Extra coordination of Zn-tetraphenylporphine with pyridine, quinoline, and acridine N-oxides

Article abstract of DOI:10.1007/s11176-005-0416-6

The log K values of zinc tetraphenylporphine (Zn-TPhP) complexes with pyridine, quinoline, and acridine N-oxides and with their nonoxidized analogs, as well as the positions of absorption maxima of the complexes with respect to Zn-TPhP linearly depend on

Full text of DOI:10.1007/s11176-005-0416-6

Russian Journal of General Chemistry, Vol. 75, No. 8, 2005, pp. 1309 1317. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 8, 2005,
pp. 1379 1387.
Original Russian Text Copyright
2005 by Andreev, Nizhnik, Bezruchko, Morozov.
Extra Coordination of Zn Tetraphenylporphine
with Pyridine, Quinoline, and Acridine N-Oxides
V. P. Andreev*, Ya. P. Nizhnik*, D. G. Bezruchko*, and A. K. Morozov**
* Petrozavodsk State University, Petrozavodsk, Russia
** Forest Research Institute, Karelian Research Center,
Russian Academy of Sciences, Petrozavodsk, Russia
Received May 3, 2004
Abstract The logK values of zinc tetraphenylporphine (Zn TPhP) complexes with pyridine, quinoline,
and acridine N-oxides and with their nonoxidized analogs, as well as the positions of absorption maxima of
+
the complexes with respect to Zn TPhP linearly depend on the pKBH of the ligands in water (methanol,
acetonitrile, nitromethane, and acetone) and on Hammett constants in the absence of steric effects.
Metal porphyrins of synthetic and natural origin
show the property of extra coordination whose
essence consists in that the central metal atom forms
donor acceptor bonds beyond the molecular plane
with one, two, or more ligands [1, 2].
growth stimulants [9] and medicinals to extremely
powerful mutagens and carcinogens [10]. Note that
heterocyclic compounds, when entering into an
organism, undergo metabolic transformations into
N-oxidized derivatives capable of reacting with
various porphyrin systems of cells. For example,
reduction of aliphatic and heteroaromatic N-oxides is
often mediated by heme-containing enzymes (for
example, trimethylamine N-oxide reductase) or even
by peptide-free hemes [11]. 2-Heptyl- and 2-nonyl-4-
hydroxyquinoline N-oxides released by bacteria of the
genus Pseudomonas being bound to heme-containing
peptides are known to inhibit electron transport in the
membranes of bacteria, chloroplasts, and mitochondria
[12].
Such molecular complexes are called axial or extra
complexes. They determine the biological activity in
vivo of such peptides and enzymes as hemoglobin,
cytochromes, catalase, guanylatecyclase NO-synthase,
and many others containing ions of various metals [3].
It is just extra coordination that determines the bio-
logical activity of some medicinals. For example, such
quinoline-based antimalarial preparations as quinine,
chloroquine, amodiaquine, and mefloquine form
adducts with hematin, which produce toxic effect
upon malaria plasmodium [4].
Previously we studied in detail molecular com-
plexes of heteroaromatic N-oxides with such -ac-
ceptors as H+ (Bronsted Lowry acids), BF3, AlCl3,
ZnCl2, and CuCl2 (Lewis acids) [13 15] and revealed
invariable formation of n, -type adducts involving the
oxygen atom of the N O group.
At present a great number of investigations is
devoted to complex formation of natural and synthetic
metal porphyrins with various nitrogen-containing
heterocycles and peptides, and certain extra complexes
were isolated and studied in the pure state [5].
However, regarding heteroaromatic N-oxides we were
able to find only three works reporting the study of
Fe(III)Cl TPhP (a synthetic analog of hemin; TPhP is
tetraphenylporphine) complexes with pyridine N-oxide
[6], Mn(III) TPhP with 2,6-dimethylpyridine N-oxide
[7], and Zn TPhP with 3-methyl-4-nitropyridine
N-oxide [8].
In this work we dwelt on donor acceptor com-
plexes of Zn TPhP with heteroaromatic N-oxides of
the pyridine (I), quinoline (II, III), acridine (IV), and
isoquinoline (V) series containing such potential
coordination centers as the macroring system, metal
ion, and nitrogen atoms.
In the first stage we determined the stability con-
stants (K) of Zn TPhP complexes with certain hetero-
cyclic compounds in chloroform (stabilized with
1-hexene, 0.1 vol%) at 298 K by means of electronic
spectroscopy. As in our previous works, we chose
chloroform as solvent, since it should not compete in
formation of donor acceptor metal porphyrin com-
Heteroaromatic N-oxides, unlike their nonoxidized
analogs, possess a unique combination of a high
donor power of the N O group and of its spatial
accessibility. The spectrum of their biological activity
is very broad: from ecologically safe agricultural plant
1070-3632/05/7508-1309 2005 Pleiades Publishing, Inc.

