Complexation of zinc(II) and ruthenium(II) porphyrinates with methyl glycinate and methyl m-aminobenzoate

Article abstract of DOI:10.1134/S1070363213050204

Zinc(II) and ruthenium(II) monohydroxyporphyrinates with a different arrangement of the reaction center in the meso-aryl moiety of the macrocycle were synthesized, and their ability of complexing with the methyl esters of glycine and m-aminobenzoic acid in toluene were studied using the methods of spectrophotometric titration and ¹H NMR spectroscopy. The stability constants of the resulting complexes and concentration ranges of their existence were determined.

Full text of DOI:10.1134/S1070363213050204

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 5, pp. 993–999. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © G.M. Mamardashvili, N.Zh. Mamardashvili, O.I. Koifman, 2013, published in Zhurnal Obshchei Khimii, 2013, Vol. 83, No. 5,
pp. 859–865.
Complexation of Zinc(II) and Ruthenium(II) Porphyrinates
with Methyl Glycinate and Methyl m-Aminobenzoate
G. M. Mamardashvili, N. Zh. Mamardashvili, and O. I. Koifman
Krestov Institute of Solution Chemistry, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: gmm@isc-ras.ru
Received April 10, 2012
Abstract―Zinc(II) and ruthenium(II) monohydroxyporphyrinates with a different arrangement of the reaction
center in the meso-aryl moiety of the macrocycle were synthesized, and their ability of complexing with the
methyl esters of glycine and m-aminobenzoic acid in toluene were studied using the methods of spectro-
1
photometric titration and H NMR spectroscopy. The stability constants of the resulting complexes and
concentration ranges of their existence were determined.
DOI: 10.1134/S1070363213050204
Analysis of published data shows that zinc(II) and
ruthenium(II) porphyrinates can show effective
complexing ability with respect to amino acids [1–7].
In the case of zinc porphyrinates [ZnP(Solv)] the main
factor for linking is the coordination interaction
between the reaction center of the substrate molecule
and the zinc porphyrinate cation. In the case of
ruthenium porphyrinates [RuP(CO)(Solv)], the metal
cation can bind successively two molecules of amino
acid. Moreover, if the binding of the first molecule of
the substrate readily occurs at the location of solvent
molecule, the binding of the second molecule of the
substrate, which occurs at the location of the CO
group, requires more rigid conditions [8].
complexes. The methods of spectrophotometric
titration and 1H NMR spectroscopy were used to
investigate the complexing ability of the synthesized
porphyrinates with respect to methyl glycinate and
methyl m-aminobenzoate. The constants of stability of
the resulting complexes and concentration ranges of
their existence were determined.
In this paper, by the reaction of 5,5'-diformyl-4,4'-
dimethyl-3,3'-diethyl-2,2'-dipyrrolylmethane (I) with
meso-(2-X-phenylene)dipyrrolylmethanes [X = H (II),
OH (III), OCH2OH (IV)] in ethanol in the presence of
hydrobromic acid followed by oxidation of the inter-
mediate porphyrinogenes by tetrachlorbenzoquinone
we synthesized 10-phenyl-2,18-diethyl-3,17-dimethyl-
porphyrin (V), 10-(2-hydroxyphenylene)-2,18-diethyl-
3,17-dimethylporphyrin (VI), and 10-(2-hydroxy-
methyleneoxyphenylene)-2,18-diethyl-3,17-dimethyl-
porphyrin (VII) (see scheme). Average yield of the
desired products was 25%. By the reaction of the
porphyrin ligands (V–VII) with zinc acetate in DMF
the corresponding zinc porphyrinates (VIII–X) were
obtained. Ruthenium porphyrinates RuP(CO)(H2O)
(XI-XIII) were obtained by boiling the porphyrin
ligand (V–VII) with Ru3(CO)12 in phenol.
