Synthesis, acid-base properties, and deselenation of 5,6,8,9,11,12- hexakis(4-tert-butylphenyl)[1,2,5]selenadiazolo[3,4-b]porphyrazine

Article abstract of DOI:10.1134/S1070428013060195

Cross cyclotetramerization of bis(4-tert-butylphenyl)fumaronitrile with 1,2,5-selenadiazole-3,4-dicarbonitrile in the presence of magnesium butoxide as template afforded a mixture of magnesium(II) porphyrazine complexes, from which magnesium complex of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5] selenadiazolo[3,4-b]porphyrazine was isolated by column chromatography and was subjected to demetalation on treatment with trifluoroacetic acid. The free ligand was found to undergo protonation at one meso-nitrogen atom in acid medium and deprotonation of one pyrrole ring to form monoanion by the action of bases. Reductive deselenation of the title compound with formation of vicinal diamino porphyrazine was studied by spectral and kinetic methods, and a mechanism involving two hydrosulfide ions was proposed.

Full text of DOI:10.1134/S1070428013060195

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 6, pp. 913–921. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.V. Kozlov, P.A. Stuzhin, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 6, pp. 928–935.
Synthesis, Acid–Base Properties, and Deselenation
of 5,6,8,9,11,12-Hexakis(4-tert-butylphenyl)[1,2,5]selena-
diazolo[3,4-b]porphyrazine
A. V. Kozlov and P. A. Stuzhin
Ivanovo State University of Chemistry and Technology, pr. F. Engel’sa 7, Ivanovo, 153000 Russia
e-mail: stuzhin@isuct.ru
Received October 1, 2012
Abstract—Cross cyclotetramerization of bis(4-tert-butylphenyl)fumaronitrile with 1,2,5-selenadiazole-3,4-di-
carbonitrile in the presence of magnesium butoxide as template afforded a mixture of magnesium(II) porphyr-
azine complexes, from which magnesium complex of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)[1,2,5]selena-
diazolo[3,4-b]porphyrazine was isolated by column chromatography and was subjected to demetalation on
treatment with trifluoroacetic acid. The free ligand was found to undergo protonation at one meso-nitrogen
atom in acid medium and deprotonation of one pyrrole ring to form monoanion by the action of bases.
Reductive deselenation of the title compound with formation of vicinal diamino porphyrazine was studied by
spectral and kinetic methods, and a mechanism involving two hydrosulfide ions was proposed.
DOI: 10.1134/S1070428013060195
Owing to specific electronic structure and unique
spectral properties phthalocyanines are widely used as
dyes and pigments and basic materials for various
electronic, photoelectronic, and optical devices [1, 2]
and are promising as materials for nonlinear optics [3],
agents for diagnostics and photodynamic therapy of
cancer [4, 5], sensors [6], and catalysts [7]. Low-sym-
metry porphyrazines that may be regarded as analogs
of phthalocyanines exhibit a broad spectrum of prop-
erties due to the presence of different substituents in
a single molecule [8]. A combination of donor aryl
and/or alkyl groups with acceptor electron-deficient
aromatic heterocycles, such as pyridine, pyrazine, and
1,2,5-thia- and selenadiazole, seems to be appropriate.
Introduction of aryl (alkyl) groups enhances the solu-
bility in organic solvents, whereas fusion of the above
listed heterocycles strongly affects physicochemical
properties of the porphyrazine macroring [9, 10]. Por-
phyrazines with fused 1,2,5-chalcogenadiazole rings
were recently found to possess valuable properties
which make them promising as materials for organic
electronics [11, 12] and solar energy converters [13].
In recent years increasing attention is given to the syn-
thesis and properties of low-symmetry porphyrazines
containing 1,2,5-selenadiazole fragments [14–18]. In-
terest in these compounds is determined by the pos-
sibility for their transformation into chemically active
vicinal aminoporphyrazines [19] and their derivatives
[20, 21], including those having peripheral chelating
centers [22, 23], which may be used in the design of
complex multimetal molecular systems with unusual
magnetic and optical properties. On the other hand, the
reductive deselenation reaction itself remains poorly
studied, which restricts the scope of its practical ap-
plications.