1310
ANDREEV et al.
NO2
X
X
Me
X
N
O
N
O
N
N
O
O
Ia Ie, Ii Ij Il
IIa IIh, IIj IIk
IIIb, IIIh IIIj
X
X
N
N
O
N
O
IVa, IVd, IVe
V
VIa, VIb
X = H (a), Me (b), MeO (c), NO2 (d), Cl (e), N3 (f), NHNH2 (g), PhCH=CH (h), 4-MeOC6H4CH=CH (i), 4-Me2NC6H4
CH=CH (j) PhO (k).
plexes. The initial concentration of Zn TPhP was 2
10 M. At this concentration, metal porphyrins are
even larger and the higher, the smaller E (21.8 and
14.9) and the higher the general basicity (nucleo-
philicity) B (156 and 218) of the solvent [23]. There-
fore, to predict stability of the complexes, we can use
data on the basicity of the ligands in polar solvents
strongly differing in the nature of their interaction
with solute. This fact is of great importance, since the
stability constants of many adducts of metal por-
phyrins are easier to determine in solvents unable to
competing interactions. At the same time, to calculate
5
not associated, which is evidenced by the fulfillment
of the Bouguer Lambert Beer law. The stability
constants of the adducts were from the difference in
the optical densities of the solutions at the metal
porphyrin and adduct absorption wavelengths (see
Experimental). Typical changes in the electronic
spectrum of Zn TPhP in chloroform upon addition of
heteroaromatic N-oxides are illustrated in Fig. 1.
+
the pKBH values of the ligands requires use of a fairly
The resulting K value for the adduct with pyridine
(3920 220) were almost coincident with the value
(4100 65) obtained in CHCl3 stabilized with 2-me-
thyl-2-butene [16].
polar medium that favors dissociation of the conjugate
BH+ acid.
Our data show (Fig. 2) that the points for pyridine
+
(VIa) and 4-methylpyridine (VIb) in the logK pKBH
We found that the dependences of logK for Zn
TPhP complexes with pyridine N-oxides from
(H2O) coordinates lie lower than the straight lines for
N-oxides. Moreover, the K values calculated by
Eq. (1) (Fig. 2) for the Zn TPhP N-oxide complexes
that would be expected to be as basic as compounds
VIa and VIb, are 5 8 times higher than the experi-
mental values for the corresponding pyridines. Since
the macroring in Zn TPhP is planar, it is unlikely that
the easier steric accessibility of the oxygen atom in
N-oxides would affect the gas-phase reaction. Ho-
wever, in solution, the starting pyridines and N-oxides,
on the one hand and the intermediates and products
of the donor acceptor interaction on the other hand,
should be much differently solvated. To solve this
problem requires additional studies.
Hammett
constants (and on specially introduced
substituent constants for pyridine N-oxides [17])
PyO
and also from the basicities of the ligands in water
[18], acetonitrile, nitromethane, acetone, and methanol
[19] are linear (Figs. 2 and 3; Table 1). A similar
phenomenon has been described by Kirksey and
Hambright [22] who obtained linear dependences of
the logK values of axial Zn TPhP complexes in
benzene with -substituted pyridines on the basicity
of the ligands in water and on Hammett constants.
In the case of aprotic solvents (acetonitrile, nitro-
methane, and acetone), the linear dependences of
+
logK on pKBH of N-oxides are almost parallel to each
other and locate the higher, the smaller is the general
acidity (electrophilicity) parameter E (5.2, 5.1, and
2.1). At the same time, in the case of water and
methanol, that are capable of specific interactions
(H-bond formation with the N O group and its pro-
tonated form), the slopes of the straight lines become
Along with pyridine N-oxides Ia and Ib capable of
coordinating via the N O group only, we also stu-
died compounds Ic Ie, Ii, Ij, and Il, that possess one
more functional group as a second possible coordina-
tion center. In all the cases we found a good correla-
tion between logK and Hammett constants, except
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

EXTRA COORDINATION OF Zn TETRAPHENYLPORPHINE
1311
D
D
1
2
1
2
Soret
400
III II I
500 600 , nm
Cope
III
II
I
400
500
600
, nm
Fig. 1. Changes in the electronic absorption spectrum of Zn TPhP in chloroform upon addition of 2-methylquinoline N-oxide
6
5
(IIIb) [c
1.6 10 M (Soret band) and 2 10 M]. (1) Zn TPhP and (2) Zn TPhP L.