The processes of selective binding of amino acids
by zinc and ruthenium porphyrinates are of particular
interest, when the substrate is recognized through
coordination interaction of the metal cation of the
porphyrin receptor reaction center with the
simultaneous formation of H-bonds on the periphery of
the macrocycle (the so-called two-center binding of the
substrate molecule by the receptor molecule) [1, 2].
In continuation of our research on the creation of
tetrapyrrole receptors for selective binding of amino
acids [9-11], we synthesized 10–aryl-2,18-diethyl-3,17-
dimethylporphyrin ligands with different arrangements
of the reaction center in the meso-aryl moiety of the
macrocycle, as well as related zinc and ruthenium
Coordinatively unsaturated zinc porphyrinates
VIII–X coordinate amino acid molecules to the zinc
cation axially to form complexes ZnP(L) according to
Eq. (1):
993

994
MAMARDASHVILI et al.
(1)
ZnP + L ↔ ZnP(L).
At the axial coordination of multifunctional organic
ligands on the central cation of zinc (IX, X) and
ruthenium (XII, XIII) porphyrinates, when the
receptor molecule and the substrate contain comple-
mentary reaction centers, the formation is possible of
the porphyrinate-ligand complexes with two sites of
binding.
The six-coordinated ruthenium porphyrinates RuP
(CO)(Solv), where Solv = H2O or EtOH, form stable
complexes with amino acids RuP(CO)L according to
Eq. (2):
RuP(CO)(Solv) + L ⇄ RuP(CO)L + Solv.
C2H5 C2H5
(2)
H3C
OHC
CH3
CHO
N
N
X
H
I
+
H
H+, [O]
N
N
N
N
M
H
H
H
H
N
N
V_ХIII
X
II_IV
X = H (II, V, VIII, XI), OH (III, VI, IX, XII), O(CH2)OH (IV, VII, X, XIII), M = H2 (V–VII), Zn (VIII–X),
Ru(CO)(H2O) (XI–XIII).
The process of the formation by ligand I of the
axial complexes ZnP–L with one donor-acceptor bond
or with multiple binding sites is accompanied by
one type. The complex composition 1:1 follows from
the graphic dependence log [(Ao – Ad)/(Ad – Ae)] vs.
logs of the ligand, which has a slope of ~1. As can be
seen from the table, stability of the ruthenium
porphyrinate-amino acid complexes with a single
binding site is by about two orders of magnitude
higher than that of the corresponding zinc porphyrinate
complexes with the same substrate.
1
upfield shifts in H NMR spectra of the proton signals
of axial-coordinated aromatic ligands and the red shift
by10–15 nm of absorption bands in the EAS of the
reaction system receptor-substrate.
Complexation of ligand II is characterized by ever
stronger upfield shifts of proton signals of the ligands
(~0.6 ppm) in 1H NMR spectra, but a much smaller red
shift of the absorption bands (1–3 nm) in the electron
absorption spectra of the reaction system.
Spectral changes at the titration of porphyrinates IX
and XII by the substrate L1 are similar to the changes
shown in Fig. 1, but the saturation of the reaction
system in these cases occurs at lower concentrations of
the substrate. The slope of the plot log [(Ao – Ad)/
(Ad – Ae)] vs. log cligand for these systems also equals to
unity. The increase in stability constants Kstab (~4-fold)
in the systems of IX–L1 and XII–L1 compared with
the systems of VIII–L1 and XI–L1 suggests that a
complex is formed with two binding sites between the
porphyrinate and methyl ester of α-amino acid (donor-
acceptor M–N bond and a hydrogen bond between the
carbonyl oxygen atom of the ester and hydroxy group
of the porphyrinate). Probably, in the cases of the zinc
and ruthenium porphyrinates IX and XII there is a
good geometric correspondence between the reaction
Spectrophotometric study of complexation of zinc
porphyrinate VIII and ruthenium porphyrinate XI,
which have no hydroxy groups, with methyl glycinate
(L1) and methyl m-aminobenzoare (L2) showed the
formation of complexes with a donor-acceptor bond
(Zn–N). The spectral changes observed during the
formation of the complexes VIII–L1, XI–L1, VIII–
L2, and XI–L2, and the corresponding titration curves
by an example of a system of VIII–L1 are shown in
Fig. 1. The existence of a single step in the
spectrophotometric titration curve indicates that under
these conditions the system forms a complex of only
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

COMPLEXATION OF ZINC(II) AND RUTHENIUM(II) PORPHYRINATES
(b)
995
(a)
ΔА
сL1/c8
λ, nm
Fig. 1. (a) Electron absorption spectra of complex VIII (cporph = 1.2×10–5 M) at the addition of L1 from 0 to 10–3 in toluene and
(b) the spectrophotometric titration curves of complex VIII with L1 on “descending” and “growing” wavelengths (20°C), cporph
=
1.2×10–5 M , cL1 = 0–10–3 M).
