Coordination of 5,10,15,20-tetraphenyl-21H,23H-porphin by rhenium in various oxidation states

Article abstract of DOI:10.1134/S0036023612090203

A method was developed for the synthesis of three rhenium complexes, (5,10,15,20-tetraphenyl- 21H,23H-porphinato)(phenoxo)rhenium(III) (PhO)ReTPP, (5,10,15,20-tetraphenyl-21H,23H-porphi- nato)(chloro)rhenium(III) (Cl)ReTPP, and μ-oxo-bis[(oxo)-(5,10,15,20-tetraphenyl-21H,23H-porphi- nato)rhenium(V)] [O=ReTPP]₂O, by one reaction between porphyrin H₂TPP and H₂ReCl₆ in boiling phe- nol. In the complex formation reaction accompanied by the redox process, only the metal cation is involved in the transformation. Rhenium(IV) as chlororhenic acid dispropoportionates without participation of sol- vent or porphyrin to give Re(III) and Re(V) complexes. The chemical structures of the products were estab- lished by spectral and elemental analysis. Characteristics of the UV, Vis, IR, and 1H NMR spectra, the chro- matographic mobility, and stability of the complexes were determined. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S0036023612090203

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2012, Vol. 57, No. 9, pp. 1295–1301. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © E.Yu. Tyulyaeva, N.G. Bichan, T.N. Lomova, E.G. Mozhzhukhina, 2012, published in Zhurnal Neorganicheskoi Khimii, 2012, Vol. 57, No. 9, pp. 1378–1384.
PHYSICAL CHEMISTRY
OF SOLUTIONS
Coordination of 5,10,15,20ꢀTetraphenylꢀ21
H,23Hꢀporphin
by Rhenium in Various Oxidation States
E. Yu. Tyulyaeva, N. G. Bichan, T. N. Lomova, and E. G. Mozhzhukhina
Institute of Solution Chemistry, Russian Academy of Sciences, Akademicheskaya 1, Ivanovo, 153045 Russia
Received June 24, 2011.
Abstract—A method was developed for the synthesis of three rhenium complexes, (5,10,15,20ꢀtetraphenylꢀ
21
H
,23
H
ꢀporphinato)(phenoxo)rhenium(III) (PhO)ReTPP, (5,10,15,20ꢀtetraphenylꢀ21
H
,23
,23
H
H
ꢀporphiꢀ
ꢀporphiꢀ
nato)(chloro)rhenium(III) (Cl)ReTPP, and
µ
ꢀoxoꢀbis[(oxo)ꢀ(5,10,15,20ꢀtetraphenylꢀ21
H
nato)rhenium(V)] [O=ReTPP]2O, by one reaction between porphyrin H2TPP and H2ReCl6 in boiling pheꢀ
nol. In the complex formation reaction accompanied by the redox process, only the metal cation is involved
in the transformation. Rhenium(IV) as chlororhenic acid dispropoportionates without participation of solꢀ
vent or porphyrin to give Re(III) and Re(V) complexes. The chemical structures of the products were estabꢀ
lished by spectral and elemental analysis. Characteristics of the UV, Vis, IR, and 1H NMR spectra, the chroꢀ
matographic mobility, and stability of the complexes were determined.
DOI: 10.1134/S0036023612090203
Group 7 and 8 elements of the Periodic System
have high coordinating ability. The diversity of oxidaꢀ
tion states varying from 0 to +6 and coordination
numbers in the coordination compounds gives rise to
numerous combinations: 23 for Re, 17 for Ru, and 21
for Os [1]. Many complexes exhibit high catalytic and
biological activities. Owing to the ability of macrocyꢀ
clic ligands, especially aromatic, to stabilize unstable
oxidation states of metals, the porphyrin complexes of 21
these metals (metal porphyrins, MP) can be used as
components of inorganic and organometallic materiꢀ
als [2].
EXPERIMENTAL
The starting rhenium compound H2ReCl6 was preꢀ
pared by the reaction of ReO2 with HCl on heating.
(5,10,15,20ꢀTetraphenylꢀ21
(phenoxo)rhenium(III) (PhO)ReTPP, (5,10,15,20ꢀ
tetraphenylꢀ21 ,23 ꢀporphinato)(chloro)rhenium(III)
(Cl)ReTPP, and ꢀoxoꢀbis[(oxo)(5,10,15,20ꢀ tetraphenylꢀ
,23 ꢀporphinato)]rhenium(V) [O=ReTPP]2O.