Zn TPhP
for N-oxide Il (Fig. 3), which may result from a
certain turn of the NO2 group out of the conjugation
plane with the heteroring because of steric interaction
with the neighboring CH3 group [24]. The negative
sign of the coefficient at points to the fact that in
N-oxides act as electron donors in complex formation
with Zn TPhP, and the moderate absolute value of
points to a moderate interaction with the reaction
center.
Compound Ij is known to show extremely unusual
properties in reaction with Broensted Lowry acids: It
takes up the first proton to the amino group (pKBH
log K
4
+
VIb
4.30) and the second proton, to the oxygen atom of
the N O group (pKBH 1.43) [20]. However, for
VIa
3
4
5
1
2
Ic
Ij
Ib
Ia Ii
+
log K
3
2
4
3
VIb
VIa
Ie
Ic
Il
Id
Ij
Ib
Ii
Ia
Il
Ie
0
5
10 pKBH+
2
1
Id
2
Fig. 2. Plot of the logK of Zn TPhP complexes of
pyridine N-oxides in chloroform at 298 K vs. pK
1
0
1 ,
PyO
+
of
BH
+
ligands in (1) water (logK = 0.33pK
+ 2.78, r 0.986),
+ 1.53, r 0.933),
+ 2.04, r 0.999),
+ 1.42, r 0.994),
BH
+
(2) methanol (logK = 0.44pK
(3) acetone (logK = 0.19pK
Fig. 3. Plot of the logK of Zn TPhP complexes with
pyridine N-oxides in chloroform at 298 K vs. (1) Ham-
BH
+
BH
+
(4) nitromethane (logK = 0.19pK
mett
(2)
constants (logK = 1.15 + 3.08, r 0.988) and
constants (logK = 0.71 + 3.03, r 0.988)
BH
+
and (5) acetonitrile (logK = 0.18pK
+ 1.23, r 0.996)
BH
PyO
PyO
+
(VIa and VIb are the points corresponding to the pK
of pyridine and 4-methylpyridine in water).
(compound Il was excluded from correlation; VIa and
VIb are the points for pyridine and 4-methylpyridine).
BH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

1312
ANDREEV et al.
Table 1. Stability constants (K) of Zn TPhP complexes at 298 K in chloroform, Hammet constants and
constants
PyO
+
of substituents, and pKBH of ligands in various solvents
+
pKBH
K,
l mol
PyO
[18]
Ligand
1
[17]
water [18] MeCN [19] MeNO2 [19] acetone [19] MeOH [19]
VIa
VIb
Ia
Ib
Ic
Id
Ie
Ii
3920 220
6482 244
1039 55
1782 161
2856 192
165 22
618 18
1050 20
2110 125
0
0.17
0
0.17
0.268
+0.778
+0.227
0.03a
0.15a
5.25
6.02
0.79
1.29
2.05
1.70
0
0.24
9.97
11.00
12.37
5.35
8.45
9.42
10.58
4.02
5.11
6.20
3.28
3.63
4.49
0.603
+1.19
+0.206
0.10b
0.31b
0.89
0.36
9.06
7.68
3.12
1.00c
Ij
4.30 (NMe2)
1.43 (N O)
[20]
Il
346 17
+0.778
+1.19
0.069
0.97
0.139
[21]
a
c
b
The value was calculated by equations given in the legend to Fig. 4 for the absorption bands I and II. The
value was ob-
PyO
+
tained from the correlation equation
=
0.48 pK
= 0.38 (r 1.000) we derived from data in [18] for 15 compounds.
PyO
BH
Estimated by the equations given in the legend to Fig. 5 for the absorption bands I and II.
example, transfer of the dimethylcarbamoyl group
between pyridine N-oxide [25] and this compound
involves the N-oxide function. The fact that the
point for compound Ij in its complex formation with
We also showed that in the absence of steric effects
the bathochromic shift of the Soret, III, II, and I
absorption bands in the electronic spectra of Zn TPhP
in chloroform on adding heteroaromatic N-oxides of
the pyridine, quinoline (Figs. 4 and 6), and acridine
+
Zn TPhP falls quite well on the logK pKBH
+
plot (Fig. 2) when using pKBH 1.43 (instead of 4.30)
(
= 12.45 4.85 , r 0.999;
= 14.87 - 6.74 ,
II
points to the fact that the reaction with the metal
porphyrin involves the oxygen rather than nitrogen
atom.