centers in the receptor-substrate system and the
stituent and the carboxy group of glycine, which
hydroxy group in ortho-position of the phenyl sub-
ensures the formation of a second bond.
CH3O
H3CO
O
O
OH
NH2
NH2
OH
O
N
N
N
N
N
N
N
N
Zn
Zn
Х_L2
IХ_L1
CH3O
O
H3CO
OH
O
O
NH2
NH2
OH
N
N
N
N
N
N
N
N
Ru
Ru
CO
CO
ХII_L1
ХIII_L2
The corresponding 1H NMR spectra of the complex
provide the confirmation of the formation of porphy-
rinate–amino acid complexes with two sites of binding.
In the presence of L1, in the spectrum of ruthenium
porphyrinate XII in deuterochloroform the signal of
the OH group proton in the aryl moiety of the tetra-
pyrrole macrocycle is shifted downfield by 1.35 ppm,
and in the spectrum of zinc porphyrinate IX, by 12 ppm.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

996
MAMARDASHVILI et al.
(a)
ΔGtot,
kJ mol–1
δ, ppm
(b)
δ, ppm
1
Fig. 2. Fragments of the H NMR spectrum (region 1.5–
6.1 ppm) of porphyrinate X (a) and its complex with L2
(b), deuterochloroform (25°C).
Fig. 3. Contributions to the total binding energy (ΔGtot) of
complexes porphyrinates–amino acid of the energy axial coor-
dination (ΔGax.c) and the hydrogen bond energy (ΔGHB).
A significant increase in the stability constants Kstab.
(more than 7 times in the zinc porphyrinate X and
more than 6 times in the ruthenium porphyrinate XIII)
was found also for the porphyrinates with the hydroxy
group in the hydroxymethyleneoxyphenylene fragment
at their interaction with L2 (see the table). At the
additional hydrogen bond may be the ratio of K'' /
stab
K' , where the K'' is the binding constant of
stab
stab
porphyrin with the hydroxy group, K'bind is the binding
constant of a porphyrin of similar structure, but
without the hydroxy group [1] (see the table). The total
binding energies ΔGtotal of the complexes and the
energies of individual bonds ΔGaxial and ΔGH-bond
calculated by standard methods [1] using the formulas (3)–
(5) are shown in the diagram in Fig. 3.
1
formation of these complexes, in the corresponding H
NMR spectra the signal of the proton of OH group of
the porphyrinate aryl moiety is shifted downfield (by
~1.20 ppm), whereas the signals of the protons of
benzene ring of the ligand are shifted upfield (by
~5.0 ppm for the ortho-aryl protons of the substrate)
(Fig. 2).
As is evident from these data, the strongest
hydrogen bonds with amino acid esters form the zinc
porphyrinates, and the strongest electron-donating
bonds with amino groups of the esters form ruthenium
porphyrinates.
A quantitative measure of the increasing stability of
the porphyrinate-amino acid complexes due to
Thus, the techniques described in this paper
allowed us to synthesize zinc and ruthenium hydroxy-
porphyrinates showing the ability to two-center
binding methyl glycinate and methyl m-aminobenzate.
