Variations in functional substitution of the macroheterocycle and structure of stable rhenium(V) porphyrins

Article abstract of DOI:10.1134/S1070428014090218

Rhenium(V) porphyrin complexes with different natures of substituents and substitution patterns in the organic fragment (5,10,15,20-tetraphenylporphyrin, 2,3,7,8,12,13,17,18-octaethylporphyrin, 2,3,7,8,12,13,17,18-octaethyl-5-phenylporphyrin, and 2,3,7,8,

Full text of DOI:10.1134/S1070428014090218

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 9, pp. 1361–1368. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © N.G. Bichan, E.Yu. Tyulyaeva, T.N. Lomova, A.S. Semeikin, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 9,
pp. 1376–1383.
Variations in Functional Substitution of the Macroheterocycle
and Structure of Stable Rhenium(V) Porphyrins
a
a
a
b
N. G. Bichan , E. Yu. Tyulyaeva , T. N. Lomova , and A. S. Semeikin
a
Krestov Institute of Solution Chemistry, Russian Academy of Sciences,
ul. Akademicheskaya 1, Ivanovo, 153045 Russia
e-mail: tnl@isc-ras.ru
b
Ivanovo State University of Chemistry and Technology, pr. Sheremetevskii 7, Ivanovo, 153000 Russia
Received December 20, 2013
Abstract—Rhenium(V) porphyrin complexes with different natures of substituents and substitution patterns in
the organic fragment (5,10,15,20-tetraphenylporphyrin, 2,3,7,8,12,13,17,18-octaethylporphyrin,
2
,3,7,8,12,13,17,18-octaethyl-5-phenylporphyrin, and 2,3,7,8,12,13,17,18-octaethyl-5,15-diphenylporphyrin di-
anions) and different axial ligands {phenoxide and chloride ions, 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-(pyridin-
-ylmethyl)pyrrolidino[3′,4′:1,9](C60-I )[5,6]fullerene} have been synthesized, and their principal properties
spectral parameters and reactivity toward fullerene-containing base) have been studied.
3
(
h
DOI: 10.1134/S1070428014090218
Interest in purposeful structural modification of
aromatic macroheterocyclic porphyrin molecules
fragment and different axial ligands. Compounds II,
IV, and VII were previously unknown.
equally applies to both free bases (H P) and metal
2
Rhenium(V) porphyrin complexes I, II, IV, and V
were synthesized by reaction of the corresponding
porphyrin as free base with H ReCl in boiling phenol
complexes. In some cases, of primary interest are just
metal porphyrins, e.g., in catalysis. The presence of
a metal atom is responsible for a useful property of
an organic compound, whereas functional substitution
in the aromatic fragment allows control over that prop-
erty. Rhenium porphyrins are not an exception; there are
published data on their use in radiopharmacology [1]
and catalysis [2]. According to [3], a very promising
property of rhenium porphyrins is their ability to form
in acids various oxidized and protonated species whose
stability is an important factor determining their cata-
lytic activity in specific reactions in aggressive media
2
6
(
Scheme 1) according to the procedure developed for
the preparation of complex I [7]. Although the reac-
tions were carried out under the same conditions, com-
plexes I, IV and II, V had different compositions.
Octaethylporphyrins gave rise to mononuclear com-
plexes in 70–75% yield. Bridged dinuclear complex I
O
N
[
4]. Modification of porphyrin complexes, in particular
N
Re
with rhenium(V), via variation of axial ligands makes
it possible to obtain such active photovoltaic systems
as porphyrin–fullerenes. Porphyrin–fullerene compos-
ite materials are now used as organic thin-film [5] and
bulk [6] solar cells, which are more advantageous than
inorganic analogs due to their flexibility and lower cost.
N
N
O
N
N
Re
Taking into account the above stated, the goal of the
present work was to synthesize and examine principal
properties (spectral parameters and reactivity toward
a fullerene-containing base) of rhenium(V) porphyrins
I–VII with different substitution patterns in the organic
N
N
O
I
1
361

1
362
BICHAN et al.
It should also be noted that octaethylporphyrins
Et
O
Et
gave rise to rhenium(V) complexes containing either
phenoxide or chloride ion as axial ligand. Presumably,
both these types of complexes are formed in reactions
with all the examined porphyrins, but only one of them
can be isolated because of their different stabilities.
Chloride-containing complexes can be obtained in
quantitative yield from the corresponding phenoxide
derivative. Compounds III and VI were synthesized by
passing gaseous hydrogen chloride over a period of
Et
R1
N
Re
N
Et
Et
Et
N
N
R2
X
Et
Et
II–VII
1
2
1
2
II, R = Ph, R = H, X = PhO; III, R = Ph, R = H, X = Cl;
1
2
1
2
1
IV, R = R = Ph, X = Cl; V, R = R = H, X = PhO; VI, R =
2
1
2
R = H, X = Cl; VII, R = Ph, R = H, X = 2′-(pyridin-4-yl)-
′-(pyridin-2-yl)-1′-(pyridin-3-ylmethyl)pyrrolidino-
3′,4′:1,9](C60-I )[5,6]fullerene.