H,23Hꢀporphinato)
H
H
µ
H
H
H2TPP andH2ReCl6 in 1 : 2 molar ratio were refluxed in
phenol at 454 K for 2 h. After reaction completion
detected by the disappearance of band for H2TPP and
termination of changes in the UV/Vis spectrum of the
reaction mixture in chloroform, the contents of the
reaction vessel were cooled and, after dilution with
water, the products were extracted into chloroform.
The CHCl3 solution was repeatedly washed with warm
water to remove phenol, concentrated by partly evapꢀ
orating the solvent, and chromatographed on a colꢀ
umn with Al2O3 (Brockman activity II) using chloroꢀ
form. This gave two zones, a diffuse green zone (Fig. 1,
A large number of publications consider the synꢀ
thesis and properties of MP [3] and the practical use of
rhenium macrocyclic coordination compounds, in
particular, in radiopharmacology for photodynamic
therapy [4, 5]. However, rhenium porphyrin comꢀ
plexes remain little studied. The published data are
limited to the works dealing with the synthesis and
study of monomers and dimers of Re(I), Re(II),
Re(III), and Re(V) compounds of various structure line 1) and concentrated greenꢀbrown zone (Fig. 1, 2).
The substances isolated from the first and second
zones were chromatographed once again.
[6–11].
This communication reports the new method of
The greenꢀzone compound was chromatographed
on a silica gel (40/100 Chemapol) column, elution
being performed first by benzene and then by a CHCl3
с C2H5OH mixture (1 : 1). This gave three zones
(orange, lilac, and green): (1) (Cl)ReTPP with the
simultaneous synthesis of three rhenium complexes:
(5,10,15,20ꢀtetraphenylꢀ21
,23 ꢀporphinato)(pheꢀ
noxo)rhenium(III) (PhO)ReTPP, (5,10,15,20ꢀtetꢀ
raphenylꢀ21 ,23 ꢀporphinato)(chloro)rhenium(III)
(Cl)ReTPP, and ꢀoxoꢀbis[(oxo)(5,10,15,20ꢀtetraphenylꢀ
21 ,23 ꢀporphinato)rhenium(V)] [O=ReTPP]2O
in one reaction. The quantitative spectral characterisꢀ
tics and stability data for the complexes are presented.
These data were used, together with elemental analyꢀ
sis, to determine the structures of the complexes.
H
H
H
H
μ
UV/Vis spectrum of a typical MP (Fig. 2,
(2) Н2TPP; (3) [O=ReTPP]2O (Fig. 2, ).
1);
H
H
,
2
Chromatography of the substance of the greenꢀ
brown zone on a silica gel column using first benzene
and then a CHCl3 с C2H5OH mixture (1 : 1) gave pink
1295

1296
TYULYAEVA et al.
A
А
467
422
458
1
2
3
400
500
600
700
λ
, nm
Fig. 2. UV/Vis spectra in CHCl of (1) (Cl)ReTPP, (2)
3
[O=ReTPP] O, and (3) (PhO)ReTPP.
2
nation center, 418 (Re–N); 663 (Re–O); axial ligand,
1265, 1462, 1542 (–OPh).
514
558
1H NMR (CDCl3,
, ppm): 8.95 (d, 8H ), 8.25,
δ
2
8.15 (d, m, 8Hо); 7.80 8Hm), 7.55 (m, 4Hp),β3.63 (s,
2Ho (OPh)), 4,71 (s, 2Hm (OPh)), 5.37 (s, 1Hp,
(OPh)).
1
λ
, nm
Fig. 1. UV/Vis spectra of samples isolated upon the first
chromatography (Al O , elution with CHCl ) of the prodꢀ
[O=ReTPP]2O. Yield 75%. UV/Vis (CHCl3, λmax
nm (log ): 620 (sh), 582 (4.51), 461 (5.34), 333 (4.88).
IR (solid random layer,
, cm–1): phenyl groups,
702, 754 ( (C–H)); 1072, 1179 ( (C–H)); 1485,
1575, 1597 ( (C=C)); 2954, 3056 ( (C–H)); pyrrole
) and green [O=ReTPP]2O groups, 801 (
(C–H)); 1018 ((C3–C4), (C–N),
(C–H)); 1341 ( (C–N)); 1440 ( (C=N)); coordinaꢀ
,
2
3
3
ε
ucts of reaction of H ReCl with H TPP: (1) green zone;
2
6
2
ν
(2) greenꢀbrown zone.