We were the first to synthesize magnesium(II) com-
plex of 5,6,8,9,11,12-hexakis(4-tert-butylphenyl)-
[1,2,5]selenadiazolo[3,4-b]porphyrazine (MgPASe,
IV) and the corresponding free ligand H2PASe (V)
(Scheme 1) and study their spectral properties in dif-
ferent media and reductive deselenation by the action
of hydrogen sulfide.
Because of the low reactivity of tert-butylphenyl-
substituted fumaronitrile I in the Linsted macrocycliza-
tion, its direct condensation with 1,2,5-selenadiazole-
3,4-dicarbonitrile (III) turned out to be unfeasible. The
reactivity of dinitrile I was enhanced via transforma-
tion into 2-imino-2H-pyrrole-5-amine (II) by treatment
with ammonia in the presence of a catalytic amount of
sodium alkoxide (Scheme 1). Unlike standard proce-
dure for the synthesis of 3,4-substituted 2-imino-2H-
pyrrol-5-amines [24], the reaction was carried out in
butan-1-ol rather than in ethylene glycol. In this case,
we were able to avoid intermediate isolation of com-
913

KOZLOV, STUZHIN
914
Scheme 1.
t-Bu
Bu-t
NH
N
CN
NH3, BuOH, Δ
CN
t-Bu
NH2
t-Bu
I
II
Bu-t
Bu-t
t-Bu
t-Bu
B
A
NC
N
N
Se
t-Bu
t-Bu
NC
III
N
N
N
N
C
N
N
H
(BuO)2Mg
BuOH, Δ
N
N
N
N
CF3COOH
Se
Se
Mg
N
N
N
N
N
H
N
C
N
N
N
N
t-Bu
t-Bu
B
A
Bu-t
Bu-t
t-Bu
t-Bu
IV
V
pound II, and the latter was directly brought into tem-
plate cyclotetramerization with dinitrile III. The con-
densation of compounds II and III could give rise to
both symmetric porphyrazine complexes MgPA and
MgPASe4 and four low-symmetry Mg(II) porphyr-
azines: MgPASe (3:1), cis- and trans-MgPASe2 (2:2),
and MgPASe3 (1:3). In order to increase the relative
yield of low-symmetry porphyrazine IV (MgPASe),
initial compounds I and III were taken at a ratio of
3:1. Fusion of a heterocycle reduces the solubility of
Mg(II) porphyrazines and their chromatographic
mobility. Symmetric porphyrazine MgPASe4 is almost
insoluble in methylene chloride. By column chroma-
tography of the methylene chloride extract we isolated
symmetric octakis(4-tert-butylphenyl)porphyrazine
MgPA (in the first fraction) whose spectral parameters
coincided with those reported in [25] for the conden-
sation product obtained directly from dinitrile I and
magnesium. Low-symmetry Mg(II)-porphyrazine
MgPASe (3:1) was eluted with methylene chloride
containing 0.5% of methanol.
Abundance×108
1235
8
(b)
6
(a)
4
The MALDI-TOF mass spectrum of IV contained
the strong molecular ion peak with m/z 1235 and
isotope distribution typical of the assumed structure
(Fig. 1). Demetalation of IV with trifluoroacetic acid
in methylene chloride gave the corresponding metal-
free porphyrazine H2PASe (V). Likewise, H2PA was
synthesized from MgPA [25].
2
1230 1235
1240 m/z
0
0
1000
2000
3000
m/z
Fig. 1. MALDI-TOF mass spectrum of magnesium(II) com-
plex IV. The insert shows the (a) experimental and (b) theo-
retical isotope distributions in the molecular ion cluster.
1
Figure 2 shows the H NMR spectra of porphyr-
azine V in CDCl3 and of its Mg(II) complex IV in
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

SYNTHESIS, ACID–BASE PROPERTIES, AND DESELENATION
915
*
*
*
t-Bu
B, C
(c)
H2O
NH2
A
m-H
m-H
o-H
(b)
B, C
A
o-H
(a)
o-H
B, C
*
NH
B, C
#
#
A
m-H
A
–1
–2
9
8
7
6
5
δ, ppm
1.6
1.4
1.2
1.0
Fig. 2. 1H NMR spectra of (a) porphyrazine V in CDCl3, (b) magnesium complex IV, and (c) product of deselenation of the
latter with hydrogen sulfide in C5D5N; residual proton signals are marked with an asterisk, and signals from associates, with
a number sign.
tially overlapped by each other, especially in the aro-
matic region. The inner NH protons in V resonated in
a strong field, at –1.58 ppm (Fig. 2).