1
0 min through a solution of compound II or V,
5
[
h
respectively, in methylene chloride.
The optimal reaction time for the synthesis of II
and IV was 5–6 h, and of V, 9 h. Introduction of one or
two meso-phenyl substituents into 2,3,7,8,12,13,17,18-
octaethylporphyrin molecule facilitates coordination
with rhenium(V); however, 2,3,7,8,12,13,17,18-octa-
ethyl-5,10,15,20-tetraphenylporphyrin failed to react
with H ReCl despite variation of the reactant ratio and
was isolated in a good yield (75%) from the product
mixture containing minor rhenium(III) complexes,
(
chloro)(5,10,15,20-tetraphenylporphyrinato)rheni-
um(III) (VIII, 0.5%) and (phenoxo)(5,10,15,20-tetra-
phenylporphyrinato)rhenium(III) (IX, 7%), and the
results of this reaction were well reproducible. Obvi-
ously, in this case a mixture of three stable organic
complexes is obtained in a one-pot mode. The forma-
tion of rhenium(V) porphyrin I from rhenium(IV)
compound is likely to be accompanied by dispropor-
2
6
solvent nature (benzonitrile, pyridine, DMF). Presum-
ably, the reason is steric hindrances.
Stoichiometry and charge of the metal cation in
rhenium porphyrins. Both μ-oxo dinuclear complex I
and mononuclear complexes II–VII isolated by chro-
matography (see Experimental) displayed hyper-type
electronic absorption spectra typical of rhenium(V)
porphyrins (Fig. 1), which contained an additional
band in the region 300–800 nm. These spectra can
readily be distinguished from those of hypso-type
commonly observed for rhenium(III) porphyrins and
3
+
5+
tionation of rhenium(IV) into Re and Re within the
complexes [7]. Presumably, in the presence of HCl
liberated during the process, rhenium(III) complexes
only with 5,10,15,20-tetraphenylporphyrin are stable.
For the same reason, the μ-oxo bridge in I does not
undergo protonation and rupture with formation of
mononuclear rhenium(V) complexes. Such complexes
were obtained only from 2,3,7,8,12,13,17,18-octa-
ethylporphyrin (compounds II, IV, V).
0
n
complexes with other d and d (n > 6) metal cations
Scheme 1.
OPh
Cl
Ph
Ph
Ph
Ph
N
H
Ph
N Re
Ph
N Re
PhOH, 3H O
2
N
N
N
4
+
4H ReCl
I
+
+
2
6
N
H
N
–23HCl
N
N
Ph
N
Ph
N
Ph
Ph
Ph
Ph
H TPP
2
Et
Et
O
Et
Et
Et
Et
Et
R1
Et
R1
N
H
N
Re
2
PhOH
N
Et
N
+ H ReCl6
2
–6HCl, –PhO–
Et
Et
N
H
N
N
R2
or –4HCl, –Cl–
N
R2
Et
Et
X
Et
Et
Et
II, IV, V
H OEP, H POEP, H DPOEP
2
2
2
H
2
TPP is 5,10,15,20-tetraphenylporpphyrin, H
2
OEP is 2,3,7,8,12,13,17,18-octaethylporphyrin, H
2
2
POEP is 2,3,7,8,12,13,17,18-octa-
ethyl-5-phenyl-porphyrin, and H
DPOEP is 2,3,7,8,12,13,17,18-octaethyl-5,15-diphenylporphyrin.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

VARIATIONS IN FUNCTIONAL SUBSTITUTION OF THE MACROHETEROCYCLE
1363
A
[
7–10]. Thus, compounds I–VI, and hence VII, are
1
2
rhenium(V) derivatives.
The electronic absorption spectrum of dinuclear
complex I essentially differs from the spectra of mono-
nuclear complexes II–VI. The latter showed strong
absorption in the region λ ~350 nm, while the absorp-
tion of I in that region was very weak (Fig. 1). Spectral
variations accompanying mutual transformations of the
mononuclear and μ-oxo dinuclear complexes and the
composition of the equilibrium mixture were studied in
2
1
0
3
4
4
00
500
600
700 λ, nm
Fig. 1. Electronic absorption spectra of complexes (1) I,
2, 3) V, and (4) VI in (1, 2) benzene and (3, 4) methylene
chloride.
[
3] using the reaction of I with acetic acid in benzene
(
as an example.