γ
δ
ν
ν
(PhO)ReTPP (Fig. 2,
zones.
3
γ
ν
δ
ν
ν
tion centre, 418 (Re–N); 568, 630, 854 (Re–O–Re);
961, 946 (Re–O).
Solid amorphous samples were isolated from soluꢀ
tions by solvent evaporation at room temperature. The
individual character and chromatographic purity of
the products isolated in this way were confirmed by
TLC on Silufol plates using the CHCl3–2% C2H5OH
1H NMR (CDCl3,
7.6 Hz), 8.79 (s, 16 ), 8.01 (t, 8Hm,
δ
, ppm): 9.07 (d, 8Hо,
= 7.6 Hz), 7.60
= 7.6 Hz), 7.04,
J =
H
J
β
(t, 8Hp,
J
= 7.6 Hz), 7.47 (d,
8
J
Ho',
solvent for [O=ReTPP]2O (Rf = 0.42) and benzene for
6.87 (t, t,
8
J = 7.6 Hz).
Hm',
(Cl)ReTPP (Rf = 0.80) and (PhO)ReTPP (Rf = 0.83).
1H NMR (D2SO4,
δ, ppm): 9.13 (m, 8H ), 8.52,
β
(Cl)ReTPP. Yield 0.5%. UV/Vis (CHCl3, λmax
,
8.23 (t, t, 8Hо), 8.06 (t, 8Hm, 4 Hp).
For C88H56N8O3Re2 anal. calcd. (%): C, 64.22;
H, 3.41; N, 6.81.
nm): 555 (sh), 525, 495 (sh), 416. UV/Vis (AcOH,
λmax, nm): 540 (sh), 520, 480, 437 (sh), 417.
IR (300–2000 cm–1) (KBr pellets,
groups, 705, 759 ( (C–H)); 1075, 1172 (
1466, 1595, 1614 ( (C=C)); pyrrole groups, 799
(C–H)); 1029 ((C3–C4), (C–N), (C–H)); 1350
(C–N)); 1377 ( (C=N)); coordination center, 408
ν
, cm–1): phenyl
Found (%): C, 63.14; H, 3.52; N, 5.59.
γ
δ
(C–H));
The UV/Vis spectra were measured on Agilent
8453 UVꢀVis and Specord Mꢀ400 spectrophotomeꢀ
ters; IR spectra were recorded on a VERTEX 80v
spectrometer; the 1H NMR spectrum was recorded on
a Bruker AVANCEꢀ500 spectrometer, using TMS as
the internal standard; elemental analysis was perꢀ
formed on a CHNSꢀO Analyzer Flash EA 1112 Series.
The solid layers of complexes for IR spectroscopy
was formed by evaporating the CHCl3 solvent from a
solution of the complex on a silicon plate.
ν
(
γ
ν
δ
(ν
ν
(Re–N); 374, 392 (Re–Cl).
The 1H NMR spectrum was not studied due to low
product yield. The product was identified based on the
hypsoꢀtype UV/Vis spectrum typical of metal porphyꢀ
rins [12] (table).
(PhO)ReTPP. Yield 7%. UV/Vis (CHCl3, λmax
,
nm, (log ): 660 (sh), 551 (2.3), 436 (sh), 425 (4.3).
ε
RESULTS AND DISCUSSION
IR (solid random layer,
, cm–1): phenyl groups,
702, 758 ( (C–H)); 1068, 1178 ( (C–H)); 1487,
1578, 1600 ( (C=C)); 2956, 3060 (
groups, 806 ( (C–H)); 997 ((C3–C4),
(C–H)); 1340 ( (C–N)); 1377 ( (C=N)); coordiꢀ plexes. In this case, CO ligands are always present at
ν
γ
δ
Analysis of published data [13] indicates that metal
ν
ν(C–H)); pyrrole carbonyls are used most often as complexing ions for
γ
ν
(C–N), the synthesis of Group 7 and 8 metal porphyrin comꢀ
δ
ν
ν
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 9 2012

COORDINATION OF 5,10,15,20ꢀTETRAPHENYLꢀ21
H
,23H
ꢀPORPHIN
1297
Metal porphyrins with hypsoꢀtype UV/Vis spectrum and parameters of the spectrum in CHCl3
Metal
porphyrin MP
M
λ
max, nm (log
4.64)a, 461(3.91), 497(3.67), 538(4.16)b, 563(sh)
373(5.11), 416 4.39), 494(4.14), 521(sh)
ε
)
Refs.