The zinc and ruthenium o-hydroxyphenylporphyrinates
due to the formation of additional hydrogen bonds at the
periphery of the macrocycle effectively bind methyl
glycinate, while the zinc and ruthenium porphyrinates
with the hydroxy group in the conformationally mobile
ortho-hydroxymethyleneoxyphenylene fragment of the
macrocycle form stable complexes with two sites of
binding to methyl m-aminobenzate. In general, com-
plexes of ruthenium porphyrinates with the amino acid
esters are characterized by a higher stability, but lesser
selectivity than similar complexes formed by the zinc
porphyrinates.
The stability constants of complexes of porphyrinates VIII–
XIII–amino acid ester (Kst, M–1) in toluene at 25°Ca
Complexes with L1
Complexes with L2
Porphyrinates
Kst, M–1
Kst/K
Kst, M–1 Kst/K
compare
st
compare
st
1510
–
1023
1200
–
VIII
IX
6850
4.5b
1.1b
–
3.8c
1.1c
1.2b
7.5b
–
0.9c
6.2c
1680
7610
X
5.1×105
19.5×105
4.7×105
2.8×105
2.5×105
9.7×105
XI
XII
XIII
a
The error in estimation of Kst zinc porphyrinates is 3–5%, for
ruthenium porphirinates, 5–7%. b Complex VIII for comparison.
c Complex XI for comparison.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

COMPLEXATION OF ZINC(II) AND RUTHENIUM(II) PORPHYRINATES
997
EXPERIMENTAL
10-Phenyl-2,18-diethyl-3,17-dimethylporphyrin
(V). Yield: 23%. Rf 0.53, (Al2O3, eluent – benzene). IR
spectrum (KВr), ν, cm–1: 3310 (NH), 2980, 2929, 2870
(СH), 1663, 1616 (С–С), 1505, 1482, 1170, 1108,
1069 (δСH), 1350, 1306 (С≡N), 967 (δNH), 830, 752,
723, 548 (γСH), 691 (γNH). EAS (toluene), λ, nm (log
ε): 631 (3.33), 579 (3.89), 550 (3.70), 517 (4.24), 404
(5.13). 1Н NMR spectrum, δ, ppm: 10.10 s (2H, ms-H),
10.06 s (1H, ms-H), 8.80 d (2Н, СНPyr, J 4.6), 8.73 d
(2Н, СНРyr, J 4.6), 7.52 t (1Н, Ar, J 7.8), 7.26 m (4H,
Ar), 2.95 q (4H, CH2CH3, J 8.2), 2.22 s (6Н, СН3),
1.15 t (6H, CH2CH3, J 8.2), –3.50 br.s (1H, NH), –3.54
br.s (1H, NH). Found, %: С 83.50; Н 6.19; N 10.23.
С38Н34N4O. Calculated, %: С 83.82; Н 6.26; N 10.41.
The electron absorption spectra (EAS) of por-
phyrinates and their complexes with amino acid esters
in toluene were recorded on a spectrophotometer “Cary
100.” H NMR spectra were recorded on a spectrometer
Brusker VC-500 at operating frequency 500.17 MHz
in deuterochloroform, internal reference TMS.
1
The stability constants (Kst) of complexes of zinc
bisporphyrinates (A) with the corresponding substrates
(B) were evaluated by spectrophotometric titration:
[AB]
Kst = –——– = 1/[B] ——— · ——— ,
[A][B] ΔAo,λ1 ΔAi,λ2
ΔAi,λ1 ΔAo,λ2
10-(2-Hydroxymethyleneoxyphenylene)-2,18-di-
ethyl-3,17-dimethylporphyrin (VII). Yield: 21%. Rf
0.49, (Al2O3, eluent – benzene). IR spectrum (KВr), ν,
cm–1: 3310 (NH), 3215 (ОH), 2989, 2930, 2878 (СH),
1677, 1620 (С–С), 1511, 1485, 1175, 1110, 1064
(δСH), 1356, 1308 (С≡N), 1245, 1030 (С–O–C), 1237,
1014 (δOH), 969 (δNH), 838, 755, 728, 520 (γСH), 697
(γNH). EAS (toluene), λ, nm (log ε): 632 (3.31), 580
where λ1 is the decreasing wavelength, λ2 is the
increasing wavelength [A] is the concentration of
bisporphyrinate, [S] is the concentration of substrate,
ΔAo is the maximum change in optical density of the
solution at a given wavelength, ΔAi is the change in
optical density solution at a given wavelength at a
given concentration as described in [9–11].