The number and structure of heterocyclic frag-
ments, as well as the site of their fusion to porphyr-
azine macroring, strongly affect the macrocyclic
π-chromophore [15, 26]. Therefore, structurally differ-
ent porphyrazines can be reliably distinguished by
pyridine-d5. Complex IV in non-coordinating solvents
(chloroform, benzene) at a concentration of higher than
1 mg/ml is strongly associated. The spectra contain
signals from three types of tert-butylphenyl groups
(A–C), which is consistent with the 3 :1 structure.
Signals from protons in the two A rings nearest to the
1,2,5-selenadiazole ring appear in a stronger field than
those in B and C; signals from the latter were essen-
370
(a)
(b)
644
700
348
380
373
681
671
582 614
605
400
500
600
700
λ, nm
400
500
600
700
λ, nm
Fig. 3. Electronic absorption spectra of (a) symmetric porphyrazines H2PA and MgPA and (b) low-symmetry [1,2,5]selenadiazolo-
porphyrazines H2PASe (V) and MgPASe (IV) in methylene chloride; the spectra of the free ligands are shown with solid curves, and
those of the magnesium complexes, with dashed curves.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

KOZLOV, STUZHIN
bilization of one of them [16, 17]; splitting of the
916
700
Q band into Qx and Qy components is characterized by
ΔE(Q) = 1528 cm–1. Demetalation of the symmetric
Mg(II) porphyrazine complex MgPA to H2PA reduces
the molecular symmetry to D2h, and the Q band is also
split into two components due to lifting of the LUMO
degeneracy [λmax 671 and 605 nm, ΔE(Q) = 1626 cm–1;
Fig. 3a]. Demetalation of IV (MgPASe) with formation
of V (H2PASe) increases the ΔE(Q) value to 2896 cm–1
(λmax 700 and 582 nm; Fig. 3b). In keeping with the
theoretical calculation data for the 1,2,5-thiadiazole
analog [15, 17], this may be rationalized by some
stabilization of the HOMO and stronger stabilization
of the LUMO, the energy of the LUMO+1 changing
only slightly. In all cases, the spectra of pure porphyr-
azines displayed a red shift of the long-wave Q-band
component by 20–30 nm as a result of polarization of
the π-chromophore arising from the appearance of
pyrrole and dihydropyrrole fragments. The Q band
maxima in the spectra of 4-tert-butylphenyl-substituted
porphyrazines, both low-symmetric IV and V and
symmetric MgPA and H2PA, are displaced toward
longer wavelengths by 4–10 nm as compared to phe-
nyl-substituted analogs due to electron-donating effect
of tert-butyl groups [15, 17].
738
578
400
500
600
700
λ, nm
Fig. 4. Spectrophotometric titration of a solution of H2PASe
(V) in methylene chloride with CF3COOH (c = 0–0.3 M).
700
379
633
373
651
582
Porphyrazines act as multicenter ampholytes in
acid–base processes, and their electronic absorption
spectra in acidic or basic medium essentially differ
from those in neutral solvents. Complex IV in acidic
medium undergoes fast demetalation, so that its spec-
trum becomes similar to the spectrum of V, which in
turn strongly depends on the acidity.
The acid–base properties of porphyrazine V were
estimated by spectrophotometric titration with a solu-
tion of trifluoroacetic acid in methylene chloride
(Fig. 4). Increase in the acidity was accompanied by
increased splitting of the Q band via red shift of its
long-wave component Qx by 838 cm–1, while the posi-
tion of the Qy component remained almost unchanged.
Analogous spectral variations are typical of protona-
tion of meso-nitrogen atom in the porphyrazine macro-
ring [27, 28]; they were also observed for both sym-
metric [29, 30] and unsymmetric β-aryl-substituted
porphyrazines [31]. The concentration stability con-
stant of the protonated form of H2PASe (V) (pKa 0.82±
0.01) is lower than that found for symmetric porphyr-
azine H2PA and its β-phenyl-substituted analog
H2PAPh4 (pKa ~1.1 [30]); this indicates reduction of
the basicity of the meso-nitrogen atoms upon introduc-
tion of a fused 1,2,5-selenadiazole fragment, despite
400
500
600
700
λ, nm
Fig. 5. Spectrophotometric titration of a solution of H2PASe
(V) in THF with Bu4NOH (c = 0–0.5 mM).
their electronic absorption spectra, and electronic spec-
troscopy ensures express monitoring of chromatog-
raphic separation of porphyrazine mixtures.