The structure of the isolated rhenium complexes
was also studied by NMR spectroscopy. The number of
1
lished data [11] and our H NMR data for compound I,
the signal at δ 10.77 ppm can be assigned to a mono-
nuclear complex of rhenium(V) with octaethylpor-
phyrin, and the upfield signal at δ 9.51 ppm, to the
µ-oxo dinuclear complex. Insofar as compound V was
homogeneous (see Experimental), we presumed that it
exists in benzene solution as an equilibrium mixture of
mononuclear and dinuclear complexes. The electronic
absorption spectrum of V in methylene chloride
(Fig. 1, 3) shows prevalence of the mononuclear com-
1
signals and their intensities in the H NMR spectra of
III and IV indicated 1:1 composition of these com-
plexes. Their purity and the absence of dinuclear com-
1
1
plexes were confirmed by the H– H 2D DOSY data
(
Fig. 2).
1
Compound V in C D displayed in the H NMR
6
6
spectrum two signals from protons in the meso posi-
tions at δ 10.77 and 9.51 ppm. The lack of correlation
1
1
between these signals in the H– H 2D COSY and
plex since the intensity of the Soret band (λ 343 nm)
max
1
1
H– H 2D ROESY spectra in C D , as well as signal
is higher than the intensity of the charge transfer band
6
6
1
1
separation by the diffusion coefficients in the H– H
(λ 469 nm). The difference in the intensities of these
max
2
D DOSY spectrum, indicated the presence of two
bands decreases in going to benzene solution (Fig. 1,
compounds in solution. With account taken of pub-
2). Taking into account that benzene favors formation
(
a)
(b)
4
2
3
4
6
8
1
0
5
δ, ppm
10
8
6
4
δ, ppm
1
1
Fig. 2. H– H 2D DOSY spectra of complexes (a) III and (b) IV.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

1
364
BICHAN et al.
–
of μ-oxo dinuclear complexes [12], decrease of the
above difference may be related to the presence of
traces of dinuclear complex, in keeping with the NMR
data.
No bands assignable to PhO were observed in the
IR spectra of chlorine-containing complexes III and
VI. The Re–N stretching vibration frequency remains
almost the same, which suggests major contribution of
the macrocyle to the force constant of that bond as
opposed to the contribution of axial ligands. The
presence of a meso-phenyl substituent (weak electron
acceptor) in II and III leads to a small low-frequency
shift of the Re–N vibration band relative to the corre-
sponding band in the spectra of meso-unsubstituted
compounds V and VI (see Experimental). A probable
reason is the contribution of dative π-bonds involving
aromatic system of the macrocycle. The IR spectrum
1
1
The H– H 2D COSY spectrum of VI in CDCl
3
contained cross-peaks corresponding to only interac-
tion between CH and CH protons. Compounds III
2
3
and IV displayed correlations between protons in the
meso-phenyl substituents (see Experimental).
Axial ligand nature. Rhenium complexes of octa-
ethyl-substituted porphyrins contain an axial oxo
ligand in the coordination sphere, which is confirmed
by the presence in their IR spectra of a Re=O stretch-
–1
of V contained an additional band at 454 cm in the
–
1
ing vibration band at 950 cm . Strong bands corre-
region of Re–N vibrations and a weak absorption band
–
1
sponding to phenoxy group (1451, 1589, 1486 cm )
–1
at 619 cm (Fig. 3a), the latter being analogous to that
–
1
and Re–O bond (670, 668 cm ) in the IR spectra of
observed for compound I and absent in the spectrum of
–
1
II and V (Fig. 3a) proved the presence of an axial
VI. Strong absorption in the region 650–550 cm was
assigned [12] to Mo–O–Mo vibrations in the μ-oxo
dinuclear molybdenum(V) complex with 5,10,15,20-
tetraphenylporphyrin. We can conclude that complex V
in KBr, as well as in C D (see above), is represented
–
PhO ligand. No such bands were observed in the IR
spectrum of IV (Fig. 3b).
(
a)
6
6
by an equilibrium mixture with a small amount of the
corresponding µ-oxo dinuclear complex.
–
The presence of PhO ligand in II and V was also
1
1
1
1
confirmed by the H– H 2D COSY and H– H 2D
ROESY spectra (see experimental) where the chemical
shifts of aromatic protons were similar to those typical
of phenol (δ 6.68, 7.15, and 6.82 ppm for o-H, m-H,
and p-H, respectively [13]). No additional signals that
could be assigned to protons in axial ligands were
detected in the spectra of III, IV, and VI.
The presence of aromatic macroheterocycle. As
noted above, the electronic absorption spectra of
mononuclear complexes II–VI belong to the hyper
type which is characterized by the presence of addi-
tional bands in the region λ 300–800 nm (Fig. 1).