1
10-(2-hydroxyphenylene)-2,18-diethyl-3,17-di-
methylporphyrin (VI). 5,5'-Diformyl-4,4'-dimethyl-
3,3'-diethyl-2,2'-dipyrrolylmethane (0.5 g, 1.5 mmol)
and meso-(2-hydroxyphenylene)dipyrrolylmethane
(0.5 g, 1.7 mmol) were dissolved in 50 ml of ethanol
containing 1 ml of hydrobromic acid. The solution was
stirred for 2 h, and to the reaction mixture was added
tetrachloro-1,2-benzoquinone (1 g, 4.1 mmol) in 10 ml
of chloroform. The solvent was evaporated and the
residue was washed with 10% KOH solution, dried,
and chromatographed on silica gel eluting with
benzene. 3312 (NH), 3210 (OH), 2982, 2928, 2875
(CH), 1665, 1617 (С–С), 1507, 1480, 1170, 1109,
1068 (δСH), 1353, 1307 (С≡N), 1230 (δOH), 967 (δNH),
832, 753, 723 (γСH), 696 (γNH). EAS (toluene), λ, nm
(log ε): 630 (3.36), 579 (3.89), 551 (3.70), 517 (4.24),
405 (5.13). 1Н NMR spectrum, δ, ppm (J, Hz): 10.12 s
(2H, ms-H), 10.08 s (1H, ms-H), 8.82 d (2Н, СНРyr, J
4.8), 8.76 d (2Н, СНРyr, J 4.8), 7.52 t (1Н, Ar, J 7.7),
7.36 m (2H, Ar), 7.21 d (1H, Ar, J 7.7), 2.97 q (4H,
CH2CH3, J 8.2), 5.31 s (1H, OH), 2.24 s (6Н, СН3),
1.18 t (6H, CH2CH3, J 8.2), –3.53 br.s (1H, NH), –3.56
br.s (1H, NH). Found, %: С 81.23; Н 6.04; N 9.94.
С38Н34N4O. Calculated, %: С 81.54; Н 6.08; N 10.17.
(3.81), 551 (3.73), 518 (4.21), 406 (5.11). Н NMR
spectrum, δ, ppm: 10.09 s (2H, ms-H), 10.01 s (1H,
ms-H), 8.78 d (2Н, СНРyr, J 4.8), 8.71 d (2Н, СНРyr, J
4.8), 7.50 t (1Н, Ar, J 7.7), 7.31 m (2H, Ar), 7.19 d
(1H, Ar, J 7.7), 2.90 q (4H, CH2CH3, J 8.0), 1.68 s
(1H, OH), 3.53 s (2H, ОCH2), 2.21 s (6Н, СН3), 1.13 t
(6H, CH2CH3, J 8.0), –3.57 br.s (1H, NH), –3.59 br.s
(1H, NH). Found, %: С 79.19; Н 6.01; N 9.42.
С39Н36N4O2. Calculated, %: С 79.41; Н 6.08; N 9.76.
Zn(II) 10-(2-hydroxyphenylene)-2,18-diethyl-3,18-
dimethylporphyrinate (IX). To a solution of the
porphyrin ligand (30 mg) in DMF (70 ml) was added
an excess (1:10 mole) of zinc acetate and the reaction
mixture was boiled for 30 min. The content of the flask
was cooled and diluted with water (1:1). The
precipitate was filtered off, dried, and chromato-
graphed on alumina, eluting with CH2Cl2–C6H14, 1–1.
