Reaction of substituted iron phthalocyanines with dioxygen in acidic medium 1. Oxidation of iron 5,5′,5″,5?-tetra(tert-butyl)-3, 3′,3″,3?-tetra(phenylthio)phthalocyanine

Article abstract of DOI:10.1007/s11172-005-0012-2

The reaction of acidic form of the substituted iron phthalocyanine complex (3-PhS-5-Bu^t)₄pc′Fe (pc″Fe) with dioxygen in o-dichlorobenzene in the presence of dichloroacetic acid (HX) was investigated. The oxidation of Hpc″FeX gives the corresponding radical cation, which was confirmed by the stoichiometry of reduction of the product formed in this reaction with a two-electron reducing agent. The kinetic equation obtained on the basis of dependences of the oxidation rate on the Hpc″FeX, HX, and O₂ concentrations are consistent with the reaction mechanism that implies the formation of a Hpc″FeX complex with O₂ and its transformation to give a radical cation under the action of HX.

Full text of DOI:10.1007/s11172-005-0012-2

Russian Chemical Bulletin, International Edition, Vol. 53, No. 8, pp. 1655—1660, August, 2004
1655
Reaction of substituted iron phthalocyanines
with dioxygen in acidic medium
1
. Oxidation of iron 5,5´,5´´,5´´´ ꢀtetra(tertꢀbutyl)ꢀ
3
,3´,3´´,3´´´ ꢀtetra(phenylthio)phthalocyanine
ꢀ
T. M. Fedorova, S. S. Topol´, V. M. Derkacheva, E. A. Luk´yanets, and O. L. Kaliya
State Scientific Center
"
Research Institute of Organic Intermediates and Dyes,"
1
/4 ul. Bol´shaya Sadovaya, 123995 Moscow, Russian Federation.
Fax: +7 (095) 254 1200. Eꢀmail: jerrik@rol.ru
The reaction of acidic form of the substituted iron phthalocyanine complex (3ꢀPhSꢀ
t
5
ꢀBu ) pc´Fe (pc″Fe) with dioxygen in oꢀdichlorobenzene in the presence of dichloroacetic
4
acid (HX) was investigated. The oxidation of Hpc″FeX gives the corresponding radical cation,
which was confirmed by the stoichiometry of reduction of the product formed in this reaction
with a twoꢀelectron reducing agent. The kinetic equation obtained on the basis of dependences
of the oxidation rate on the Hpc″FeX, HX, and O2 concentrations are consistent with the
reaction mechanism that implies the formation of a Hpc″FeX complex with O and its transforꢀ
2
mation to give a radical cation under the action of HX.
Key words: iron phthalocyanine, oxidation, dioxygen, catalysis.
The problem of creation of oxidative systems simulatꢀ
ing the functions of heme oxidases, in particular, oxyꢀ
genases, is fairly topical for the development of effective
environmentally safe oxidation processes. The known
chemical models of cytochrome Рꢀ450, for example,
the problem of the nature and the efficiency of the interꢀ
action of azaporphin, for example, pcFe, with oxygen is
the central point.
Unlike iron porphyrins, which react with oxygen with
oxidation of the Fe atom and, if no special substituents
TpivPPFeBr—Zn(Hg)—MV2+—Ac O—O2 (TpivPP is
are introduced, to give Fe µꢀoxo dimers, iron phthaloꢀ
III
9
2
α,α,α,αꢀmesoꢀtetrakis(orthoꢀpivaloylphenyl)porphyrin,
MV is methylviologen) contain iron porphyrin (P) deꢀ
cyanines form, in neutral organic media, rather stable
µꢀoxo dimers that are believed to be Fe derivatives of the
1
II
1
0
11
rivatives as catalysts, which form ferryl type active speꢀ
type HpcFe—O—FepcH. It has been also suggested
cies, P•+Fe =O or PFe =O, during oxidation. These
species react subsequently with the substrates. The proꢀ
portion of the products formed by a radical mechanism
does not exceed 20%.2 However, due to complexity of
the synthesis, these models have no prospects in the deꢀ
velopment of practically valuable catalyst systems. This
accounts for the interest in the study of iron phthaloꢀ
cyanine (pcFe), the aza analog of porphyrins, and cataꢀ
lytic oxidation of organic substrates using phthalocyanine
IV
IV
that these products are Fe derivatives, structural anaꢀ
logs of the corresponding porphyrins. No definite data on
the reactions of substituted pcFe with oxygen in neutral
III
,3
12
aqueous media have been obtained so far.