2
000
1600
1200
800
400
–
1
ν, cm
(
b)
These are charge transfer bands, λ
440–480 nm
max
[14]. The position of absorption bands in the electronic
spectra of II–VI changes depending on the macro-
cyclic and axial ligand nature. The absorption maxima
of II appear are located at longer wavelengths than
those of V by 5–8 nm. Introduction of meso-phenyl
substituents induces red shift of most absorption
maxima in the spectra of chlorine-containing analogs
III, IV, and VI. The Soret band therein is located at
λ 351, 354, and 347 nm, and the charge transfer band,
at λ 520, 525, and 518 nm, respectively. Analogous
relation between the positions of absorption maxima
and degree of meso-phenyl substitution was reported
for manganese(III) octaethylporphyrin complexes [15].
2
000
1600
1200
ν, cm
800
400
–
1
Fig. 3. IR spectra of complexes (a) V and (b) IV in KBr. The
Re–O vibration band is marked with an asterisk (*), and
vibration bands of the axial phenoxo ligand are marked with
a bullet (•).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

VARIATIONS IN FUNCTIONAL SUBSTITUTION OF THE MACROHETEROCYCLE
1365
A
The change in the position of the Soret band upon
–
–
replacement of the PhO axial ligand by Cl is ~5 nm,
whereas the charge transfer band shifts more signif-
icantly, by 45–50 nm red. The same tendency is ob-
served in the electronic absorption spectra of molyb-
denum(V) oxo complexes with 5,10,15,20-tetraphenyl-
porphyrin in going from axial hydroxo ligand to
chloride [12].
0
0
.15
.10
0.05
Regardless of the singly charge axial ligand, com-
pounds II–VI displayed in the IR spectra main absorp-
tion bands corresponding to vibrations of bonds in the
macrocyclic ligands.
0
.00
5
00
600
700
λ, nm
Fig. 4. Variation of the electronic absorption spectrum of
complex II in methylene chloride in the presence of Py F;
3
Kinetics of formation of porphyrin–fullerene.
The high reactivity of the axial positions, which was
revealed in the synthesis of I–VI, opens new prospects
in the modification of rhenium(V) porphyrins. We
have found that axial ligand in rhenium(V) porphyrin
can be replaced by the action of not only other anion
but also excess neutral organic base. We examined the
kinetics of the reaction of complex II with 2′-(pyridin-
–
5
[
3
Py F] = 6.6×10 M, observation time 0 to 9240 s, 298 K.
that at all Py F concentrations the axial phenoxide ion
in II is replaced by Py F molecule (Scheme 2).
3
3
Scheme 2.
k
+
–
II
+
Py3F
[II·Py F] PhO
3
4
-yl)-5′-(pyridin-2-yl)-1′-(pyridin-3-ylmethyl)pyrroli-
The absence of the reverse reaction was determined
experimentally by dilution of the reaction mixtures
after reaction completion. The stability of the porphy-
rin–fullerene dyad is also confirmed by the high rate
constant for its formation. Such donor–acceptor por-
phyrin–fullerenes attract strong interest. First, their
photoexcitation gives rise to long-lived states with
charge separation like natural photosynthetic antennas;
second, they are soluble in organic solvents and there-
fore can be successfully studied as soluble analogs of
coordinately-bound phthalocyanine–fullerene dyads.
The latter are nowadays extensively used as photoac-
tive materials in organic solar cells [6, 16–18].
dino[3′,4′:1,9](C -I )[5,6]fullerene (Py F) at 298 K
6
0
h
3
using Ostwald’s isolation method. This reaction leads
to the formation of donor–acceptor porphyrin–fuller-
ene dyad (VII) which is promising from the practical
viewpoint. The ratio II–Py F was minimum admissible
3
for the selected method due to low molar absorption
coefficient of II and limited solubility of Py F in
3
methylene chloride.
Figure 4 shows variation of the electronic absorp-
tion spectrum of a mixture of complex II and Py F in
3
CH Cl with time; analogous variations were observed
2
2
at all the examined Py F concentrations. The reaction
3
kinetics follow common pseudofirst-order equation
with respect to porphyrin II (see Experimental). The
EXPERIMENTAL
order of the reaction with respect to Py F (~1) was
3
determined from the linear dependence of the first-
The electronic absorption spectra were recorded on
an Agilent 8453 UV-Vis spectrophotometer. The IR
spectra were measured on a Bruker Vertex 80v spec-
order rate constant on Py F concentration: logk =
3
ef
0
.892log[Py F] + 0.152; r = 0.933.