The solvents were distilled off in a vacuum, the residue
was recrystallized from a mixture of CH2Cl2-CH3OH,
1:2. Yield: 81%. Rf 0.78, (Al2O3, eluent – benzene). IR
spectrum (KВr), ν, cm–1: 3216 (ОH), 3058, 2928, 2850
(NH); 1665, 1617 (С–С), 1507, 1480, 1170, 1094,
1068 (δСH), 1353, 1307 (С≡N), 1233 (δОH), 999 (Zn–
N), 829, 753, 703 (γСH), 454, 404 (Zn–N). EAS
(toluene), λ, nm (log ε): 579 (3.45), 540 (4.23), 405
(5.01). 1Н NMR spectrum, δ, ppm: 10.14 s (2H, ms-H),
10.11 s (1H, ms-H), 8.79 d (2Н, СНРyr, J 4.8), 8.71 d
Similarly, 10-phenyl-2,18-diethyl-3,17-dimethylpor-
phyrin (V) and 10-(2-hydroxymethyleneoxyphenylene)-
2,18-diethyl-3,17-dimethylporphyrin (VII) were obtained.
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998
MAMARDASHVILI et al.
(2Н, СНРyr, J 4.8), 7.49 t (1Н, Ar, J 7.7), 7.32 m (2H,
Ar), 7.19 d (1H, Ar, J 7.7), 2.94 q (4H, CH2CH3, J
8.0), 5.29 s (1H, OH), 2.21 s (6Н, СН3), 1.14 t (6H,
CH2CH3, J 8.0).
Complex IX–L1. 1H NMR spectrum, δ, ppm:
10.18 s (2H, ms-H), 10.06 s (1H, ms-H), 8.75 d (2Н,
СНРyr, J 4.6), 8.68 d (2Н, СНРyr, J 4.6), 7.46 t (1Н, Ar,
J 7.7), 7.29 m (2H, Ar), 7.15 d (1H, Ar, J 7.7), 6.41 s
(1H, OH), 5.02 br.s (2H, NH2), 3.89 s (3Н, ОСН3),
2.90 q (4H, CH2CH3, J 8.0), 2.19 s (6Н, СН3), 1.16 t
(6H, CH2CH3, J 8.0), 3.05 m (2H, CH2), 3.83 s (3H,
OCH3).
5.81 s (2H, NH2), 3.82 s (3H, ОСН3), 3.45 s (2H,
ОCH2), 3.21 m (2Н, Ar), 2.85 q (4H, CH2CH3, J 8.0),
2.18 s (6Н, СН3), 1.16 t (6H, CH2CH3, J 8.0).
Ruthenium(II) 10-(2-hydroxyphenylene)-2.18-di-
ethyl-3,17-dimethylporphyrinate (CO)(H2O) (XII).
A mixture of porphyrin I (50 mg, 0.059 mmol) and
Ru3(CO)12 (40 mg, 0.06 mmol) was boiled in 5 g of
phenol for 3 min. The reaction mixture was cooled,
dissolved in 20 ml of DMF, poured into water, washed
with hot water, twice chromatographed on silica gel
eluting with chloroform. Yield: 39%. Rf 0.67, (Al2O3,
eluent – benzene). IR spectrum (KВr), ν, cm–1: 3217
(ОH), 2985, 2928, 2850 (СH), 1940 (С=О), 1665,
1617 (С–С), 1507, 1480, 1170, 1109, 1068 (δСH),
1353, 1307 (С≡N), 1230 (δОH), 1012 (Ru–N), 830,
763, 723 (γСH), 520 (Ru–СО), 464, 407 (Ru–N). EAS
(toluene), λ, nm (log ε): 547 (4.57), 517 (4.01), 404
(5.12). 1Н NMR spectrum, δ, ppm: 10.12 s (2H, ms-H),
10.07 s (1H, ms-H), 8.77 d (2Н, СНРyr, J 4.8), 8.69 d
(2Н, СНРyr, J 4.8), 7.44 t (1Н, Ar, J 7.8), 7.33 m (2H,
Ar), 7.17 d (1H, Ar, J 7.8), 2.91 q (4H, CH2CH3, J
8.2), 5.30 s (1H, OH), 2.17 s (6Н, СН3), 1.11 t (6H,
CH2CH3, J 8.2).