In acid media, iron(II) porphyrin complexes are oxiꢀ
9
dized with dioxygen to PFeX (X = Cl). The reaction of
pcFe with oxygen in the presence of acids has scarcely
been studied, although substituted pcFe are effective cataꢀ
lysts for oxidation of, for example, aromatic amines, with
4
—7
8,13
catalysts.
This interest is due, on the one hand, to high
oxygen or hydrogen peroxide exactly in acid media.
1
4
catalytic activity of pcFe in oxidation and, on the other
hand, to the ready availability and relatively high stability
Previously, we found that substituted pcFe containꢀ
ing electronꢀreleasing or weak electronꢀwithdrawing subꢀ
stituents (Bu , PhO, PhS) efficiently react with oxygen in
8
t
of phthalocyanines and their substituted derivatives. Preꢀ
viously, attempts to use azaporphins for modeling of the
active sites of heme oxidases have been made only occaꢀ
sionally. This is also true for modeling of the total enzyme
system of monooxygenases, in which dioxygen itself acts
as the oxidant, rather than the shunted one, which makes
use of reduced forms of oxygen. It is quite obvious that
acidic solutions in which they exist in soꢀcalled acidic
1
5,16
forms.
This is indicated by a decrease in the solution
absorbance at the wavelength of the phthalocyanine
Qꢀband. The introduction of strong electronꢀwithdrawꢀ
ing groups (PhSO , Bu NSO ) into the pcFe molecule
2
2
2
makes the complex inert toward oxygen; in any case, this
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1592—1597, August, 2004.
066ꢀ5285/04/5308ꢀ1655 © 2004 Springer Science+Business Media, Inc.
1

1
656
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
Fedorova et al.
interaction cannot be detected by spectroscopy. The efꢀ
points at 431, 741, 889, and 941 nm remaining intact,
which indicates the absence of side processes (Fig. 1).
fect of the nature of substituents in the HR pc´FeX
4
complexes on the rate of oxidation with oxygen
–
1
–1
(
1
W /mol L
s ) is shown below ([HR pc´FeX] =
0
4 0
Experimental
–
5
–1
–3
–1
.4•10 mol L , [HX] = 5•10 mol L , 25 °C,
0
oꢀdichlorobenzene (DCB), air).
t
The complex (3ꢀPhSꢀ5ꢀBu ) pc´Fe was synthesized as the
4
3ꢀPhSꢀ5ꢀBut 4ꢀPhO 4ꢀBut 4ꢀPhS 3ꢀoꢀClC H4
µꢀoxo dimer by a previously described procedure. oꢀDichloꢀ
robenzene was purified on a column with Al O3 (Brockmann
17
R
6
9
W •10
5.0
1.43
0.9
0.7
0.1
0
2
neutral) followed by distillation in vacuo in a flow of argon.
Dichloroacetic acid was distilled in vacuo. Commercial
PhI(OAc)2 was used (Aldrich).
