S107042801110023X
Biologically active porphyrin complexes, in partic-
ular chlorophyll, blood heme in hemoglobin, catalases,
and peroxidases, are characterized by a developed
system of functional substituents. The action of these
complexes in natural entities implies coordinative satu-
ration of the central metal ion [1–3]. Coordinative
unsaturation is achieved by choice of metal atom and
formation of periphery of macroheterocycle; the larger
the formal charge on the metal ion, the higher its
coordinative unsaturation. Complexes of metal cations
whose charge exceeds in absolute value the charge of
porphyrin dianion (P2–) attract the strongest interest.
Coordination of bases to complexes of highly charged
cations is complicated due to possibility for redox
transformations of the central atom and replacement of
existing acyclic ligands [4–6]. Manganese(III) com-
plexes are appropriate subjects for studying the effect
of structural modification of organic ligand in such
reactions. Strong bases, such as piperidine, diethyl-
amine, triethylamine, and 3-hydroxypiperidine, favor
reduction of (X)MnIIITPP (where X is a singly charged
anionic ligand, and TPP is 5,10,15,20-tetraphenyl-
21H,23H-porphyrin dianion) to manganese(II) com-
plexes in toluene [7, 8]. The resulting molecular com-
plexes possess different properties. Solutions of
(L)MnIIP (L is methylimidazole or pyridine) are fairly
resistant to atmospheric oxygen: irreversible oxidation
to manganese(III) porphyrins is slow (it takes several
hours), whereas MnIIP is oxidized instantaneously [9].
Comparison with analogous porphyrazine complexes
makes it possible to estimate the role of aromatic
system in the transmission of substituent effects on the
reaction center in base coordination processes.
An attempt was made [6] to determine a relation
between the stability of donor–acceptor complexes of
(X)MnIIITPP with bases [molecular complexes
(L)(X)MnIIITPP] and the nature of anionic ligand X–.
However, the effect of the structure of the organic part
on the formation of molecular complexes remains
an open and important problem.
In the present work we studied the stoichiometry,
quantitative parameters of complex formation process,
and spectral properties of soluble donor–acceptor com-
plexes of imidazole (Im) with heavily substituted por-
phyrazine and phthalocyanine manganese(III) com-
plexes I–V [(AcO)MnIIITAP and (AcO)MnIIIPc, re-
spectively].
The purity of complexes I–V was confirmed by
their elemental compositions and electronic absorption,
IR, and mass spectra which coincided with the data
reported in [10]. The electronic absorption spectra
were typical of five-coordinate manganese complexes
(AcO)MnIIIP. In the spectrum of I and II in toluene we
observed two intense absorption bands at λ 650–675
(I) and 405–420 nm (III); in going to more extended
π-system in phthalocyanine complexes III–V, these
bands were displaced to red and blue regions, respec-
tively (λ 725–740 and 395–410 nm). The observed
variations are consistent with the theoretical data [11].
1581

OVCHENKOVA, LOMOVA
1582
R
R
R
R
R
R
N
OAc
N
OAc
R
R
N
N
N
N
Mn
N
Mn
N
N
N
N
N
N
N
R
R
N
N
R
R
R
R
R
R
I, II
III–V
I, R = 3-F3CC6H4 (AcO)MnTAP(3-F3CC6H4)8; II, R = 4-t-BuC6H4, (AcO)MnTAP(4-t-BuC6H4)8; III, R = 3-F3CC6H4,
AcO)MnPc(3-CF3C6H4)8]; IV, R = 3-F3CC6H4O (AcO)MnPc(3-CF3C6H4O)8]; V, R = 3,5-(t-Bu)2C6H3O,
(AcO)MnPc[(3,5-(t-Bu)2C6H3O)8.
Manganese(II) complexes MnIITAP and MnIIPc are
characterized by radically different spectral parameters
[12, 13]. The axial AcO– ligand was identified by IR
spectroscopy [10].
absorption spectra of the products do not change
drastically, and they remain typical of macrocyclic
chromophore coordinated to manganese(III). Our ex-
periments showed that the observed spectral variations
are reversible, i.e., reactions of complexes I–V with
imidazole go to some equilibrium state.