3
1
trometer. The H NMR spectra were obtained on
[
Py
3
F]×105,
6.0
6.6
7.2
7.8
8.4
9.0
a Bruker Avance III-500 instrument. The mass spec-
tra were taken on a Bruker Autoflex spectrometer. The
elemental compositions were determined on a Euro
EA 3000 elemental analyzer.
M
4
–1
k
ef ×10 , s
2.4±0.2 2.7±0.1 2.9±0.1 3.0±0.3 3.3±0.1 3.5±0.2
Consequently, the reaction is of overall second
order and first in each reactant. The true rate constant
The kinetics of the reaction of complex II with
3
–
1 –1
at 298 K is k = 1.42 L mol s (r = 0.985).
Py F were studied by spectrophotometry at 298±0.1 K
As seen from Fig. 4, the electronic absorption
spectrum of the product is almost similar to that of
initial compound II; only characteristic shift of absorp-
tion bands is observed. Therefore, we can conclude
in closed quartz cells using a special compartment.
Solutions of II and Py F in methylene chloride were
3
prepared just before use. The optical density of a series
of solutions with a constant concentration of rheni-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

1
366
BICHAN et al.
um(V) porphyrin (c = 1.7×10–5 M) was measured
at λ 481 and 515 nm at definite time intervals; during
the reaction, the color changed from yellow–green
to light red.
(γC–Harom); 1440 (C=N), 1341 (C–N), 1018 (C –C ,
C–N, δC–Hpyrrole), 801 (γC–Hpyrrole), 463 (Re–N); 854,
3
4
1
723 (Re–O–Re); 961 (Re=O). H NMR spectrum
(CDCl ), δ, ppm: 7.04 t and 6.87 t (8H, m′-H, J =
3
7
.6 Hz),* 7.47 d (8H, o′-H, J = 7.6 Hz), 7.60 t (8H,
p-H, J = 7.6 Hz), 8.01 t (8H, m-H, J = 7.6 Hz), 8.79 s
The effective rate constants k were determined
ef
using first-order equation for complex II with least-
1
1
(
16H, β-H), 9.07 d (8H, o-H, J = 7.6 Hz). H– H 2D
squares optimization. The relative error in the deter-
COSY NMR spectrum, δ, ppm: in C D : 6.67 t (2H,
6
6
mination of k was less than 10%.
ef
m″-H, J = 7.3 Hz)–6.32 d (2H, p″-H, J = 8.6 Hz),
6
8
.85 t (2H, m′-H, J = 7.3 Hz)–6.42 d (2H, p′-H, J =
.3 Hz), 8.00 t (8H, m-H, J = 7.1 Hz)–7.47 m (16H,
kef = 1/τ ln[(A
0
– A
∞
)/(A
τ
– A )].
∞
Here, A , A , and A are the optical densities of the
m-H, p-H), 8.10 d (8H, o-H, J = 7.1 Hz)–7.47 m (16H,
0
τ
∞
reaction mixture at λ 515 nm (where Py F does not
m-H, p-H); in CD COOD: 8.51 d (4H, o-H, J =
3
3
absorb) at the initial moment, time τ, and by the end of
the reaction, respectively. To obtain a clear spectral
pattern, the spectrum of fullerene with the same con-
centration as in the kinetic experiment was subtracted
from the spectrum of the reaction solution.
7.32 Hz)–7.93 m (12H, m-H, p-H), 8.37 d (4H, o′-H,
J = 7.3 Hz)–7.93 m (12H, m-H, p-H). Found, %:
C 63.14; H 3.52; N 5.59. C H N O Re . Calculated,
88 56
8
3
2
%
: C 64.22; H 3.41; N 6.81.
2,3,7,8,12,13,17,18-Octaethyl-5-phenylporphy-
rinato)(oxo)(phenoxo)rhenium(V) (II). A mixture of
,3,7,8,12,13,17,18-octaethyl-5-phenylporphyrin and
H ReCl at a molar ratio of 1:5 was heated for 5 h in
(
µ-Oxobis[(oxo)(5,10,15,20-tetraphenylporphy-
rinato)]rhenium(V) (I). A mixture of 5,10,15,20-tetra-
phenylporphyrin and H ReCl at a ratio of 1:2 was
2
2
6
2
6
boiling phenol (454 K) under reflux. The progress of
the reaction was monitored by spectrophotometry fol-
lowing disappearance of absorption bands belonging to
the initial porphyrin. The mixture was diluted with
water and extracted with methylene chloride. The
extract was repeatedly washed with warm water to
remove phenol and concentrated, and the residue was
subjected to column chromatography on alumina
heated in boiling phenol at 454 K as described in [7].