r 0.999) series linearly vary with I the Hammett
constants and basicity of the ligands. In this case, too,
the coordination-induced band shifts for compound Il
, nm
20
, nm
20
I
Il
II
15
10
I
III
Soret
Ic
10
0
II
Ic
Ib
Ib
Ia
III
Ia
5
0
Il
Id
Soret
Id
0
3
0
1
pKBH+
Fig. 5. Plot of the shift of the Soret (
=
+
Soret
+
+
Fig. 4. Plot of the shift of the Soret (
8.65, r 0.999), III (
5.00 + 13.80, r 0.993), and I (
17.75, r 0.999) absorption bands in the electronic spectra
=
4.74
+
1.33pK
+ 7.51, r 0.992), III (
= 1.34pK
+ 12.59, r 0.996),
Soret
BH
III
BH
+
=
4.55 + 11.11, r 0.995), II
4.57
9.91, r 0.999), II (
= 1.42pK
III
II
BH
+
(
=
=
+
and I ( = 1.35pK
+ 16.45, r 0.995) absorption
II
I
I
BH
bands in the electronic spectra of Zn TPhP in chloroform
+
of Zn TPhP in chloroform vs. Hammett
constants
vs. pK
of ligands in water upon coordination with
BH
upon coordination with pyridine N-oxides.
pyridine N-oxides.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

EXTRA COORDINATION OF Zn TETRAPHENYLPORPHINE
deviate from the correlation straight lines. Comparison
1313
of the bathochromic shifts of the adducts with 2- and
4-substituted pyridine and quinoline N-oxides shows
that those of the former change in a more complicated
fashion, probably, by steric reasons. We emphasize
that band III, in view of its low intensity, is the least
suitable for correlation. Moreover, absorption bands
of organic compounds can overlap with the Soret and
III bands. However, we found (at least with hetero-
aromatic N-oxides) that the use of several bands in
parallel can serve as a sufficiently reliable procedure
, nm 20
IIg
IIk
IIb
IIa
IIf
15
IIc
IIe
I
10
5
II
III
Soret
+
for calculating K and pKBH in various solvents and
constants (as well as dipole moments, electrochemical
oxidation half-waves, etc.).
0
1
Fig. 6. Plot of the shift of the Soret (
9.17, r 0.985, III ( 3.74 + 11.39, r 0.958),
II ( ) = 4.94 + 12.67, r 0.976), and I (
4.97 + 14.95, r 0.987) bands in the electronic spectra
= 4.21 +
Soret
The resulting
correlation equations for the
=
III
absorption bands I and II allowed us to calculate the
Hammett constant for the 4-Me2NC6H4CH=CH sub-
stituent ( 0.15), which drastically differs from that
for Me2N ( 0.84 [17]). Probably, the styryl group
much attenuates direct resonance conjugation between
the Me2N and N O functions. Other styryl substi-
tuents, too, show a similar bridging effect. For ex-
ample, our value of 0.03 for the 4-MeOC6H4CH=CH
group is also essentially lower than the value given in
[17] for the MeO group ( 0.268). This fact is not very
=
I
II
of Zn TPhF in chloroform vs. Hammett
constants
upon coordination with quinoline N-oxides.
of complexes, used in this paper, requires that their
extinction coefficients are calculated under conditions
of a 1000 2000 fold excess of ligand with respect to
metal porphyrin. However, this is not always possible:
Ligands are rather often poorly or moderately soluble
in required solvents.
+
surprising. Previously, based on the pKBH values and
changes in the electronic absorption spectra, induced
by protonation and complex formation with BF3, the
authors of [26, 27] suggested a weak interaction
between the nitro group and heteroring basicity center
(nitrogen or oxygen atoms, respectively) in nitro
derivatives of 4-trans-styryl- and 4-phenylpyridines
+
The use of
for these purposes does not require
that metal porphyrin completely passes into donor
acceptor complex, but suggests that the amount of
ligand is sufficient that the absorption maximum
shifts distinctly and does not change position with
increasing N-oxide concentration.
and their N-oxides. From the
pKBH correlation
straight lines (Fig. 5) we estimated the basicities of
compounds Ii and Ij (1.00 and 1.46, respectively).
Note that our pKBH value for N-oxide Ij quite well
agrees with the value of 1.43 in [20].
Unfortunately, the electronic absorption spectra of
metal porphyrins not always show trends similar to
those described above. For example, in the case of
Cu TPhP, no changes in the spectra were observed
even with a 1000-fold excess of N-oxide, in ag-
reement with data in [1]. Coordinately unsaturated
metal porphyrins, in particular, including the Cu2+ ion
(unlike coordinately unsaturated Zn TPhP) are known
to form unstable complexes even with ligands more
basic than heteroaromatic N-oxides, for example,
pyridine [1].
+
Our preliminary data show that for the coordinately
unsaturated Fe3+-containing metal porphyrin hemin in
acetone (it is scarcely soluble in chloroform) the
dependence between the shifts of bands I III on
adding an N-oxide and the Hammett
constants of
the substituents in the heteroring is also linear.
