Aza-substitution, benzo-annulation effects and catalytic activity of β-octaphenyl-substituted tetrapyrrolic macroheterocyclic cobalt complexes. I. heterogeneous catalysis

Article abstract of DOI:10.1007/s10847-016-0674-4

The influence of the size of conjugated π-system on catalytic activity of cobalt complex with β-octaphenylporphyrin and its tetraaza-, tetrabenzo and tetrabenzotetraaza derivatives was studied in present work. It is found that catalytic activity for oxidation of sulfur-containing compounds increases under extension of conjugated macrocycle system according to the following series CoP?

Full text of DOI:10.1007/s10847-016-0674-4

J Incl Phenom Macrocycl Chem
DOI 10.1007/s10847-016-0674-4
ORIGINAL ARTICLE
Aza-substitution, benzo-annulation effects and catalytic activity
of b-octaphenyl-substituted tetrapyrrolic macroheterocyclic
cobalt complexes. I. heterogeneous catalysis
Artur Vashurin1,2,5 Vladimir Maizlish3 Ilya Kuzmin1 Oleg Petrov4
•
•
•
•
Mikhail Razumov2 Svetlana Pukhovskaya1 Oleg Golubchikov4
Oscar Koifman2
•
•
•
Received: 17 May 2016 / Accepted: 23 October 2016
Ó Springer Science+Business Media Dordrecht 2016
Abstract The influence of the size of conjugated p-system
on catalytic activity of cobalt complex with b-oc-
taphenylporphyrin and its tetraaza-, tetrabenzo and tetra-
benzotetraaza derivatives was studied in present work. It is
found that catalytic activity for oxidation of sulfur-con-
taining compounds increases under extension of conjugated
macrocycle system according to the following series
CoP \ CoBP B CoPz \ CoPPz ꢀ CoPc.
Introduction
The investigation of oxidation mechanisms of sulfur-con-
taining compound of high toxicity and corrosive activity, the
searchof optimalcatalyst composition are very significant for
the development of novel catalytically active materials for
sulfur refining processes, protection and preservation of the
environment. Cobalt complexes with tetrapyrrolic macro-
heterocyclic ligands are perspective as catalysts for mercap-
tanes and carbamates (RSH) oxidation to the disulfides [1–4].
Moreover, the use of mild oxidizers allows to obtain practi-
cally useful for organic synthesis compounds under milder
conditions. For example, it allows to increase the selectivity
of the N,N-carbomoditiolate oxidation during the thiuram E
obtainment. The obtained product does not need additional
purification and can be immediately used for rubber vulcan-
ization process [5] or fine organic synthesis of drugs [6].
The main task for the creation of catalytically active
materials based on tetrapyrrolic macroheterocyclic com-
pounds is detection of the relationship between the struc-
ture of the macrocycle and its catalytic activity that is
directly connected with the oxidation mechanisms. Several
mechanisms for the oxidation of the RSH compounds in
presence of porphyrin metal complexes and their structural
analogues are known [7–9].
Keywords b-Octaphenylporphyrin Á Metal complex Á
Benzo-annulation Á Aza-substitution Á Sodium N,N-
carbomodithiolate Á Oxidation Á Catalyst
Electronic supplementary material The online version of this
article (doi:10.1007/s10847-016-0674-4) contains supplementary
material, which is available to authorized users.
& Artur Vashurin
asvashurin@mail.ru
1
Department of Inorganic Chemistry, Ivanovo State University
of Chemistry and Technology, 153000 Ivanovo, Russia
Usually, it is considered to be a single-electron charge
transfer from oxygen to metal in a lower oxidation state or
the formation of an intermediate complex (substrate-cata-
lyst-oxygen) with a general charge [8–10]. Obviously, that
in both cases the size of p-conjugated system and the
magnitude of the partial positive charge on the central
metal cation in macroheterocyclic molecule will have a
significant effect on the catalytic activity.
2
Research Institute of Macroheterocycles, Ivanovo State
University of Chemistry and Technology, 153000 Ivanovo,
Russia
3
Department of Technology of Fine Organic Synthesis,
Ivanovo State University of Chemistry and Technology,
153000 Ivanovo, Russia
4
Department of Organic Chemistry, Ivanovo State University
of Chemistry and Technology, 153000 Ivanovo, Russia
The most interesting molecules having extended p-sys-
tem are metal phthalocyanines and their aza-derivatives.
5
Kazan Federal University, 420008 Kazan, Russia
123