The reaction was assumed to be complete when ab-
sorption bands belonging to the initial porphyrin disap-
peared from the spectrum of a sample of the reaction
mixture dissolved in chloroform and the spectrum no
longer changed. The mixture was cooled, treated with
water, and extracted with chloroform. The extract was
repeatedly washed with warm water to remove phenol
and concentrated, and the residue was subjected to
column chromatography on alumina (Brockmann ac-
tivity grade II) using chloroform as eluent to obtain
two zones, diffuse green and sharp green–brown. The
product isolated from the green zone was chroma-
tographed on a column charged with silica gel (40–
(
Brockmann activity grade II) using methylene
chloride as eluent to obtain two zones, light red (unre-
acted porphyrin) and diffuse green–brown. The prod-
uct isolated from the green–brown zone was chromato-
graphed on silica gel (40–100 μm, Chemapol) using
benzene as eluent to obtain two zones, orange and
green–brown. The product was washed off from the
1
00 μm, Chemapol) using first benzene and then
latter zone with CH Cl –EtOH (1:1) and chromato-
chloroform–ethanol (1:1) as eluents to isolate complex
VIII (orange zone), initial porphyrin (light violet zone)
and complex I (green zone). Silica gel column chroma-
tography of the product isolated from the green–brown
2
2
graphed again on a column charged with silica gel
40–100 μm, Chemapol) using methylene chloride as
eluent to isolate compound II. Yield 75%. Electronic
absorption spectrum (CH Cl ), λ , nm (logε): 595
(
zone (benzene, CHCl –EtOH, 1:1) gave compound IX
2
2
max
3
(
3.64), 477 (4.02), 348 (4.38). IR spectrum (KBr), ν,
(
light red) and complex I (green). The purity of the
–1
cm : 3024, 3059 (C–H
); 1546, 1600, 1631
isolated amorphous solids was checked by TLC on
arom
(
C=C
); 1074, 1101 (δ C–H
); 707, 741
Silufol plates using CHCl –EtOH (50:1) as eluent for
arom
arom
3
3 4
(
γC–H ); 1464 (C=N), 1378 (C–N), 1058 (C –C ,
complex I (R 0.42) and benzene for compounds VIII
arom
f
(
C–N); 1401, 1340 (δC–H ); 1253, 1269 (δC–H );
(R 0.80) and IX (R 0.83).
aliph
meso
f
f
–
8
42, 853 (γC–H ); 1486 (PhO ), 946 (Re=O), 668
Re–O), 464 (Re–N). H NMR spectrum, δ, ppm: in
meso
Complex I. Yield 75%. Electronic absorption spec-
1
(
trum (CHCl ), λ , nm (logε): 620 sh, 582 (4.51), 461
3
max
CDCl : 1.57 s, 1.28 s, and 0.90 m (24H, CH ); 4.28 m,
3
3
(
5.34), 333 (4.88). IR spectrum (random solid film),
–1
ν, cm : 3056, 3022 (C–H ); 1597, 1575, 1485
arom
* Primed and double-primed locants refer to aromatic rings at-
tached to different porphyrin macrocycles.
(
C=Carom); 1179, 1072 (δ C–Harom); 754, 702
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

VARIATIONS IN FUNCTIONAL SUBSTITUTION OF THE MACROHETEROCYCLE
1367
1
1
3
.84 s, 3.74 s, 3.67 s, and 3.58 s (16H, CH ); 7.79 m
– –
H– H 2D COSY NMR spectrum (CDCl ), δ, ppm:
2
3
(
2H, m-H, PhO ), 7.95 d (1H, p-H, PhO , J = 7.3 Hz),
2.70 s (CH )–1.95 t (CH ), 4.20 s (CH )–1.56 t (CH ),
4.20 s (CH )–1.95 t (CH ), 7.85 m (2H, m-H)–7.55 q
2
3
2
3
–
8
.35 d (1H, o-H, PhO , J = 7.3 Hz), 8.45 d (1H, o-H,
2
3
–
PhO , J = 6.7 Hz), 10.70 m (3H, meso-H); in
(1H, p-H, J = 7.3 Hz), 7.91 m (2H, m-H)–7.73 q (1H,
p-H, J = 7.3 Hz), 8.20 d (2H, o-H, J = 8.0 Hz)–7.85 d
(2H, m-H), 8.29 d (2H, o-H, J = 8.1 Hz)–7.91 m
(2H, m-H). Found, %: C 61.05; H 5.45; N 5.41.
C H N OClRe. Calculated, %: C 62.51; H 5.64;
CD COOD: 1.32 m and 0.92 m (24H, CH ); 3.51 m,
3
3
3
7
.71 m, 3.87 s, 3.95 s, 4.26 s, and 4.41 s (16H, CH );
2
.62 t (1H, p-H), 7.88 m (2H, m-H), 8.31 t (1H, o-H,
J = 7.31 Hz), 8.50 t (1H, o-H, J = 6.7 Hz), 11.06 m
3
6
44
4
–
(
3H, meso-H), 7.07 s (2H, o-H, PhO ), 6.93 s (2H,
N 6.08.