This fact is of utmost importance, since, with
corresponding correlation equations in hand, by
simply comparing the electronic absorption spectra of
metal porphyrin solutions and their axial complexes
with various ligands one might gain a precious in-
formation about stability of the resulting adducts and
To confirm the structure of spectrally detected axial
complexes, we separated 22 pure molecular com-
plexes of Zn TPhP with heteroaromatic N-oxides and
with some nonoxidized analogs (Table 2) as violet
(with the shades from blue to red) crystalline sub-
stances melting (decomposing) above 300 C.
calculate hitherto unknown
constants, basicity
constants of the ligands, and stability constants of
extra complexes with them.
According to the elemental analysis (Table 2), the
Zn TPhP:ligand ratio in all the adducts is 1:1.
The procedure for determining stability constants
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

1314
ANDREEV et al.
Table 2. Yields and elemental analyses of Zn TPhP extra complexes with heteroaromatic N-oxides and quinoline
Found, %
H
Calculated, %
H
Ligand
Yield, %
Formula
C
N
C
N
Ia
Ib
Ic
Id
Ii
Ij
IIa
IIb
IId
IIe
IIf
61
62
64
70
61
91
84
81
73
76
90
40
74
70
66
70
71
32
66
41
70
54
76.09
76.31
74.91
71.75
76.98
76.94
77.46
77.45
73.56
74.25
73.60
75.28
78.23
77.66
79.14
77.96
78.16
78.35
75.41
75.13
77.29
78.30
4.36
4.38
4.31
4.08
4.72
4.92
4.35
4.47
3.99
4.19
4.14
4.49
4.95
4.46
4.53
4.62
4.76
4.60
4.46
4.29
4.44
4.57
8.62
8.21
8.52
10.24
7.53
8.73
8.55
8.49
9.59
8.14
12.68
9.70
8.47
8.49
7.42
7.24
8.51
8.38
9.45
7.53
8.33
8.95
C49H33N5OZn
C50H35N5OZn
C50H35N5O2Zn
C49H32N6O3Zn
C58H41N5O2Zn
C59H44N6OZn
C53H35N5OZn
C54H37N5OZn
C53H34N6O3Zn
C53H34ClN5OZn
C53H34N8OZn
C53H37N7OZn
C63H46N6OZn
C54H37N5OZn
C61H41N5OZn
C62H43N5O2Zn
C63H46N6OZn
C57H37N5OZn
C57H36N6O3Zn
C57H36ClN5OZn
C53H35N5OZn
C53H35N5Zn
76.12
76.28
74.77
71.93
76.94
77.16
77.32
77.46
73.32
74.22
73.65
74.60
78.31
77.46
79.17
77.94
78.31
78.39
74.55
75.42
77.32
78.86
4.30
4.48
4.39
3.94
4.56
4.83
4.29
4.45
3.95
4.00
3.97
4.37
4.79
4.45
4.47
4.54
4.79
4.27
3.95
4.00
4.29
4.37
9.06
8.90
8.72
10.27
7.74
9.15
8.51
8.36
9.68
8.17
12.97
11.49
8.68
8.36
7.57
7.33
8.68
8.02
9.15
7.72
8.51
8.68
IIg
IIj
IIIb
IIIh
IIIi
IIIj
IVa
IVd
IVe
V
Quinoline
The positions of the IR absorption bands of Zn
TPhP scarcely change in going to these compounds.
However, the presence of three characteristic peaks at
of heteroaromatic N-oxides are caused by the decrease
in double bonding between the nitrogen and oxygen
atoms, induced by complex formation [15].
1
795 798, 749 755, and 701 704 cm , whose posi-
We noted above complex formation of heteroaro-
matic N-oxide to Zn TPhP in chloroform gives rise
to new absorption bands whose position depends on
the structure of the ligand (Table 3) and intensity, in
addition, on its amount. As follows from the elec-
tronic absorption spectra, in chloroform, acetone,
CCl4, and dioxane solutions adducts are in equilib-
rium with their components.
tion and intensity ratio are strictly individual for each
complex (Table 3), as well as a noticeable attenuation
1
of the very strong band at 1003 cm are worthy of
special mention. The last band relates to in-plane
bending (C-H) and stretching [C C ] and [C N]
vibrations of pyrrole fragments [28, 29]. The co-
ordination of Zn TPhP with N-oxides seems to result
in a certain displacement of the zinc atom from the
porphyrin ring plane [18], thus changing parameters
of the above-noted bonds and their spectral
appearance.
Therefore, the elemental analyses and electronic
absorption and IR spectra establish that the reaction
of Zn TPhP with the ligands studied gives rise to
1:1 n, -type molecular complexes with a donor
The IR spectra of the starting N-oxides contain
acceptor bond between the oxygen atom of the N
O
strong stretching absorption bands in the region of
group and the zinc atom of the metal porphyrin (as
with pyridines [22]). However, we do not exclude the
possibility of formation under certain conditions of
other types of complexes undetectable in our experi-
mental conditions.