The electronic absorption spectrum of the magne-
sium(II) complex of symmetric octakis(4-tert-butyl-
phenyl)porphyrazine MgPA contains a single narrow Q
band in the visible region (λmax 642 nm; Fig. 3a),
which is typical of D4h-symmetric porphyrazine com-
plexes. Next eluted low-symmetry complex IV dis-
played a double Q band with its maxima at λ 614 and
681 nm (Fig. 3b) due to lower symmetry (C2v) of the
π-chromophore in which the lower unoccupied molec-
ular orbitals become non-degenerate as a result of sta-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

SYNTHESIS, ACID–BASE PROPERTIES, AND DESELENATION
the presence of electron-donor tert-butyl groups in the
917
(a)
683
374
benzene rings.
Figure 5 illustrates spectrophotometric titration of
a solution of H2PASe in tetrahydrofuran with tetra-
butylammonium hydroxide. Addition of base reduces
the magnitude of splitting of the Q band, but the
spectral pattern differs from that observed for MgPASe
which is the Mg(II) complex with macrocyclic dianion
(Fig. 3b). Presumably, the titration with base yields not
dianion PASe2– but monoanion HPASe– where the
proton is likely to reside on one of β-tert-butyl-substi-
tuted pyrrole ring.
614
649
Deselenation of 1,2,5-selenadiazoles by the action
of various reducing agents (H2S, Na2S2O4, HI)
provides a synthetic route to vicinal diamines, e.g.,
substituted phenylenediamines [32]. Deselenation of
the 1,2,5-selenadiazole fragment fused to porphyrazine
macroring smoothly occurred upon treatment with
hydrogen sulfide in pyridine and afforded porphyrazin-
amines [19]. Therefore, [1,2,5]selenadiazoloporphyr-
azines attract interest as convenient precursors of
vicinal porphyrazinediamines which are promising as
ligands for the preparation of multimetal complexes
[22, 23]. However, the reductive deselenation reaction
remains poorly studied, in particular, the role of the
nature of the reducing agent and solvent is unclear.
With a view to elucidate the mechanism of deselena-
tion, we examined the kinetics of the reaction of
H2PASe (V) and its Mg(II) complex MgPASe (IV)
with hydrogen sulfide in pyridine and pyridine–methy-
lene chloride mixtures. Figure 6 shows variations in
the electronic absorption spectra in the course of
reductive deselenation of compounds IV and V.
400
500
600
700
700
λ, nm
(b)
363
576
400
500
600
700
λ, nm
Fig. 6. Spectrophotometric monitoring of the reductive
deselenation of (a) MgPASe (IV) and (b) H2PASe (V) with
hydrogen sulfide ([H2S] = 7.62 and 0.22 mM, respectively)
in pyridine.
1 2
3
4
3.0
2.5
2.0
1.5
1.0
0.5
0.0
It is seen that the reactions are accompanied by
considerable changes in the spectral patterns in the
visible region: narrow Qx and Qy bands typical of the
initial compounds disappear, and broadened Q bands
appear with their maxima at λ 649 nm for complex IV
and λ 576 nm for free ligand V; in both cases,
a shoulder at λ 610–620 nm was observed. The distinct
isosbestic points indicate participation of two spec-
trally distinguishable species. The electronic absorp-
tion spectra of the resulting porphyrazinediamines
H2PA(NH2)2 and MgPA(NH2)2 are analogous to those
of bis(dimethylamino)-substituted hexapropylporphyr-
azine H2PAPr6(NMe2)2 and its Zn(II) complex
ZnPAPr6(NMe2)2 [33].
5
6
0
100
200
300
400
500
τ, s
Fig. 7. Plot of ln(c/c0) versus time for the reaction of
MgPASe (IV) with hydrogen sulfide in pyridine. Hydrogen
sulfide concentration: (1) 1.02, (2) 0.762, (3) 0.508,
(4) 0.254, (5) 0.152, and (6) 0.044 mM.