2,3,7,8,12,13,17,18-Octaethylporphyrinato)-
–
–
m-H, PhO ), 6.83 s (1H, p-H, PhO ). Found, %:
(
C 64.57; H 6.14; N 5.84. C H N O Re. Calculated,
4
8
53
4
2
(
oxo)(phenoxo)rhenium(V) (V) was synthesized as
%
: C 63.79; H 5.87; N 6.20.
described above for complex II; reaction time 9 h.
(
Chloro)(2,3,7,8,12,13,17,18-octaethyl-5-phenyl-
Yield 70%. Electronic absorption spectrum (CH Cl ),
2
2
porphyrinato)rhenium(V) (III). Gaseous hydrogen
chloride was passed over a period of 10 min through
a solution of complex II in methylene chloride. During
that time, the originally green–yellow solution changed
to dark red. Yield 100%. Electronic absorption spec-
λ
, nm: 613, 580, 469, 343. IR spectrum (KBr), ν,
max
–
1
3 4
cm : 1468 (C=N), 1376 (C–N), 1057 (C –C , C–N),
1
(
317 (δC–H); 873, 844 (γC–H ); 1223, 1273
meso
–
δC–H ); 1589, 1451 (PhO ); 959 (Re=O), 670
meso
1
(
Re–O); 454, 466 (Re–N). H NMR spectrum (C D ),
6
6
trum (CH Cl ), λ , nm (logε): 620 (3.67), 520 (4.13),
2
2
max
δ, ppm: 0.38 m, 0.91 m, 1.31 m, and 1.83 s (24H,
CH ); 4.03 m and 4.43 m (16H, CH ), 6.85 s (1H, p-H,
–
1
3
51 (4.73). IR spectrum (KBr), ν, cm : 3060, 3024
3
2
–
–
(
(
(
C–H ); 1630, 1599, 1547 (C=C ); 1097, 1059
arom
arom
PhO ), 6.95 s (2H, m-H, PhO ), 7.04 s (2H, o-H,
–
1
1
δC–H ); 740, 705 (γC–H ); 1464 (C=N), 1383
C–N), 1059 (C –C , (C–N); 1401, 1340 (δC–H );
arom
arom
PhO ), 10.77 m and 9.51 m (4H, meso-H). H– H 2D
COSY NMR spectrum (C D ), δ, ppm: 4.43 m (CH )–
3
4
aliph
6
6
2
1
4
0
3
261 (δC–H ); 865, 908 (γC–H ); 946 (Re=O),
meso
meso
1.83 s (CH ), 4.03 m (CH )–1.83 s (CH ). Found, %:
3
2
3
1
64 (Re–N). H NMR spectrum (CDCl ), δ, ppm:
3
C 62.17; H 6.31; N 7.15. C H N O Re. Calculated,
4
2
49
4
2
.93 t, 1.34 m, and 2.08 m (24H, CH ); 2.94 m,
3
%
: C 60.94; H 5.93; N 6.77.
Chloro)(2,3,7,8,12,13,17,18-octaethylporphy-
.79 m, 3.87 m, and 4.27 m (16H, CH ); 7.55 q (1H,
2
(
p-H, J = 7.3 Hz), 7.76 m (2H, m-H), 7.92 t (1H, o-H,
J = 7.6 Hz), 8.36 t (1H, o-H, J = 7.0 Hz), 10.88 m (3H,
rinato)(oxo)rhenium(V) (VI). Gaseous hydrogen
chloride was passed over a period of 10 min through
a solution of complex V in methylene chloride. The
originally green–yellow solution turned light red. Yield
1
1
meso-H). H– H 2D COSY NMR spectrum (CDCl ),
3
δ ppm: 4.27 m (CH )–2.08 t (CH ), 3,87 m (CH )–
2
3
2
1
.34 m (CH ), 3.79 m (CH )–1.34 m (CH ), 2.94 m
3
2
3
1
00%. Electronic absorption spectrum (CH Cl ), λ
,
2
2
max
(
CH )–1.34 m (CH ), 7.76 m (2H, m-H)–7.55 q (1H,
2
3
nm (logε): 620 (3.90), 518 (4.30), 347 (4.92). IR spec-
p-H, J = 7.3 Hz), 8.36 t (1H, o-H, J = 7.0 Hz)–7.76 m
2H, m-H).