The reaction of complexes I–V with imidazole (Im)
was studied in toluene over a wide range of concen-
trations of the latter (0 to 1.47×10–2 M) at 298 K. The
upper imidazole concentration limit is determined by
its solubility in toluene. Imidazole molecule exhibits
σ-donor and π-acceptor properties [14] and it well
matches porphyrin macroring in a single coordination
sphere, which predetermined the choice of organic bio-
active base. The optical densities used in the calcula-
tion of equilibrium constants were measured at those
wavelengths which corresponded to the maximal dif-
ference between the electronic absorption spectra of
complexes I–V and products of their reaction with
imidazole (see table).
The spectrophotometric titration curves smoothly
descend up to a minimal optical density (straight line
with a bent, Fig. 1). All complexes I–V took up one
imidazole molecule, as followed from the slope of the
logI—f(logcIm) dependences (see table, Fig. 2). The
stability constants (l/mol) of the complexes of I–V
with Im are considerably higher than unity (see table).
Thus the complexation process between (AcO)MnP
and Im can be represented by equilibrium (1).
Ks
(AcO)MnP
+
Im
(AcO)(Im)MnP
(1)
Addition of imidazole to a solution of compound I,
III, or IV in toluene induced blue shifts of the long-
wave absorption band by 3–5 nm and of the short-
wave absorption band by 6–8 nm (see table, Fig. 1a).
Compounds II and V displayed a blue shift of the
short-wave absorption band by 9–13 nm and red shift
of the long-wave absorption band by 2–4 nm (see
table, Fig. 1b). As follows from Fig. 1, the electronic
The stability constants of donor–acceptor com-
plexes with imidazole (Ks) were calculated by the
equation for a three-component equilibrium system
with two colored components:
(Ai – A0)/(A∞ – A0)
1 – (Ai – A0)/(A∞ – A0) [c0Im – c0(AcO)MnP(Ai – A0)/(A∞ – A0)]
1
Ks =
.
Quantitative parameters of the reactions of complexes I–V with imidazole in toluenea
Complex
λmax, nm
λanal, nm
n
Ks, l/mol
I
399, 461, 650
408, 498, 675
389, 503, 733
387, 719
399, 653
408, 673
389, 738
387, 723
388, 727
0.98
0.97
1.01
1.06
0.94
143±23
099±12
32±3
II
III
IV
V
26±5
388, 731
44±4
a
λanal stands for analytical wavelength, p is the number of added imidazole molecules, and λmax and stability constants Ks refer to the
complexes with imidazole.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

EFFECT OF PERIPHERAL MODIFICATION OF MANGANESE(III) PORPHYRAZINE
1583
(a)
A
(b)
727
A
A
738
733
A
0.78
0.8
0.80
731
0.74
0.70
0.8
0.76
0.72
0.005 0.010 0.015
0.6
0.4
0.2
0.0
0.005 0.010 0.015
cIm, M
cIm, M
388
407
389
0.4
0.0
397
514
450
600
750
λ, nm
450
600
750
λ, nm
Fig. 1. Electronic absorption spectra of compounds (a) III and (b) V in toluene–imidazole mixture (cIm = 0–1.5×10–2 M) and the
corresponding spectrophotometric titration curves at (a) λ 738 and (b) 727 nm.
Here, c0Im and c0(AcO)MnP are, respectively, the initial
concentrations of imidazole and complexes I–V in
toluene; A0, Ai, and A∞ are the optical densities at
a working wavelength of the initial manganese com-
plex, equilibrium mixture at a definite imidazole con-
centration, and donor–acceptor complex with imidaz-
ole. The Ks values were optimized by the least squares
procedure using Microsoft Excel. The relative error in
determination of Ks did not exceed 15%. The number
of imidazole molecules in the complex with I–V was
determined by the least squares optimization of the de-
pendence logI = f(logcIm) where I = (Ai – A0)/(A∞ – Ai).
the corresponding band of the initial five-coordinate
manganese complex. Unlike compounds I, III, and IV,
the substituents in (AcO)MnOPTAP are electron-
donor, but tetrahydrofuran exhibits π-donor properties
instead of π-acceptor typical of imidazole.