This study deals with the stoichiometry, kinetics, and
mechanism of the interaction of pcFe derivatives with
dioxygen using the most active of the considered comꢀ
Procedure for kinetic measurements. The kinetic studies were
carried out on an НРꢀ845x UVꢀVis spectrophotometer at 25 °C
in a quartz cell with a layer thickness of 1 or 0.5 cm. The oxygen
content in nitrogen—oxygen gas mixtures was determined on a
Tsvet chromatograph (5 Å molecular sieves; helium as the carꢀ
rier gas; temperature of the column thermostat, 60 °C; temperaꢀ
ture of the chamber and detector, 70 °C). Prior to mixing, soluꢀ
tions of the pc″Fe µꢀoxo dimer and НХ in DCB were purged
with a gas mixture dried by passing through calcined molecular
sieves. The initial oxidation rate was determined by differentiatꢀ
ing the curves for time variation of the concentration of Hpc″FeX
for τ = 0.
t
plexes, (3ꢀPhSꢀ5ꢀBu ) pc´Fe (pc″Fe), in a DCB—diꢀ
4
chloroacetic acid (НХ) solution, as an example. The
choice of the complex containing simultaneously both
t
the Bu group and a bulky substituent in position 3 of the
benzene ring attached to the macrocycle allows one to
avoid complications related to the aggregation of phthaloꢀ
cyanines and the possible presence of positional isomers,
which could be formed during the synthesis of phthaloꢀ
cyanines from 4ꢀsubstituted phthalogens.
It was found that pc″Fe existing as the acidic complex
Procedure for determining the process stoichiometry. A mixꢀ
(
Hpc″FeX) reacts rather actively with dioxygen to give
–
5
–1
ture of solutions of the pc″Fe µꢀoxo dimer (1.4•10 mol L
)
the oxidized form. This reaction was monitored by specꢀ
troscopy based on a decrease in the absorbance of the
solution at the absorption maximum of Hpc″FeX (706 nm)
and an increase in the absorbance at 810 nm, the isosbestic
and НХ (5•10–3 mol L ) in DCB was kept in the dark at ∼ 20 °C
for 2, 3, and 15 h. After a specified time period, the absorption
spectrum of the solution was recorded and the concentrations of
–1
•
+ –
the starting (Hpc″FeX (А)) and final (Hpc″FeX X (В)) forms
were determined from the relations
D
C = (D – D ε a/ε b)/(ε – εBaε b/ε b),
a
b
a
Hpc″FeX
A
B
B
A
A
B
C = (D – D εAb/εAa)/(ε b – ε bεBa/εAa),
b
a
B
B
A
2
1
1
1
1
0
0
0
.00
.75
.50
.25
.00
.75
.50
.25
a
b
where D and D are the absorbancies of the solution at 706 and
10 nm, respectively; εA and εB are the molar extinction coeffiꢀ
cients of the starting and final forms of the phthalocyanine comꢀ
8
a
5
b
5
a
5
b
plexes: εA = 0.788•10 , ε = 0.113•10 , ε = 0.196•10 , εB
.407•105 L mol cm (the εB and εB values were deterꢀ
mined using PhI(OAc) as the oxidant to attain complete conꢀ
version of Hpc″FeX into the oxidized form). Dioxygen was reꢀ
moved from the solution by bubbling argon for 1 h. A solution of
the reducing agent (leuco base of crystal violet, DH) freed from
O was added to an O ꢀfree mixture of Hpc″FeX and the reacꢀ
tion product, the cell was sealed, and the absorbancies of the
solution at 706 (Hpc″FeX), 810 (Hpc″FeX X ), and 595 nm
oxidized form of the reducing agent, the D X dye) were moniꢀ
tored (Fig. 2).
The concentrations of D X– were calculated from the
equation
=
A
–1
B
b
–1
a
0
2
Hpc″FeX•+X–
2
2
•+ –
+
–
(
+
c
a
CD
X D X
+ – +
= (D – D εAc/εAa)/(εc
–
l),
5
00
600
700
800
900 λ/nm
c
c
where D is the absorbance of the solution at 595 nm; ε is
A
Fig. 1. Time variation of the absorption spectra of a solution
the molar extinction coefficient of the complex Hpc″FeX at
t
5
–1
–1
с
5
of H(3ꢀPhSꢀ5ꢀBu ) pc´FeX (Hpc″FeX) ([Hpc″FeX]0
=
=
595 nm, equal to 0.0875•10 L mol cm ; ε = 1.0•10
+
D X
–
4
•10–5 mol L
–1
,
[HX]0 = 5•10–3 mol L–1
,
[O ]
–1
–1
3
1
L mol cm ; and l is the layer thickness (1 cm). The results are
2 0
00% (v/v), DCB).
presented in Table 1.