configuration
(Cl)2HfTPP
(Cl)2TiTPP
(Cl)ReTPP
(Cl)ReTPPc
(Cl)RhTPP
(Cl)IrTPP
(Cl)2PtTPP
PdTPP
d0
d2
d4
d4
d6
d6
d6
d8
d8
d8
414
(
[14]
[15]
(
416, 495(sh), 525, 555(sh)
417, 437(sh), 480, 520, 540(sh)
421
(
5.30), 533(4.33), 569(3.72), 592(3.28)
[16]
[17]
[18]
[19]
[20]
[18]
395(sh), 418(4.78), 476(sh), 508(sh), 549(3.42), 588(2.81), 640(2.63)
436
416
422
402
(
(
(
(
4.57), 517(4.26), 548(4.45), 587(4.19)
5.50), 480(3.68), 521(4.45), 552(sh), 602(3.14)
5.12), 525(4.37), 638(3.30)
PdTPP(iꢀOCH3)4
PtTPP
4.84), 511(4.11), 451(3.92)
a Soret band; b Q(0.1) band [13]; c in AcOH.
the coordination center, which considerably affects reaction. In the reaction of H2ReCl6 with H2TPP, the
the properties of MP and, therefore, it is not always
desirable. The use of oxides of metals in higher oxidaꢀ
tion states solves this problem only partially as their
inertness increases the time of synthesis up to 7 h in the
case of Re2O7 and 2,3,7,8,12,13,17,18ꢀoctaethylꢀ
redox transformation involves only the rhenium(IV)
cation as follows from the absence of traces of reduced
H2TPP in the reaction mixture.
Using spectral methods and elemental analysis, it is
possible to determine the chemical structure of the
coordination center in the synthesized rhenium comꢀ
plexes. The metal porphyrin nature of the compounds
is confirmed by the IR spectra, which exhibit absorpꢀ
tion bands for the bonds and fragments of pyrrole and
phenyl groups. The absence of strong absorption at
964 cm–1 corresponding to inꢀplane bending vibraꢀ
21H,23Hꢀporphin (H2OEP) [20]. In this study, stable
chlororhenic acid H2ReCl6 was used as the complex
cation donor instead of the volatile and extremely
toxic Re2(CO)10. This acid was prepared from rheꢀ
nium(IV) oxide by the reaction
ReO2 + 6HCl = H2ReCl6 + 2H2O.
(1)
tions, (N–H), in H2TPP implies that the porphyrin
δ
The coordination of H2TPP resulting in the formaꢀ
tion of several individual rhenium(III) and rheꢀ
nium(V) compounds is a complex redox process.
According to [1], these oxidation states of rhenium
give rise to the largest number of coordination comꢀ
pounds. The coordination of the porphyrin ligand by
highly charged metal cations accompanied by redox
processes is known for indium, lead, molybdenum,
tungsten, and iridium complexes [21, 22]. In the firstꢀ
mentioned case, the stable metal oxidation state (+3)
did not change; however, the redox reaction between
the solvent, boiling phenol, and porphyrin afforded
indium(III) complexes with porphyrin and with its
reduced form, chlorin. In all other cases, the metal
ligand is not coordinated in the molecular form (soꢀ
called sitting atop complex) but is coordinated as the
TPP2– anion. The IR spectra of (PhO)ReTPP and
[O=ReTPP]2O shows absorption with a maximum at
418 cm–1 corresponding to Re–N vibrations; in the
case of (Cl)ReTPP, the maximum is shifted to 408 cm–1.