The formation of donor–acceptor complexes with
imidazole according to reaction (1) without removal of
acetate ion from the coordination sphere was con-
firmed by analysis of the IR spectra of equilibrium
mixtures in which the concentration of imidazole was
equal to that in the equivalence point upon titration
(Fig. 1). The IR spectra (SiO2 film) were recorded on
a Bruker Vertex 80v spectrometer using the subtraction
technique; the baseline was the spectrum of a toluene–
imidazole mixture with concentration of the latter in
the equivalence point after subtraction of coordinated
imidazole. In the IR spectrum of the complex of IV
According to the data of [15], analogous reaction
of (AcO)MnOPTAP (where OPTAP is 2,3,7,8,12,13,-
17,18-octaphenyltetraazaporphyrin dianion) and tetra-
hydrofuran in toluene is accompanied by a blue shift
(by 6 nm) of the long-wave absorption band relative to
(a)
logI
0.5
(b)
logI
0.5
0.5
0.5
logcIm
–3
–2
logcIm
–3
–2
–0.5
–1.5
–2.5
–0.5
–1.0
–1.5
5
2
1
3
4
Fig. 2. Plots of logI versus concentration of imidazole logcIm for the reactions of imidazole with complexes (1) I, (2) II, (3) III, (4)
IV, and (5) V; (a) r2 = 0.97, (b), r2 = 0.98.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

OVCHENKOVA, LOMOVA
1584
1
iron(III) complexes. Replacement of the –CH= groups
by –N= is accompanied by red shift of the long-wave
absorption maxima (bands I and II) and blue shift of
the short-wave absorption band (III). The largest shift
was observed for band I. Using experimental (elec-
tronic spectroscopy) [21] and theoretical [22] methods,
frontier orbital diagram was constructed for tetraaza-
porphyrin iron(III) complexes, and absorption bands in
their electronic spectra were assigned: bands I and III
were attributed to charge transfer from the a1 orbital to
2
dπ (dπ stands for dxz and dyz orbitals) and from a1 to dz ,
2
and band II (Q), to electronic transition a2 →e. It is
seen that tetraaza substitution in (AcO)MnIIIP changes
the energy of dπ orbitals most appreciably; these
orbitals are stabilized, and the energy of the transition
a1 →dπ decreases (the corresponding absorption band
shifts to longer wavelengths). The energies of other
orbitals involved in other electronic transitions in the
optical range change to a considerably lesser extent.
*
*
* *
*
** * * *
1500
1000
ν, cm–1
500
Variations in the electronic absorption spectra of
(AcO)MnIIIP upon addition of imidazole may be inter-
preted on the basis of the above assignment of absorp-
Fig. 3. IR spectra of (1) (AcO)MnPc(3-CF3C6H4O)8 and
(2) its molecular complex with imidazole. Bands correspond-
ing to vibrations of imidazole are denoted with asterisks.
tion bands. The dz orbital participates in transmission
2
of positive σ-effect from imidazole molecule to the
manganese atom and macroring, which stabilizes the
dz2 and a1 orbitals. Regardless of the presence of elec-
tron-acceptor or electron-donor groups in molecules
I–V, addition of imidazole induces blue shift of the
with imidazole (Fig. 3) new absorption bands appeared
at 1542, 1263, 1093, 1056, 936, 843, 827, 756, 661,
and 619 cm–1 due to vibrations of coordinated imidaz-
ole [16]; no such bands were observed in the spectrum
of initial compound IV. All vibration frequencies of
coordinated imidazole are higher by 5–20 cm–1 than
those of free imidazole [17]. Analogous pattern was
observed upon coordination of imidazole to other man-
ganese complexes I–III and V. Absorption bands at
1409 and 1617 cm–1, belonging to the acetate ligand
[νs(COO) and νas(COO)] [18, 19], were present in the
spectra of both (AcO)(Im)MnPc(3-CF3C6H4O)8 and
initial complex.
charge transfer band a1→dz , while its intensity either
2
increases or remains unchanged (Fig. 1). Presumably,
the blue shift results from somewhat stronger stabiliza-
tion of the molecular orbital as compared to dz
2
(Fig. 4a). The reverse π-effect Im←Mn is transmitted
through the dxz and dyz orbitals which are also stabi-
lized by reaction of Mn(III) complex with imidazole.