Substituted iron phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
1657
t
a
Table 1. Stoichiometric parameters of the reduction of the (3ꢀPhSꢀ5ꢀBu ) pc´Fe radical cation
4
Timeb
Before the reduction
After the reduction
СHpc″FeX•+X /
–
/
h
/СD
+
–
X
СHpc″FeX•+X
–
СHpc″FeX ΣСpc″Fec СHpc″FeX•105
Irreversible
destruction (%)
СD
+
X
/mol L
–•105
–1
/
mol L–1
5
–1
•
10 /mol L
2
3
1
0.73
0.81
0.96
0.40
0.30
0.16
1.13
1.11
1.12
1.09
1.10
1.07
22
21
24
0.42
0.39
0.51
1.7
2.1
1.9
5
a
b
c
Hpc″FeX] = 1.4•10 mol L–1, [HX] = 5•10 mol L–1, and [DH] = 2•10 mol L–1
.
0 0 0
Duration of keeping the solution of Hpc″FeX in air.
–5
–3
–5
[
ΣСpc″Fe = СHpc″FeX•+X
–
+ СHpc″FeX
.
ture or band shape.19—21 The fact that the action of reducꢀ
ing agents (hydroquinone, DH) on the reaction product
under argon results in almost complete recovery of
Hpc″FeX is in line with this hypothesis. When DH is used
as the reducing agent, a wellꢀknown dye whose concenꢀ
tration in this system can be easily determined by specꢀ
troscopy is formed upon its oxidation. This was used to
determine the reduction stoichiometry and, as a conseꢀ
quence, the stoichiometry of the oxidation of the starting
complex with dioxygen. It was found that regeneration of
D
Hpc″FeX
1
1
1
0
0
0
.4
.2
.0
.8
.6
.4
Hpc″FeX•+X–
+
–
D X
1
mole of Hpc″FeX requires ∼ 0.5 mole of a twoꢀelectron
reducing agent, in this particular case, DH. This fact,
together with spectral data implies that oxidation occurs
as a oneꢀelectron process and that the macroligand rather
than the central metal atom functions as the reaction
center. Note that within the framework of the views on
2
2,10
the iron(II) oxidation state in acidic complexes,
the
oxidation of the macro ring with dioxygen indicates speꢀ
cific properties of the phthalocyanine complexes comꢀ
pared to porphyrin analogs.
6
00
700
800
λ/nm
Hpc″FeX + O + HX
Hpc″FeX•+X– + HO2•
2
Fig. 2. Reduction of Hpc″FeX•+X in the presence of DH with
–
+
•
–
–5
–1
–5
time at [HpcFeX X ] = 3•10 mol L , [DH] = 2•10
0
–3
0
For discussing the possible intermediacy of the radical
cation formed in the catalytic processes involving pcFe
derivatives, not only the reduction stoichiometry but also
its kinetics is a relevant aspect. The study of the kinetic
features of the reduction of Hpc″FeX•+X with DH unꢀ
der argon demonstrated that the reduction rate obeys firstꢀ
order kinetics with respect to concentrations of both reꢀ
actants (Figs 3, 4)
mol L , [HX] = 5•10 mol L–1.