The product of the reaction of MgPASe (IV) with
hydrogen sulfide in pyridine displayed in the H NMR
spectrum a new signal at δ 5.67 ppm, which may be
1
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

KOZLOV, STUZHIN
918
Table 1. Observed rate constants (kobs) for the reaction of
magnesium(II) complex IV with hydrogen sulfide in pyri-
dine–methylene chloride at 20°C
The ratio c0/c was determined from the variation of
the optical density Al at the absorption maximum of the
initial porphyrazine. The experimental values of kobs
for MgPASe (IV) and H2PASe (V) are given in
Tables 1 and 2, respectively.
[Py], M
[H2S], mM
kobs, s–1
12.36 (100%)
0.152
0.254
0.00156±0.00001
0.00459±0.00001
0.01439±0.00003
0.0254±0.0001
The log dependences of kobs on the concentration of
H2S are linear (Figs. 8a, b), and their slopes correspond
to the second order with respect to hydrogen sulfide.
We also examined the effect of the concentration of
pyridine on the deselenation of magnesium complex
IV and found the second order with respect to pyridine
(Fig. 8c).
0.508
0.762
1.020
0.0404±0.0003
4.95
2.940
0.00120±0.00001
0.00399±0.00004
0.00737±0.00009
0.0151±0.0003
5.880
Taking into account that the deselenation process
requires the presence of a base (pyridine) and that the
orders of the reaction with respect to pyridine and hy-
drogen sulfide are similar, the reactive species is likely
to be hydrosulfide ion HS– which is more nucleophilic
than H2S molecule. The kinetic data allowed us to
propose a mechanism shown in Scheme 2. In the first
reversible step, hydrosulfide ion is coordinated to
the selenium atom in a way similar, e.g., to the reaction
of dinitrile III with benzenethiolate ion [35], the
1,2,5-selenadiazole aromatic system remaining intact.
The second, rate-determining step implies rupture of
the aromatic system due to addition of the second
hydrosulfide ion, and the subsequent reaction with
pyridinium ion as proton donor yields final porphyr-
azinediamine.
8.820
11.8000
14.7000
8.82000
0.0196±0.0005
1.24
0.000812±0.000010
assigned to protons of the amino groups in
MgPA(NH2)2 (Fig. 2c). Insofar as porphyrazinedi-
amines MgPA(NH2)2 and H2PA(NH2)2 are very readily
oxidized on exposure to air, we failed to isolate them
from solution. Increased sensitivity to photooxidation
with atmospheric oxygen was also noted for
ZnPAPr6(NMe2)2 [34]; moreover, it was shown that the
complex itself acts as sensitizer in the generation of
singlet oxygen.
The kinetics of the reductive deselenation of por-
phyrazines IV and V were studied in pyridine or its
mixtures with methylene chloride using 10 to
1000 equiv of hydrogen sulfide, i.e., under pseudofirst-
order reaction conditions. The linear plot of ln(c0/c)
versus time (Fig. 7) indicated the first order of the
reaction in porphyrazine (c), so that the observed rate
constant kobs was calculated by the formula
The proposed scheme was qualitatively verified by
the following experiment. Complex IV was dissolved
in a neutral solvent (THF), and the solution was satu-
rated with hydrogen sulfide. According to the elec-
tronic absorption spectrum, no deselenation was ob-
served at this step. A solution of Bu4NOH was then
Scheme 2.
kobs = (1/τ)ln(c0/c).
Py
+
H2S
Se
PyH+ HS–
+
HS–
N
N
N
Table 2. Observed rate constants (kobs) for the reaction of
porphyrazine V with hydrogen sulfide in pyridine at 20°C
Se
SH
N
[H2S], mM
kobs, s–1
H
H
0.56
0.45
0.0384±0.0007
0.0164±0.0001
N
N
HS–
S
S
S
S
Se
Se
Slow
N
N
H
0.34
0.0147±0.0001
H
0.22
0.00764±0.00004
0.00191±0.00001
0.000287±0.000001
NH2
2PyH+
Fast
0.11
+
SeS2
00.056
NH2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

SYNTHESIS, ACID–BASE PROPERTIES, AND DESELENATION
919
logkobs
(a)
added to the mixture, and its electronic spectrum
–1.0
–2.0
–3.0
changed in a way similar to that shown in Fig. 6a. This
indicated reductive deselenation by the action of hy-
drosulfide ion.