1
1367 1214 cm , typical of the
N O group
(Table 3). At the same time, in the spectra of the
complexes of the N-oxides with Zn TPhP these bands
get weaker or disappear completely. Instead of them,
1
new bands appear in the region of 1210 1175 cm ,
that overlap with metal porphyrin absorption bands
(1209 and 1177 cm ). Such changes in the IR spectra
Later on we are going to study the structure of our
isolated extra complexes by X-ray diffraction.
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

EXTRA COORDINATION OF Zn TETRAPHENYLPORPHINE
1315
Table 3. Electronic and IR spectra of Zn TPhP complexes with various ligands
1
Electronic spectrum,
Cope III
max, nm (log )a
II
IR spectrum, , cm
ZnTFP Lb
Ligand
I
L [ (N O)]
Ia
8.5(5.67) 11.1(3.70) 13.5(4.39) 16.2(4.02)
9.5(5.67) 11.6(3.66) 14.5(4.40) 18.5(4.04)
10.0(5.65) 12.6(3.61) 15.5(4.39) 19.0(4.01)
1225 v.s
1215 v.s
1214 v.s
1517 v.s [ as(NO2)],
1272 v.s
798 752 701
797 752 701
798 753 702
1528 v.s [ as(NO2)],
1272 v.w, 800, 752, 704
1252 v.w, 800, 756, 704
800 752 704
Ib
Ic
Id
5.0(5.56)
7.6(3.68) 10.0(4.33) 14.2(4.00)
Ii
Ij
13.8(4.32) 18.0(3.97)
14.5(4.36) 18.5(4.06)
1250 v.s
1260 v.s
IIa
IIb
IId
8.9(5.56) 11.7(3.85) 13.3(4.35) 15.2(3.92)
9.7(5.60) 11.7(3.85) 13.6(4.35) 15.7(3.92)
1309 v.s, 1265 v.s
1314 s, 1278 s
1522 v.s [ as(NO2)],
1307 v.s
1307 v.‡, 796, 751, 703
1282 v.w, 796, 752, 702
1527 v.s [ as(NO2)],
1302 v.s, 797, 754, 703
1301 m, 1259 w, 796,
752, 703
8.3
8.6(4.22) 11.2(3.76)
IIe
IIf
8.4
10.5
11.1
13.4
12.2(4.28) 13.8(3.90)
1305 v.s, 1253 m
11.2
14.1(3.8)
2115 v.s(N3), 1314 m, 2117 v.s(N3), 1287 v.s,
1287 v.s
1297 s, 1211 s
1264 v.s, 1236 m
796, 752, 704
796, 753, 702
1260 s, 1232 w, 794,
749, 703
IIg
IIj
11.5
15.5(4.24) 18.1(3.90)
13.6 16.9(3.88)
IIIb
9.2(5.54) 12.6(3.66) 13.5(4.34) 15.5(3.89)
1272 m, 1244 s
1272 v.w, 1236 w, 796,
752, 702
IIIh
IIIi
11.6
12.1
13.5(4.22) 16.0(3.81)
14.0(4.23) 16.5(3.84)
1279 s, 1242 v.s
1257 v.s, 1239 v.s
1240 m, 796, 754, 702
1258 s, 1239 s, 796, 752,
703
IIIj
IVa
IVd
14.5
12.5(4.23) 15.0(3.75)
8.7(4.28) 9.7(3.83)
17.5(3.71)
1237 m
1330 m
1520 v.s [ as(NO2)],
1348 s, 1304 v.s
1239 w, 794, 749, 703
798, 752, 702
1525 v.s
[
as(NO2)], 1302 s, 798,
753, 703
IVe
V
11.3(4.30) 13.2(3.75)
9.6(5.60) 11.6(3.89) 12.5(4.26) 14.5(3.92)
1323 s
1331 v.s, 1254 s
1319 s, 797, 753, 702
1331 v.w, 1252 w, 798,
754, 702
Quinoline 11.0(5.39) 12.1(3.60) 13.5(4.32) 17.5(4.00)
797, 750, 702
Ie
9.5(5.66) 11.0(3.72) 12.7(4.38) 15.5(3.99)
Il
6.5(5.56)
10.4
8.6(3.78) 11.5(4.34) 15.0(3.96)
13.2(3.66) 13.8(4.37) 15.7(4.02)
12.1(3.74) 13.6(4.37) 15.7(4.00)
11.8(3.57) 13.8(4.31) 16.8(3.93)
IIc
IIh
IIk
10.7
a
is the shift of Zn TPhP absorption maxima in chloroform stabilized with 1-hexene. The absence of
b
and log at certain
wavelengths is caused by the overlap with absorption bands of colored ligands. We failed to detect absorption bands of the N
O
bond since they overlap with own Zn TPhP absorption bands (1439 s, 1339 s, 1205 m, 1175 m, 1068 m, 1001 v.s, 995 v.s, 799 s,
751 s, 702 s). Compounds Ik, Il, IIb, IIh, and IIk were not isolated pure and their IR spectral data are absent.