–
1
0
Results and Discussion
–
We will start with the discussion of the possible nature
of the products formed in the reaction between the acidic
complex Hpc″FeX and oxygen and the reaction stoichioꢀ
metry. The only reaction product exhibits a characteristic
electronic absorption spectrum with the major absorption
band at 810 nm (see Fig. 1). Comparison of this spectrum
with the reported spectra of the radical cations derived
•+
–
WD
+
X 1
–
= k •[Hpc″FeX X ]•[DH],
where k1 = 2.3 L mol–1 s–1. This suggests the following
reaction route:
1
8,19
from metal phthalocyanines
provides data for assumꢀ
Hpc″FeX•+X– + DH
Hpc″FeX + D + HX,
•
(1)
(2)
ing that the oxidation of Hpc″FeX with dioxygen affords a
radical cation with a hole located on the phthalocyanine
macro ring. The oxidation of the central atom would have
resulted in only a slight shift of the longꢀwavelength abꢀ
sorption band with almost no change in the spectral strucꢀ
Hpc″FeX•+X– + D•
+ –
Hpc″FeX + D X .
Now we turn back to the main process, namely, the
oxidation of the acidic form of pc″Fe with dioxygen. The

1
658
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
Fedorova et al.
–•10 /mol L s–1
9
–1
W •10 /mol L s–1
8
–1
WD
+
X
0
5
1
1
2
0
8
6
4
2
3
2
1
4
3
2
1
5
–1
2
4
6
[DH]•10 /mol L
) with the Hpc″FeX•+X–
Fig. 3. Rate of oxidation of DH (WD X
radical cation vs. DH concentration ([Hpc″FeX X ]
.8•10 mol L , [HX] = 5•10 mol L ).
0
+
–
0
•
+
–
20
40
60
80
[O ] (% (v/v))
=
2
0
–
5
–1
–3
–1
1
Fig. 5. Rate of oxidation of Hpc″FeX (W ) vs. partial pressure
0
of oxygen at different concentrations of the complex:
5
[
1
Hpc″FeX] •10 = 1.4 (1), 3.0 (2), 6.0 (3), 8.0 (4), and
–•10 /mol L s–1
9
–1
0
–1
WD
+
X
–3
–1
2.0 mol L (5) ([HX] = 5•10 mol L ).
0
1
1
0
0
.4
.0
.6
.2
W •10 /mol L s–1
8
–1
0
5
6
5
4
3
2
1
4
3
2
0
0
.4
0.8
1.2
1.6
–
5
–1
[
Hpc″FeX•+X ]•10 /mol L
) with the Hpc″FeX•+
–
X
X
–5
–
Fig. 4. Rate of oxidation of DH (W
radical cation vs. Hpc″FeX X concentration ([DH] = 4•10
mol L , [HX] = 5•10 mol L–1).
+
1
D
•+
–
0
–
1
–3
0
0
3
–1
1
2
3
[HX]•10 /mol L
kinetic measurements were carried out over a broad
range of concentrations of the starting complex
Fig. 6. Rate of oxidation of Hpc″FeX (W0) vs. [НХ] at different
5
concentrations of the complex: [Hpc″FeX] •10 = 1.4 (1),
0
3.0 (2), 6.0 (3), 8.0 (4), and 12.0 mol L– (5) ([О2]0 = 21% (v/v)).
1
–
5
–1
(
(
(1.4—12.0)•10
mol L ), dichloroacetic acid
(0.5—5.0)•10–3 mol L ), and oxygen (O content in
–1
2
the gas used to saturate the solution prior to the experiꢀ
ment was 10—100% (v/v)). The partial dependences of
the reaction rate measured from the consumption of
Hpc″FeX on the reactant concentrations are shown in
Figs 5—7, and the graphical processing of the whole set of
kinetic data is presented in Fig. 8. It can be seen that the
experimental plots are described satisfactorily by the
equation
with О formed in the first step reacts with НХ to give the
corresponding radical cation.
2
Hpc″FeX + O2
Hpc″FeX...O2
Hpc″FeX•+X– + HO2•
(4)
(5)
Hpc″FeX...O2 + HX
Expression (6) derived from Eqs (4) and (5) for
[
1
O ] >> [Hpc″FeX] (solubility of oxygen in DCB is
2
–
3
–1
.3•10 mol L
)
Wexp = (A[Hpc″FeX][O ][HX])/(1 + B[O ]),
(3)
2
2
W = (k K[Hpc″FeX][O ][HX])/(1 + K[O ]),
(6)
2
2
2
where А and В are constants.