Similarly, zinc(II) 10-phenyl-2,18-diethyl-3,17-di-
methylporphyrinat (VIII) and zinc(II) 10-(2-hyd-
roxymethyleneoxyphenylene)-2,18-diethyl-3,17-dimethyl-
porphyrinate (X) were obtained.
Zinc(II) 10-phenyl-2,18-diethyl-3,17-dimethyl-
porphyrinate zinc (VIII). Yield: 85%. Rf 0.73,
(Al2O3, eluent – benzene). IR spectrum (KВr), ν, cm–1:
3070, 2929, 2869 (СH), 1643, 1606 (С–С), 15010,
1482, 1170, 1086, 1074 (δСH), 1350, 1306 (С≡N), 998
(Zn–N), 826, 752, 708 (γСH), 436, 403 (Zn–N). EAS
(toluene), λ, nm (log ε): 578 (3.42), 541 (4.21), 404
(5.00). 1Н NMR spectrum, δ, ppm: 10.12 s (2H, ms-H),
10.08 s (1H, ms-H), 8.77 d (2Н, СНРyr, J 4.6), 8.69 d
(2Н, СНРyr, J 4.6), 7.47 t (1Н, Ar, J 7.8), 7.22 m (4H,
Ar), 2.92 q (4H, CH2CH3, J 8.2), 2.20 s (6Н, СН3),
1.11 t (6H, CH2CH3, J 8.2).
1
Complex XII–L1. H NMR spectrum, δ, ppm:
10.16 s (2H, ms-H), 10.01 s (1H, ms-H), 8.73 d (2Н,
СНРyr, J 4.6), 8.66 d (2Н, СНРyr, J 4.6), 7.41 t (1Н, Ar,
J 7.7), 7.30 m (2H, Ar), 7.12 d (1H, Ar, J 7.7), 3.89 s
(3Н, ОСН3), 2.85 q (4H, CH2CH3, J 8.0), 6.35 s (1H,
OH), 2.15 s (6Н, СН3), 5.12 br.s (2H, NH2), 1.13 t
(6H, CH2CH3, J 8.0), 0.96 s (3Н, СН3), 3.08 m (2H,
CH2), s (3H, OCH3).
Zinc(II) 10-(2-hydroxymethyleneoxyphenylene)-
2,18-diethyl-3,17-dimethylporphyrinate (X). Yield:
77%. Rf 0.71, (Al2O3, eluent – benzene). IR spectrum
(KВr), ν, cm–1: 3219 (ОH), 3030, 2930, 2850 (СH),
1677, 1620 (С–С), 1512, 1485, 1175, 1110, 1064
(δСH), 1356, 1308 (С≡N), 1240, 1032 (С–O–C), 12340
(δОH), 999 (Zn–N), 828, 755, 708 (γСH), 456, 403 (Zn–
N). EAS (toluene), λ, nm (log ε): 580 (3.48), 541
(4.27), 407 (5.05). 1Н NMR spectrum, δ, ppm: 10.03 s
(2H, ms-H), 9.99 s (1H, ms-H), 8.75 d (2Н, СНРyr, J
4.8), 8.69 d (2Н, СНРyr, J 4.8), 7.46 t (1Н, Ar, J 7.8),
7.28 m (2H, Ar), 7.17 d (1H, Ar, J 7.8), 2.87 q (4H,
CH2CH3, J 8.0), 1.57 s (1H, OH), 3.51 s (2H, ОCH2),
2.20 s (6Н, СН3), 1.18 t (6H, CH2CH3, J 8.0).
Similarly, ruthenium(II) 10-phenyl-2,18-diethyl-3,17-
dimethylporphyrinate (CO)(H2O) (XI) and ruthe-
nium(II) 10-(2-hydroxymethyleneoxyphenylene)-2,18-
diethyl-3,17-dimethylporphyrinate (CO)(H2O) (XIII)
were obtained.