This may be due to the reduced force constant of the
Re–N bonds caused by conjugation of Cl electron
pairs with the
d orbitals of Re. In the spectra of comꢀ
π
plexes with oxygenꢀcontaining axial ligands, the freꢀ
quency of the absorption maximum does not depend
on the metal oxidation state. A similar situation is
observed for the platinum porphyrin complexes with
cation and phenol or porphyrin underwent a redox 2+, 3+, and 4+ oxidation states of the metal for which
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 9 2012

1298
TYULYAEVA et al.
bands for (Cl)ReTPP (or 342 cm–1 in the spectrum of
[ReCl6]2– [27]) may be due to the axial ligand.
b
The –OPh ligand can be detected also by the presꢀ
ence of signals of
oꢀ, mꢀ, and pꢀprotons in the
1H NMR spectrum of (PhO)ReTPP; these signals are
shifted upfield with respect to the proton signals of free
phenol [28]. No additional signals that could be
assigned to the protons of axial ligands were found in
the 1H NMR spectrum of [O=ReTPP]2O. The
1H NMR spectrum of [O=ReTPP]2O in CDCl3 differs
from the spectra for free H2TPP [29] or 1 : 1 MP, but
bears considerable resemblance to the spectrum of
μꢀoxo dimer [HORuTPP]2O [30]. The calculation of
а
the number of protons from the integrated curves gave
more protons of each sort than in the case of 1 : 1 comꢀ
plexes. The signal splitting in the spectra of metal porꢀ
phyrin dimers is caused by change in the symmetry
dictated by the porphyrin ring. In the spectrum of
[O=ReTPP]2O, the pyrrole protons
for a sharp singlet at = 8.79 ppm; the protons of the
mesoꢀphenyl groups Hp account for a triplet at = 7.60
H are responsible
β
δ
δ
ppm, while the Hо and Hm signals are split into two
doublets and two triplets, respectively. (The highꢀfield
signal is additionally split into two triplets). The signal
splitting for these sorts of protons is due to the arrangeꢀ
ment of the phenyl groups at an angle to the macrocyꢀ
1600
1400
ν
, cm–1
cle plane. The bands for
H and Hp and the Hо and Hm
protons located inside theβcavity formed by two macꢀ
rocycles were shifted upfield relative to the signals in
the spectrum of [O=ReTPP]2O in D2SO4 where the
Fig. 3. IR spectra of (a) [O=ReTPP] O and (b)
2
(PhO)ReTPP in the region of phenyl C=C vibrations.
Solid random layer.
1
complex is monomeric. The H NMR spectra of
[O=ReTPP]2O in CDCl3 and D2SO4 differ appreciaꢀ
bly, first of all, by the number of signals in the specꢀ
the Pt–N vibration frequency in the spectra remains
constant [18].
The spectrum of [O=ReTPP]2O contains absorpꢀ trum. The number of protons calculated from the inteꢀ
tion bands for the Re–O–Re vibrations in the μꢀoxo grated curves in the spectrum in D2SO4 corresponds to
bridge; in particular, the band at 854 cm–1 close to that monomeric rhenium(V) complex with H2TPP
.
for
intensity absorption at 650–550 cm–1 (630 and
568 cm–1) is also indicative of the
ꢀoxo dimer [24].
μ
ꢀO(FeOEP)2 [23]. The presence of mediumꢀ
The formation of
μ
ꢀoxo dimer cannot be treated as
incidental. The possibility of formation of this type of
compound is supported by the existence of
Re2O3Cl4Py4 and [ReO(salpd)]2O (salpd is propaneꢀ
1,3ꢀdiylꢀbisꢀsalicylideneiminate), which were isolated
upon the reaction of ReOCl3(PPh3)2 with wet pyriꢀ
dine [4] and AlkOH [25], respectively. The porphyrin
complexes containing ꢀoxo bridge are also known for
iron(III) [31, 32], manganese [33, 34], and rutheꢀ
nium(IV) [30].
μ
The presence of the oxo ligand in the first coordinaꢀ
tion sphere is indicated by 961 and 946 cm–1 bands
typical of Re=O bonds. For example, the
quency is 976 cm–1 in the spectrum of (oxo)
(ethoxo)(N2O2ꢀcalix[4]arene)rhenium(V), O=Re(N2O2
ν
(Re=O) freꢀ
ꢀ
μ
calix)OEt [25].