The energy of the molecular orbital from which elec-
tron transition occurs (a1) changes differently for elec-
tron-deficient (I, III, IV) and electron-rich aromatic
complexes (II, V), so that opposite shifts of band I are
observed (Fig. 4b, c). Reduction of the intensity of
band I in all the examined cases is related to the
opposite direction of the π-effect Im←Mn. Thus the
Comparison of the electronic absorption spectra of
porphyrazine complexes I and II with those of Mn(III)
complexes with octaethylporphyrin [20] [CHCl3, λmax
,
nm (logε): 428 (4.17), 473 (4.68), 590 (3.76)] showed
the same relation as that reported in [21] for analogous
(a)
(b)
(c)
dz
2
dπ
a1
dπ
a1
CT
CT
CT
a1
Fig. 4. Shifts of absorption bands in the electronic spectra of complexes I–V upon addition of imidazole molecule: (a) transition
a1 →dz (I –V), (b) a1 →dπ (II, V), and (c) a1 →dπ (I, III, IV).
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

EFFECT OF PERIPHERAL MODIFICATION OF MANGANESE(III) PORPHYRAZINE
1585
effect of the ether oxygen atom is lacking, and imidaz-
ole complexes with compounds III and IV having
3-CF3C6H4 and 3-CF3C6H4O substituents, respectively,
are characterized by similar stabilities (see table).
spectral data are consistent with the nature of the trans-
formation represented by Eq. (1).
In keeping with the stability constants (see table),
the strength of the imidazole complexes with com-
pounds I–V decreases in the series (Cl)MnTPP [6]
(log Ks = 2.9) > (AcO)MnTAP(3-CF3C6H4)8 (I) >
(AcO)MnTAP(4-t-BuC6H4)8 (II) > (AcO)MnPc-
[3,5-(t-Bu)2C6H3O]8 (V) > (AcO)MnPc(3-CF3C6H4)8
(III) ≈ (AcO)MnPc(3-CF3C6H4O)8 (IV). It is seen that
the tetraazaporphyrin complexes with imidazole oc-
cupy an intermediate place between the porphyrin and
phthalocyanine complexes. The stability constant of
(AcO)(Im)MnTAP(3-CF3C6H4)8 is higher by a factor
of 5.5 than that of its phthalocyanine analog
(AcO)(Im)MnPc(3-CF3C6H4)8, but it is lower by
a factor of 5.6 than the stability constant of
(Cl)(Im)MnTPP. This general trend is likely to be
related to the size of the coordination cavity of the
macroring which decreases in going from porphyrin to
phthalocyanine ligand [23]. As a result, the MnN4
coordination entity becomes flatter, and the coordina-
tion bonds therein become stronger.
Surprisingly, the most stable among the examined
imidazole complexes with manganese(III) phthalocy-
anines was that formed by compound V. Unlike m-tri-
fluoromethylphenyl-substituted tetraazaporphyrin and
phthalocyanine derivatives, imidazole complexes with
octa- and hexadeca-tert-butyl-substituted compounds
II and V demonstrate the opposite stability series.
Most probably, high stability of the complex V–Im
may be rationalized by nearly orthogonal orientation of
the fused benzene ring and the plane passing through
the carbon atom nearest to the ether oxygen atom. In
this case, negative inductive effect of the oxygen atom
predominates, whereas positive inductive effect of tert-
butyl groups does not operate.
We can conclude that multiple substitution of tetra-
azaporphyrin macroring coordinated to manganese(III)
affects quantitative parameters of the addition of
organic base as a result of variation of electronic prop-
erties of the reaction center; the observed specificity of
electronic effect of substituents is related to the struc-
ture of the macrocyclic fragment.