Ruthenium(II) 10-phenyl-2,18-diethyl-3,17-di-
methylporphyrinate (CO)(H2O) (XI). Yield: 43%. Rf
0.61, (Al2O3, eluent – benzene). IR spectrum (KВr), ν,
cm–1: 2980, 2929, 2850 (СH), 1942 (С=О), 1663, 1616
(С–С), 15010, 1482, 1170, 1108, 1069 (δСH), 1350,
1306 (С≡N), 1010 (Ru–N), 832, 762, 723 (γСH), 548
(Ru–СО), 464, 405 (Ru–N). EAS (toluene), λ, nm (log ε):
1
545 (4.53), 515 (4.04), 406 (5.17). Н NMR spectrum,
1
Complex X–L2. H NMR spectrum of, δ, ppm:
δ, ppm: 10.09 s (2H, ms-H), 10.01 s (1H, ms-H), 8.75
d (2Н, СНРyr, J 4.8), 8.63 d (2Н, СНРyr, J 4.8), 7.46 t
(1Н, Ar, J 7.7), 7.21 m (42H, Ar), 2.90 q (4H,
CH2CH3, J 8.2), 2.13 s (6Н, СН3), 1.07 t (6H,
CH2CH3, J 8.2).
10.01 s (2H, ms-H), 9.98 s (1H, ms-H), 8.73 d (2Н,
СНРyr, J 4.6), 8.67 d (2Н, СНРyr, J 4.6), 7.69 d (1Н, Ar,
J 7.6), 7.43 t (1Н, Ar, J 7.8), 7.26 m (2H, Ar), 7.14 d
(1H, Ar, J 7.8), 2.77 s (1H, OH), 6.07 t (1Н, Ar, J 7.6),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 5 2013

COMPLEXATION OF ZINC(II) AND RUTHENIUM(II) PORPHYRINATES
999
Ruthenium(II) 10-(2-hydroxymethyleneoxyphenyl-
ene)-2,18-diethyl-3,17-dimethylporphyrinate (CO) ·
(H2O) (XIII). Yield: 33%. Rf 0.51, (Al2O3, eluent –
benzene). IR spectrum (KВr), ν, cm–1: 3220 (ОH),
2990, 2930, 2850 (СН), 1938 (С=О), 1677, 1620 (С–
С), 1512, 1485, 1175, 1110, 1064 (δСH), 1356, 1308
(С≡N), 1246, 1032 (С–O–C), 1236 (δОH), 1014 (Ru–N),
833, 765, 728 (γСH), 520 (Ru–СО), 466, 408 (Ru–N).
1Н NMR spectrum, δ, ppm: 10.09 s (2H, ms-H), 10.05
s (1H, ms-H), 8.79 d (2Н, СНРyr, J 4.8), 8.73 d (2Н,
СНРyr, J 4.8), 7.45 t (1Н, Ar, J 7.7), 7.21 m (2H, Ar),
7.04 d (1H, Ar, J 7.7), 1.45 s (1H, OH), 3.49 s (2H,
ОCH2), 2.82 q (4H, CH2CH3, J 8.2), 2.13 s (6Н, СН3),
1.13 t (6H, CH2CH3, J 8.2).
and Atomic Clusters,” the Seventh Framework
Programme of the European Community for Research,
Technological Development and Demonstration
Activities, IRSES-GA-2009-247260) and the Federal
Targeted Program “Scientific and Scientific-Peda-
gogical Staff of Innovative Russia” for 2009–2013
(state contract no. 02.740.11.0857).
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ACKNOWLEDGMENTS
8. Hopf, F.R., O’Brien, T.P., Scheidt, W.R., and Whit-
This work was supported by the Russian
Foundation for Basic Research (grants nos. 11-03-
00003_a, 12-03-00775_a), within the framework of the
programs of the Department of chemistry and material
sciences of the Russian Academy of Sciences no. 1
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