EXPERIMENTAL
The N-oxides were synthesized and purified by the
procedures in [25, 27, 30-34]. Pyridine, 4-methyl-
pyridine, and quinoline were kept over KOH and
distilled. Zn TPhP and Cu TPhP were synthesized
by the procedures in [35] and purified by column
chromatography on alumina, eluent chloroform.
The IR spectra were recorded in KBr on a Perkin
Elmer Paragon-1000FTIR device in the range 4000
300 cm . The electronic absorption spectra were
obtained on a Specord UV-Vis spectrometer and on
an FEK KFK-3 in the range 300 800 nm.
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

1316
ANDREEV et al.
Chloroform and other solvents we purified according
to [36].
5. Antina, E.V., Lebedeva, N.Sh., and V’yugin, A.I.,
Koord. Khim., 2001, vol. 27, no. 10, p. 784.
6. Mashiko, T., Kastner, M.E., Spartalian, K.,
Scheidt, W.R., and Read, C.A., J. Am. Chem. Soc.,
1978, vol. 100, no. 20, p. 6354.
The stability constants of the complexes in chloro-
form stabilized with 1-hexene (0.1 vol%) were cal-
culated using the following formulas.
7. Hill, C.L. and Williamson, M.M., Inorg. Chem., 1985,
K = [Zn TFP Ln]/([Zn TFP][L]n),
vol. 24, no. 19, p. 3024.
8. Byrn, M.P., Curtis, C.J., Hsiou, Yu., Khan, S.I.,
Sawin, P.A., Tendick, S.K., Terzis, A., and Stro-
use, C.E., J. Am. Chem. Soc., 1993, vol. 115, no. 21,
p. 9480.
c1 = (D
2cl)/[(
2c)l)].
1
Here D is the optical density of the solution at a
specified wavelength;
and 2, molar extinctions of
Zn TPhP and Zn TPhP1 Ln at a specified wavelength;
c1, concentration of Zn TPhP or TPhP Ln in the
solution (M); c, total concentration of Zn TPhP and
its TPhP Ln in the solution, numerically equal to the
starting concentration of the metal porphyrin
9. Regulyatory rostu roslin u zemlerobstvi: Zbirnik
naukovykh prats (Plant Growth Regulators in Agri-
culture: Collection of Scientific Works), Shevchen-
ko, A.O., Ed., Kiev: Agroresursy, 1998.
10. Albini, A. and Pietra, S., Heterocyclic N-oxides, Boca
5
(2 10 M).
Raton: CRC, 1991.
11. Takekawa, K., Kitamura, S., Sugihara, K., and
The extinctions of Zn TPhP at a specified wave-
length were determined from the optical density of
the reference solution of the metal porphyrin. With
TPhP Ln molecular complexes, the quantity of ligand
sufficient for complete complex formation (1000
2000-fold excess) was added to the metal porphyrin
solution; complex formation was considered complete,
when D no longer changed on further increase of
ligand concentration. With colored ligands, we con-
structed a D c calibration curve and then, by subtract-
ing the corresponding values, calculated the total
optical density defined by porphyrin absorption.
Ohta, S., Xenobiotica, 2001, vol. 31, no. 1, p. 11.
12. Dowson, R.M.C., Elliott, C., Elliott, W.H., and
Jones, K.M., Data for Biochemical Reasearch, Oxford:
Univ. Press, 1986.
13. Ryzhakov, A.V., Andreev, V.P., and Rodina, L.L.,
Heterocycles, 2003, vol. 60, no. 2, p. 419.
14. Ivashevskaja, S.N., Aleshina, L.A., Andreev, V.P.,
Nizhnik, Y.P., Chernyshev, V.V., and Schenk, H.,
Acta Crystallogr., Sect. C, 2002, vol. 58, no. 5, p. 300.
15. Andreev, V.P., Nizhnik, Ya.P., Tunina, S.G., and Be-
lashev, B.Z., Khim. Geterotsikl. Soedin., 2002, no. 5,
p. 634.
At every determination of
on a KFK-3 FEK we
detected location of absorption bands of the starting
metal porphyrin before adding ligand. The error in
was 0.2 0.3 nm.