Unlike the effect of replacement of the meso-CH
units in the macroring by nitrogen atoms, steric effect
arising from introduction of peripheral substituents R
into molecules I–V is insignificant, as was demon-
strated with octakis(pentyloxy)phthalocyanine deriva-
tives [24]. The size of the porphyrazine macroring
almost does not change, whereas deviations from
planar structure attain 0.1 Å due to steric interaction
between substituents in the neighboring fused benzene
rings. On the other hand, the macroring in six-coor-
dinate porphyrazine complexes is almost planar; for
example, deviations of atoms in (Py)2MIITAP(Ph)8 do
not exceed 0.03 Å [24]. However, the phenyl rings are
turned through angles of ~49 and 36° with respect to
the macroring plane. Taking into account the position
of two coordinated pyridine molecules in almost ortho-
gonal plane passing through two opposite meso-nitro-
gen atoms, conjugation effects in such structure are
considerably weakened.
EXPERIMENTAL
Compounds I–V were synthesized according to the
procedures reported in [10]; in particular, complexes I,
III, and IV were prepared by reactions of manga-
nese(II) acetate tetrahydrate with the corresponding
organic ligand in boiling dimethylformamide, and
compounds II and V were obtained by template cyclo-
tetramerization of bis(4-tert-butylphenyl)fumaronitrile
in 2-dimethylaminoethanol and of 4,5-bis(3,5-di-tert-
butylphenoxy)phthalonitrile in hexanol, respectively,
in the presence of manganese(II) acetate. Complexes
I–V were purified by chromatography and were char-
acterized by elemental analyses and electronic absorp-
tion, IR, and mass spectra. Their purity was checked
by invariability of their electronic absorption spectra in
subsequent purification steps.
The stability series of donor–acceptor complexes of
compounds I–V with imidazole conforms to the above
relations. Electron-withdrawing m-trifluoromethyl-
phenyl group weakens σ-bonding with the macroring,
thus enhancing σ-bond with imidazole molecule. The
molecular complex of imidazole with compound I is
more stable than analogous complex with electron-rich
compound II having eight peripheral 4-tert-butyl-
phenyl groups. Insofar as the 3-CF3C6H4O substituent
is not coplanar with the macroring, positive mesomeric
Imidazole was purified by recrystallization from
alcohol [25]. Toluene was treated with potassium hy-
droxide and was distilled prior to use (bp 110.6°C); the
concentration of water therein was determined by Karl
Fischer titration; it did not exceed 0.01%.
(Acetato)[2,3,7,8,12,13,17,18-octakis(3-trifluoro-
methylphenyl)-5,10,15,20-tetraazaporphyrinato]-
manganese(III) (AcO)MnTAP(3-CF3C6H4)8 (I) was
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 10 2011

OVCHENKOVA, LOMOVA
1586
purified by chromatography on silica gel using methyl-
ene chloride as eluent. Electronic absorption spectrum
(toluene), λmax, nm (logε): 405 (4.61), 463 (4.44),
590 sh, 653 (4.78). IR spectrum (KBr), ν, cm–1: 1719,
1620, 1481, 1420, 1384, 1330, 1312, 1279, 1169,
1128, 1098, 1076, 1016, 920, 810, 762, 722, 699. Mass
spectrum: m/z 1519.95 [M – OAc]+. Found, %:
C 54.33; H 2.40; N 6.95. C74H35N8F24O2Mn. Calculat-
ed, %: C 56.29; H 2.23; N 7.10. M – OAc 1519.0.
tion spectrum (toluene), λmax, nm (logε): 407 (4.56),
655 (4.27), 727 (5.03). IR spectrum (KBr), ν, cm–1:
2963, 2928, 2868, 1725, 1608, 1586, 1508, 1459,
1421, 1407, 1384, 1363, 1337, 1296, 1246, 1199, 1119,
1084, 1042, 1002, 961, 903, 864, 745, 707. Mass spec-
trum: m/z 2199.52 [M – OAc]+. Found, %: C 77.37;
H 8.65; N 4.74. Calculated, %: C 77.49; H 8.06;
N 4.95. M – OAc 2199.0.