This is not at variance with the stepwise oxidation
where К is the equilibrium constant, agrees with the
scheme, according to which the Hpc″FeX complex
experimental equation (3) when А = k K, B = K,
2

Substituted iron phthalocyanines
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
1659
W •10 /mol L s–1
8
–1
mol L–1 into a solution of Hpc″FeX (3•10 mol L–1
)
–5
0
4
–
3
–1
6
5
4
3
2
1
and НХ (5•10 mol L ) has virtually no influence on
the oxidation rate of Hpc″FeX with dioxygen in DCB,
which implies an insignificant participation of free radiꢀ
cals in the process. This fact is due to the consumption of
the НО2• radicals in side reactions, similarly to that obꢀ
served in the Fenton system according to the modern
3
2
2
7
views.
An increase in the inhibitor concentrations above the
aboveꢀindicated values induces effects acting in the opꢀ
posite directions, which are of interest as regards the funcꢀ
tioning of phthalocyanines as oxidation catalysts. At higher
1
•
concentrations of AmO , the consumption of Hpc″FeX
is sharply accelerated, which is probably due to the forꢀ
0
2
4
6
8
10
12
mation of H O according to reaction (8). The catalytic
5
–1
2
2
[
Hpc″FeX]•10 /mol L
•
decomposition of this compound gives rise to the OH
Fig. 7. Rate of oxidation of Hpc″FeX (W ) vs. its concentration
at different [HX]: [HX] •10 = 1.0 (1), 2.0 (2), 3.5 (3), and
.0 mol L (4) ([О ] = 21% (v/v)).
0
radicals and, hence, it is accompanied by the destruction
of the phthalocyanine complex. An increase in the [NDA]
5
0
–
1
5
–3
–1
2
0
to 5•10 mol L results, conversely, in complete retarꢀ
dation of the reaction. One reason is the nonproductive
complexation of Hpc″FeX with NDA, similar to that takꢀ
[
Hpc″FeX]•[HX]•W –1/s mol L–1
2
1
ing place in the presence of, for example, pyridine, as
indicated by the red shift of the absorption maximum of
the solution (706 nm → 722 nm). In addition, the reducꢀ
tion of the radical cation with the inhibitor found in an
independent experiment also makes a contribution.
Thus, we found that the coordination of the acidic
complex formed by substituted iron phthalocyanine to
dioxygen results in a substantial activation of the latter
and enable complete electron transfer from the macro
ring to oxygen to give the corresponding radical cation.
This bears an analogy with the combustion of crystalline
1
1
1
8
4
0
6
2
4
[O2]–1•10–3/L mol–1
Fig. 8. Dependence of the [Hpc″FeX]•[HX]•W –1 value
W is the arithmetic mean of at least five experimental W valꢀ
ues) on [O2]
2
8
(
iron phthalocyanine in air at elevated temperatures.
0
–
1
.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 02ꢀ03ꢀ
32168).
k2 = 0.25 L mol–1 s–1, K = 0.21•10 L mol (for comꢀ
4
–1
II
–1
parison, for (F TPP)Fe , K = (3± 2)•10 L mol
EtCN),23 for methmyoglobin, K = 8.1•10 L mol–1 24).
8
5
(
According to Eq. (5), the oxidation of Hpc″FeX with
References
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•–
2
radical anions have been found to arise25 in the selfꢀoxiꢀ
dation of a number of cytochromes. To estimate the deꢀ
gree of participation of the HO2• radical in the oxidation
of the Hpc″FeX complex, radical inhibitors were used,
namely, 2,2,6,6ꢀtetramethylꢀ4ꢀbenzoyloxypiperidinꢀNꢀ
1
2
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4
•
–5
–3
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–
5
–1
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2
6
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Received November 3, 2003;
in revised form February 2, 2004