Chloro)(2,3,7,8,12,13,17,18-octaethyl-5,15-di-
–
1
trum (KBr), ν, cm : 1468 (C=N), 1376 (C–N), 1057
(
3
4
(
C –C , C–N); 1316 (δ C–H
); 1271, 1223
aliph
(
(
δC–H ); 871, 854, 846 (γC–H ); 965 (Re=O),
meso
meso
phenylporphyrinato)(oxo)rhenium(V) (IV) was syn-
thesized as described above for complex II; reaction
time 6 h, eluent chloroform. Yield 75%. Electronic
absorption spectrum (CH Cl ), λ , nm (logε): 625
1
4
0
67 (Re–N). H NMR spectrum (CDCl ), δ, ppm:
.88 m, 1.28 m, 1.56 m, and 2.13 s (24H, CH ); 4.38 m
3
3
1
1
and 4.30 m (16H, CH ), 10.94 m (4H, meso-H). H– H
2
2
2
max
2
(
D COSY NMR spectrum (CDCl ), δ, ppm: 2.02 m
3
(
3.70), 525 (4.15), 354 (4.75). IR spectrum (KBr),
CH )–1.19 m (CH ), 4.36 m (CH )–2.17 s (CH ).
2
3
2
3
–1
ν, cm : 3059, 3022 (C–H ); 1600, 1532, 1491
arom
Solid amorphous complexes were isolated from
(
(
C=C
); 1125, 1073 (δ C–H
); 702, 742
arom
arom
3 4
the eluates by evaporation of the solvent at room
temperature.
γC–H ); 1465 (C=N)], (C–N), 1062 (C –C , C–N);
arom
1
400, 1341 (δC–Haliph); 1274 (δC–H ); 838, 861
meso
1
(
γC–H ); 962 (Re=O), 467 (Re–N). H NMR spec-
Complex VII was synthesized by reaction of com-
pound II with 2′-(pyridin-4-yl)-5′-(pyridin-2-yl)-1′-
(pyridin-3-ylmethyl)pyrrolidino[3′,4′:1,9](C -I )[5,6]-
meso
trum (CDCl ), δ, ppm: 0.93 t, 1.56 s, and 1.95 s (24H,
3
CH ); 2.70 m and 4.20 s (16H, CH ); 7.55 q (1H, p-H,
3
2
60
h
J = 7.3 Hz); 7.73 q (1H, p-H, J = 7.3 Hz), 7.85 m (2H,
m-H), 7.91 m (2H, m-H), 8.20 d (2H, o-H, J = 8.1 Hz),
fullerene (Py F) in methylene chloride at 298 K; Py F
3
3
was synthesized by P.A. Troshin [19] at the Institute of
Chemical Physics Problems, Russian Academy of
8
.29 d (2H, o-H, J = 8.1 Hz), 10.82 m (2H, meso-H).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

1
368
BICHAN et al.
Sciences, by reaction of C with azomethine ylide
5. Kamei, T., Kato, T., Itoh, E., and Ohta, K., J. Porphyrins
Phthalocyanines, 2012, vol. 16, p. 1261.
6. Khan, M. and Sayyad, M., J. Porphyrins Phthalo-
6
0
prepared from N-(pyridin-3-ylmethyl)pyridin-2-yl-
methanamine and pyridine-4-carbaldehyde at a molar
ratio of 1.1:1.3 in 1,2-dichlorobenzene. Electronic ab-
sorption spectrum (CH Cl ), λ , nm: 294, 313, 434.
cyanines, 2012, vol. 16, p. 1059.
7
. Tyulyaeva, E.Yu., Bichan, N.G., Lomova, T.N., and
Mozhzhukhina, E.G., Russ. J. Inorg. Chem., 2012,
vol. 57, no. 9, p. 1295.
2
2
max
The electronic absorption spectrum of Py F coincided
3
with that given in [19]: λ , nm: 294, 313, 434
max
8
. Lomova, T.N. and Berezin, B.D., Russ. J. Coord.
(
CH Cl ).
2
2
Chem., 2001, vol. 27, no. 2, p. 85.
This study was performed under financial support
9
. Stulz, E., Scott, S.M., Bond, A.D., Otto, S., and
Sanders, J.K.M., Inorg. Chem., 2003, vol. 42, p. 3086.
by the Council for Grants at the President of the
Russian Federation (project no. NSh-3993.2012.3).
The authors thank P.A. Troshin for providing a sample
of substituted fullerene. The spectral studies were
carried out using the equipment of the Upper Volga
Region Center of Physicochemical Research.
1
0. Chan, K.S. and Lau, Ch.M., Organometallics, 2006,
vol. 25, p. 260.
1
1. Cheng, L., Chen Li, Chung, H.-S., Khan, M.A., and
Richter-Addo, G.B., Organometallics, 1998, vol. 17,
p. 3853.
1
1
1
1
1
1
1
2. Ledon, H.J., Bonnet, M.C., Brigandat, Y., and
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014