No Re–O–Re bands are recorded in the IR specꢀ
trum of (PhO)ReTPP. There is absorption with the
The UV/Vis spectra of (Cl)ReTPP, (PhO)ReTPP,
and [O=ReTPP]2O (Fig. 2) are different. The specꢀ
trum of Re(V) ꢀoxo dimer exhibits a band with a
maximum at 350 nm, which is missing in the spectra of
the H2TPP complexes with Re(III). A similar absorpꢀ
tion in the UV region was noted for W(V) and Mo(V)
porphyrin complexes [26].
maximum at
ν
= 663 cm–1 due to the Re–O bond
vibrations [26]. The presence of the phenoxy ligand in
(PhO)ReTPP is confirmed by a new intense absorpꢀ
tion in the IR spectrum of the compound (mediumꢀ
intensity bands in the whole spectrum) with a maxiꢀ
μ
mum at 1285 cm–1
( (C–O)). In addition, in the
ν
region of benzene C=C bonds (1487, 1578, 1600 cm–1
and 1485, 1575, 1597 cm–1 for (PhO)ReTPP and
Considering the conditions of reaction between
[O=ReTPP]2O, respectively), additional absorption H2TPP and H2ReCl6 and the composition of the
bands of the same nature are present; these bands at resulting product mixture, the following overall reacꢀ
1462 and 1542 cm–1 are due to phenyl in the coordiꢀ tion scheme of the formation of complexes can be sugꢀ
nated phenoxy ligand (Fig. 3). The 374 and 392 cm–1 gested:
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 9 2012

COORDINATION OF 5,10,15,20ꢀTETRAPHENYLꢀ21
H
,23H
ꢀPORPHIN
1299
RhO
4H ReCl + 2PhOH + 3H O
2
+
6
2
Re
N
N
4
2
N
HN
N
N
NH
N
O
N
Re
N
N
N
+
+ 24HCl
O
N
N
N
Re
O
N
RhO
Re
N
+
N
22
N
HN
N
N
NH
N
O
N
Re
N
N
Cl
Re
N
N
4H ReCl + 3H O
2
6
2
N
24
+
+ 22PhOH
O
N
N
N
N
N
Re
O
N
It is obvious that the formation of three Re comꢀ posed scheme. Indeed, this complex is formed with
plexes depends on the ratio of the rates of reactions participation of the phenoxy complex (PhO)ReTPP
involving phenol or the phenoxy complex and is from H2ReCl6 and H2TPP, which are consumed for
largely due to different stoichiometric coefficients at the formation of (PhO)ReTPP in the first reaction. In
(PhO)ReTPP. However, it should not depend on the the case of low formation rate of (PhO)ReTPP, the
H2ReCl6 to H2TPP molar ratio, as follows from perꢀ relative yields of complexes may be expected to shift
forming the reaction at H2ReCl6 to H2TPP ratios of toward (Cl)ReTPP with time. However, in reality,
1 : 2 and 1 : 5. The low yield of the chloride complex after 10 h of the synthesis, the yield of (PhO)ReTPP
(Cl)ReTPP becomes understandable from the proꢀ markedly decreases, and (Cl)ReTPP is not detected at
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 9 2012

1300
TYULYAEVA et al.
ACKNOWLEDGMENTS
A
This work was partially supported by the Fundaꢀ
mental Research Program no. 8 of the Presidium of
the Russian Academy of Sciences “Targeted Synthesis
of Inorganic Compounds with Specified Properties
and Development of Functional Materials Based on
them,” the Russian Foundation for Basic Research
(no. 09ꢀ03ꢀ97556), the Federal Target Program “Sciꢀ
entific and Scientific Educational Cadres of the Innoꢀ
vative Russia” for 2009–2012 (State contract
no. 02.740.11.0106 (2011)), and the Program of the
Ministry of Education and Science “Development of
the Scientific Potential of Higher School”
(no. 2.2.1.1/2820, 2011).
2
1
3
4
400
500
600
700
λ
, nm
REFERENCES
1. V. P. Solov’ev, M. S. Stuklova, E. V. Koltunova, et al.,
Fig. 4. UV/Vis spectra of: (Cl)ReTPP in AcOH–3 M
H SO : ( ) immediately after dissolution and ( ) after
keeping for 3 h at 398 K, and ( ) in CHCl after precipitaꢀ
tion on ice; ( ) (PhO)ReTPP in AcOH–3 M H SO (the
Koord. Khim. 29 (9), 711 (2003).
1
2
2
4
2. N. T. Kuznetsov, Yu. G. Gorbunova, L. A. Lapkina,
et al., Targeted Synthesis of Cyclic Tetrapyrrole Comꢀ
pounds for Technical Purposes (Nauka, Moscow, 2002)
[in Russian].
3
3
4
2
4
2+
spectrum of H TPP ).
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