The reaction of complexes I–V with imidazole in
toluene was studied at 298 K by spectrophotometry
using Specord M-40 and Agilent 8453 instruments.
Series of toluene solutions with a constant concentra-
tion of the manganese complex (10–5 M) and different
concentrations of imidazole (10–5 to 10–2 M) were pre-
pared. The overall volume of equilibrium mixtures was
maintained by using required amounts of a solution of
complex I–V in toluene, a solution of imidazole in
toluene, and pure toluene.
(Acetato)[2,3,7,8,12,13,17,18-octakis(4-tert-butyl-
phenyl)-5,10,15,20-tetraazaporphyrinato]manga-
nese(III) (AcO)MnTAP(4-t-BuC6H4)8 (II) was puri-
fied by chromatography on silica gel using chloroform
containing 1% of methanol as eluent. Electronic
absorption spectrum (toluene), λmax, nm (logε): 421
(4.51), 494 (4.50), 619 sh, 673 (4.74). IR spectrum
(KBr), ν, cm–1: 2962, 2905, 2868, 1717, 1609, 1477,
1463, 1384, 1364, 1299, 1269, 1197, 1147, 1109, 997,
891, 850, 839, 811, 751, 635, 599, 585, 563. Mass
spectrum: m/z 1423.78 [M – OAc]+. Found, %:
C 78.82; H 7.47; N 7.31. C98H107N8O2Mn. Calculated,
%: C 79.32; H 7.27; N 7.55. M – OAc 1423.0.
This study was supported in part by the Program
for Basic Research of the Presidium of the Russian
Academy of Sciences “Purposeful Synthesis of
Inorganic Compounds with Specified Properties and
Design of Functional Materials on Their Base 2010,
2011,” by the Russian Foundation for Basic Research
(project no. 09-03-97556-r-tsentr-a), by the Federal
Special-Purpose Program “Scientific and Scientific–
Pedagogical Staff of Innovation Russia 2009–
2012” (state contract no. 02.740.11.0106), and by the
Ministry of Education and Science of the Russian
Federation, program “Development of Scientific
Potential at Higher School 2010, 2011” (project
no. 2.2.1.1/2820).
(Acetato)[2,3,9,10,16,17,23,24-octakis(3-trifluoro-
methylphenyl)phthalocyaninato]manganese(III)
(AcO)MnPc(3-CF3C6H4)8 (III) was purified by chro-
matography on silica gel using chloroform containing
1% of methanol as eluent. Electronic absorption spec-
trum (toluene), λmax, nm (logε): 397 (4.68), 514 (4.16),
677 (4.38), 738 (5.15). IR spectrum (KBr), ν, cm–1:
1721, 1624, 1508, 1422, 1385, 1333, 1256, 1217,
1169, 1128, 1101, 1077, 1042, 963, 899, 825, 805, 767,
749, 714, 658. Mass spectrum: m/z 1721.25 [M – OAc]+.
Found, %: C 58.66; H 2.42; N 5.86. Calculated, %:
C 60.69; H 2.55; N 6.29. M – OAc 1721.0.
REFERENCES
(Acetato)[2,3,9,10,16,17,23,24-octakis(3-trifluoro-
methylphenoxy)phthalocyaninato]manganese(III)
(AcO)MnPc(3-CF3C6H4O)8 (IV) was purified by
chromatography on silica gel using chloroform con-
taining 1% of methanol as eluent. Electronic absorp-
tion spectrum (toluene), λmax, nm (logε): 395 (4.58),
505 (4.07), 652 (4.25), 723 (5.03). IR spectrum (KBr),
ν, cm–1: 1720, 1617, 1594, 1492, 1450, 1409, 1385,
1328, 1283, 1208, 1174, 1128, 1086, 1065, 1039,
922, 794, 748, 697. Mass spectrum: m/z 1849.21
[M – OAc]+. Found, %: C 54.63; H 2.64; N 5.90. Cal-
culated, %: C 56.62; H 2.38; N 5.87. M – OAc 1849.0.
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EFFECT OF PERIPHERAL MODIFICATION OF MANGANESE(III) PORPHYRAZINE
1587
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