16. Lebedeva, N.Sh., Mikhailovskii, K.V., and V’yu-
gin, A.I., Koord. Khim., 2001, vol. 27, no. 10, p. 795.
17. Becker, H., Einfurung in die Elektronentheorie or-
ganish-chemischer Reactionen, Berlin: Wissenschaf-
ten, 1964.
The complexes of Zn TPhP were synthesized by
mixing equimolar amounts of metal porphyrin and
ligand in acetone or its mixture with hexane. The fine
crystals that formed after a time were washed with
acetone and dried in air.
18. Garvey, R.G., Nelson, J.H., and Ragsdale, R.O.,
Coord. Chem. Rev., 1968, no. 3, p. 375.
19. Chmurzynski, L., Wawrzyniak, G., and Warnke, Z.,
REFERENCES
J. Heterocycl. Chem., 1997, vol. 34, no. 1, p. 215.
20. Rybachenko, V.I., Chotii, K.Yu., Kovalenko, V.V.,
and Shreder, G., Zh. Obshch. Khim., 2001, vol. 71,
no. 5, p. 839.
1. Berezin, B.D. and Enikolopyan, N.S., Metalloporfi-
riny (Metal Porphyrins), Moscow: Nauka, 1988.
2. Porfiriny: struktura, svoistva, sintez (Porphyrins:
Structure, Properties, and Synthesis), Enikolo-
pyan, N.S., Ed., Moscow: Nauka, 1987.
21. Dega-Szafran, Z., Grundwald-Wyspianska, M., Ka-
nia, A., Kosturkiewicz, Z., Tykarska, E., and Szaf-
ran, M., J. Mol. Struct., 1995, vol. 356, no. 3, p. 169.
3. Uspekhi Khimii Porfirinov (Advances in Porphyrin
Chemistry), Golubchikov, O.A., Ed., St. Peterburg:
Nauchno-Issled. Inst. Khimii S.-Peterb. Gos. Univ.,
1997, vol. 1.
4. Egan, T.J., Hunter, R., Kashula, C.H., Marques, H.M.,
Misplon, A., and Walden, J., J. Med. Chem., 2000,
vol. 43, no. 2, p. 283.
22. Kirksey, C.H. and Hambright, P., Inorg. Chem., 1970,
vol. 9, no. 4, p. 958.
23. Pal’m, V.A., Osnovy kolichestvennoi teorii organi-
cheskikh reaktsii (Principles of Quantitative Theory of
Organic Reactions), Leningrad: Khimiya, 1977.
24. Prezhdo, V.V., Vashchenko, E.V., Prezhdo, O.V.,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005

EXTRA COORDINATION OF Zn TETRAPHENYLPORPHINE
1317
Pushko, A., and Lorents, Ya., Zh. Obshch. Khim.,
30. Ochiai, E., Aromatic Amine Oxides, New York:
1997, vol. 67, no. 6, p. 1009.
Elsevier, 1967.
25. Shreder, G., Rybachenko, V.I., Chotii, K.Yu., Ko-
valenko, V.V., Grebenyuk, L.V., Lenska, B., and
Eitner, K., Zh. Obshch. Khim., 2003, vol. 73, no. 3,
p. 486.
31. Itai, T. and Kamiya, S., Chem. Pharm. Bull., 1961,
vol. 9, no. 2, p. 87.
32. Kamiya, S., Sueyoshi, S., Miyahara, M., Yanagima-
chi, K., and Nakashima, T., Chem. Pharm. Bull., 1980,
vol. 28, no. 5, p. 1485.
26. Katritzky, A.R., Short, D.L., and Boulton, A.J.,
J. Chem. Soc., 1960, no. 4, p. 1516.
33. Acheson, R.M., Adcock, B., Glover, G.M., and Sut-
27. Andreev, V.P., Batotsyrenova, E.G., Ryzhakov, A.V.,
and Rodina, L.L., Khim. Geterotsikl. Soedin., 1998,
no. 8, p. 1093.
28. Lomov, T.N. and Berezin, B.D., Koord. Khim., 2001,
vol. 27, no. 2, p. 96.
29. Zaitseva, S.V., Zdanovich, S.A., Semeikin, A.S., and
Golubchikov, O.A., Zh. Obshch. Khim., 2003,
vol. 73, no. 3, p. 499.
ton, L.E., J. Chem. Soc., 1960, no. 8, p. 3367.
34. Nizhnik, Ya.P. and Ryzhakov, A.V., Zh. Org. Khim.,
1998, vol. 34, no. 6, p. 958.
35. Rothemund, P. and Menotti, A.R., J. Am. Chem. Soc.,
1948, vol. 70, no. 5, p. 1808.
36. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion, New York: Wiley, 1972.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 8 2005