n = 2.00
EXPERIMENTAL
The electronic absorption spectra were measured on
a Hitachi U-2000 spectrophotometer from solutions
with a concentration of 10–5 to 10–6 M using quartz
cells with a cell path length of 1 cm. The mass spectra
(MALDI-TOF) were recorded on a Bruker Daltonics
1
Ultraflex mass spectrometer. The H NMR spectra
were obtained on a Bruker AM-500 instrument. Com-
mercial reagents (Aldrich, Merck, Reakhim) were used
for the syntheses and chromatographic separations.
Methylene chloride was distilled over K2CO3, and
butan-1-ol was purified by azeotropic distillation and
by treatment with metallic sodium. Dinitriles I [24]
and III [19] were synthesized by known methods.
–4.4
–4.2
–4.0
–3.8
–3.6
–3.4 log[H2S]
(b)
logkobs
–1.0
n = 1.63
[5,6,8,9,11,12-Hexakis(4-tert-butylphenyl)[1,2,5]-
selenadiazolo[3,4-b]porphyrazinato]magnesium
(MgPASe, IV). Gaseous ammonia was bubbled over
a period of 2 h through a boiling suspension of 2.5 g
(0.007 mol) of bis(4-tert-butylphenyl)fumaronitrile (I)
in 60 ml of anhydrous butan-1-ol containing ~15 mg of
sodium to obtain a light green solution of iminopyr-
rolamine II. Simultaneously, 60 mg of magnesium
turnings was dissolved under stirring in 50 ml of
thoroughly dried butan-1-ol on heating under reflux.
The solution of magnesium butoxide was cooled to
room temperature and mixed with the solution of II,
0.67 g (0.003 mol) of 1,2,5-selenadiazole-3,4-dicarbo-
nitrile (III) was added, and the mixture was heated for
6 h under reflux with vigorous stirring. The mixture
was cooled and evaporated, the residue was extracted
with methylene chloride, and the products were sepa-
rated by column chromatography on aluminum oxide
(gradient elution with methylene chloride–methanol).
The first fraction eluted with methylene chloride con-
tained Mg(II) complex of symmetric octakis(4-tert-
butylphenyl)porphyrazine (MgPA), and from the
second fraction eluted with methylene chloride con-
taining 0.5% of methanol we isolated low-symmetry
Mg(II) complex MgPASe (IV). Yield 10% of the over-
–2.0
–3.0
–3.6
logkobs
–3.4
–3.2
–3.0
–2.8 log[H2S]
(c)
n = 1.74
–2.0
–3.0
1
all amount of Mg(II) porphyrazines. H NMR spec-
trum (pyridine-d5), δ, ppm: 1.35 s (18H), 1.46 s (18H),
0.0 0.1
0.2
0.3
0.4
0.5
0.6
0.7 log[Py]
1.51 s (18H), 7.75 d (4H, 3J = 7.9 Hz), 7.79 d (4H, 3J =
3
3
Fig. 8. Log dependences of kobs on the concentration of
(a, b) hydrogen sulfide and (c) pyridine for the deselenation
of (a) porphyrazine V and (b, c) its magnesium complex in
(a, b) pyridine and (c) pyridine–methylene chloride ([H2S] =
8.82 mM) at 20°C.
7.9 Hz), 7.80 d (4H, J = 7.9 Hz), 8.69 d (4H, J =
3
8 Hz), 8.71 d (8H, J = 8 Hz). Electronic absorption
spectrum (CH2Cl2), λmax, nm (logε): 370 (4.44), 615
(4.05), 681 (4.29).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

KOZLOV, STUZHIN
920
7. Sorokin, A.B. and Kudrik, E.V., Catal. Today, 2011,
vol. 159, p. 37.
8. Mack, J. and Kobayashi, N., Chem. Rev., 2011, vol. 111,
5,6,8,9,11,12-Hexakis(4-tert-butylphenyl)[1,2,5]-
selenadiazolo[3,4-b]porphyrazine (H2PASe, V).
Complex IV, 0.1 g (0.081 mmol), was dissolved in
20 ml of a 10% solution of trifluoroacetic acid in
methylene chloride, the solvent was evaporated at
room temperature, the dry residue was dissolved in
30 ml of methylene chloride, the solution was filtered,
p. 281.
9. Stuzhin, P.A. and Ercolani, C., The Porphyrin Hand-
book, Kadish, K.M., Smith, K.M., and Guilard, R., Eds.,
San Diego: Academic, 2003, vol. 15, p. 263.
1
10. Donzello, M.P., Ercolani, C., and Stuzhin, P.A., Coord.
Chem. Rev., 2006, vol. 250, p. 1530.
11. Miyoshi, Y., Fujimoto, T., Yoshikawa, H., Matsu-
shita, M.M., Awaga, K., Yamada, T., and Ito, H., Org.
Electronics, 2011, vol. 12, p. 239.
12. Stuzhin, P.A., Mikhailov, M.S., Yurina, E.S., Baza-
nov, M.I., Koifman, O.I., Pakhomov, G.L., Trav-
kin, V.V., and Sinelshchikova, A.A., Chem. Commun.,
2012, vol. 48, p. 10135.
13. Stuzhin, P.A., Mikhailov, M.S., Travkin, V.V., Gud-
kov, E.Y., and Pakhomov, G.L., Macroheterocycles,
2012, vol. 5, p. 162.
and the solvent was removed. Yield 98%. H NMR
spectrum (CDCl3), δ, ppm: –1.58 (2H), 1.54 s (18H),
3
1.55 s (36H), 7.63 m (8H), 7.77 d (4H, J = 7.9 Hz),
3
3
8.26 d (4H, J = 7.9 Hz), 8.36 d (8H, J = 7.9 Hz).
Electronic absorption spectrum (CHCl3), λmax, nm
(logε): 348 (4.61), 367 (4.60), 582 (4.31), 700 (4.73).
The acid–base properties of porphyrazine V in
CH2Cl2–CF3COOH were studied by spectrophoto-
metric titration [30, 31].
The kinetic measurements were performed under
pseudofirst-order reaction conditions using a large
excess of hydrogen sulfide relative to porphyrazines
IV and V. A solution of hydrogen sulfide was prepared
by saturation of cold pyridine with dry H2S. The
amount of absorbed H2S was determined by the gain in
weight, and the solution was then diluted with pyridine
and/or methylene chloride to a required concentration
and used within 24 h. Solutions of porphyrazines IV
and V and hydrogen sulfide were adjusted to 20°C and
mixed, and the progress of the deselenation reaction
was monitored by spectrophotometry, following the
absorbance at λ 700 nm for V and at λ 680 nm for
Mg(II) complex IV.
14. Kudrik, E.V., Bauer, E.M., Ercolani, C., Chiesi-
Villa, A., Rizzoli, C., Gaberkorn, A., and Stuzhin, P.A.,
Mendeleev Commun., 2001, p. 43.
15. Stuzhin, P.A., Pimkov, I.V., Ul’-Khak, A., Ivanova, S.S.,
Popkova, I.A., Volkovich, D.I., Kuz’mitskii, V.A., and
Donzello, M.-P., Russ. J. Org. Chem., 2007, vol. 43,
p. 1854.
16. Knyukshto, V.N., Volkovich, D.I., Gladkov, L.L., Kuz’-
mitskii, V.A., Ul’-Khak, A., Popkova, I.A., Stuzhin, P.A.,
and Solov’ev, K.N., Opt. Spektrosk., 2012, vol. 113,
p. 401.
17. Solovyov, K.N., Stuzhin, P.A., Kuzmitskiy, V.A., Volko-
vich, D.I., Knyukshto, V.N., Borisevich, E.A., and
Ul-Haque, A., Macroheterocycles, 2010, vol. 3, p. 51.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 10-03-01069-a).
18. Baum, S.M., Trabanco, A.A., Montalban, A.G.,
Micallef, A.S., Zhong, C., Meunier, H.G., Suhling, K.,
Phillips, D., White, A.J.P., Williams, D.J., Bar-
rett, A.G.M., and Hoffman, B.M., J. Org. Chem., 2003,
vol. 68, p. 1665.
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