J Incl Phenom Macrocycl Chem
Thus, it is important to reveal the regularity of consistent
change of p-electronic effects inside of macrocyclic ring
under transformation from porphyrin to phthalocyanine and
their analogues. Possibility to coordinate additional axial
ligands [10–12] may be used for obtaining of novel cata-
lysts, for example the use of phthalocyanine l-dimers for
the oxidation catalysis of C-H bond in aromatic and ali-
phatic compounds [13]. The size of conjugated macro-
cyclic system influences significantly the coordination of
ligands by stabilization of axial complex due to p-inter-
action. Central metal cation plays important role in these
processes. Cobalt is able to take part in redox processes
showing the whole spectrum of oxidation degrees CoI-CoII-
CoIII due to the structure of its outer electronic shell.
Coordination ability of cobalt cation as a part of tetra-
pyrrolic macrocycles, for example cobalamin [14], deter-
mines properties of the whole compound including the
catalytic activity.
opportunities of chemical modification of porphyrazine-like
compounds are very promising for their practical use [15].
They have pretty close and at the same time different from
porphyrins and phthalocyanines structure, and correspond-
ingly properties that makes them unique. Existance of addi-
tional nitrogen atoms creates preconditions to form
stabilizing coordination including hydrogen bonds on the
periphery of the molecule.
Besides, studied compounds are interesting due to
existance of the phenyl fragments on the periphery of
macrocyclic molecule, which are able during the transfor-
mations [16] to act as anchoring groups. Such process
allows obtain the compounds by immobilization on the
surface of polymer matrix [17, 18].
Experimental
Equipment
The present work is devoted to the study of sodium N,N-
carbomodithiolate (DTC) oxidation in presence of cobalt
complexes with tetrapyrrolic macroheterocyclic com-
pounds with regularly changing substituents system and the
length of the macrocycle p-system. The structures of
investigated compounds are shown on Fig. 1.
Elemental analysis has been carried out by means of chro-
matographic analyzer Flash HCNS-OEA 1112 (Germany).
The flow rates of helium and oxygen were 140 mL/min and
250 mL/min, respectively; the temperature of the reactor was
900 °C, oxygen was supplied into the reactor for 250 mL/min
with 12 s time delay. FT-IR spectra were recorded using IR-
Fourier spectrophotometer Avatar 360 (USA) in
400–4000 cm-1 frequency range. NMR spectra of the
Porphyrazine (Co(II)Pz)andits benzo-annulatedanalogue
pyrazinoporphyrazine (Co(II)PPz) should be particular noted
among the compounds presented on Fig. 1. The chemistry of
these compounds is developing quite vigorously. Ample
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Co
N
N
N
Co
N
N
N
N
Co(II)PPz
Co(II)BP
N
N
Co
N
N
N
N
Co
N
N
N
N
Co
N
Co(II)P
N
N
N
N
N
N
N
N
Co(II)Pz
Co(II)Pc
Fig. 1 Structure of catalysts
123

J Incl Phenom Macrocycl Chem
solutions were recorded by means of NMR spectrometer
Bruker AVANCE-500 (Germany) at operating frequency
500 MHz (1H) and 100 MHz (13C). Measurements were
performed under the Fourier transformation conditions in
5 mm cells at various temperatures. Chemical shifts were
measured with reference to the internal standard—tetram-
experiment. The air was passed through the reaction mix-
ture with the rate of 1–2 L/min. The time of air feeding
start was chosen as the beginning of the experiment.
Considering the constancy of oxygen concentration the
reaction rate is described by kinetic equation of fist order:
dc=ds ¼ Àkobsc;
ð1Þ
ethylsilane.
The
accuracy
of
measurements
where c—current concentration of DTC, s—time, kobs
observed rate constant of the reaction.
—
was 0.005 ppm. Electron absorption spectra (UV–Vis)
were registered by means of Unico 2800 (USA) spectropho-
tometer in a spectral range of 200–1000 nm. Quarts optical
cell were used for the measurements. UV–Vis spectra were
recordedat298.15 0.03 K. Massspectraweremeasuredon
an Axima MALDI-TOF mass-spectrometer (Shimadzu,
Japan). Solution pH was controlled by pH meter
SevenCompact (Mettler Toledo, Switzerland).
It is confirmed by rectilinear character of the depen-
dence lnc = f(s) and constancy of rate constants calculated
by the equation:
kobs ¼ ð1=sÞlnðc0=cÞ
here c0—initial concentration of diethyldithiocarbamate,
ð2Þ
c—current DTC concentration at a time s.
It was found in prior experiences, that non-catalytic
oxidation of DTC is very slow (kobs = 1.7 9 10-5 s-1
)
Reagents
[27].
The activation energy (Ea) for the studied temperature
range was calculated by the Arrhenius equation in the
integrated form:
Purification of the solvent was carried out according to
[19]. The portion of fresh distilled solvent was used for the
experiment.
T2T1
k2
Ea ¼ 19:1
lg
T2 À T1 k1
where T1 and T2—temperatures (K) and k2 and k1—ef-
ð3Þ
Synthesis
Cobalt(II) complex of 2,3,7,8,12,13,17,18-octaphenylpor-
phyrine (Co(II)P) was synthesized according to the method
recommended in [20]. Cobalt(II) complex of 2,3,7,8,12,
13,17,18-octaphenyl-5,10,15,20-tetraazaporphyrine (Co(II)Pz)
was synthesized according to the method recommended in
[21–23]. Cobalt(II) complex of 2,3,910,16,17,23,24-oc-
taphenyltetrabenzoporphyrine (Co(II)BP) was synthesized
according to the method recommended in [24]. Cobalt(II)
complex of 2,9,16,23-tetraphenylphthalocyanine (Co(II)Pc)
was synthesized according to the method recommended in [25].
Cobalt(II) complex of 2,3,910,16,17,23,24-octaphenylte-
trapyrazinoporphyrazine (Co(II)PPz) was synthesized accord-
ing to the [26]. Details of the synthesis are shown in
Supplementary data.
fective rate constants at current temperatures.
Results and discussion
Oxidation of mercaptans by oxygen proceeds according to
general Scheme 2.
Application of air oxygen as oxidizer instead of
molecular oxygen allows to avoid the further oxidation of
thio-bridges and interrupt the process after the first trans-
formation, thereby to increase the yield of desired product.
Earlier we showed [18, 29–31] that the heterogeneous
catalysis may realize the mechanism described by the
following set of elementary steps:
Oxidation of sodium N,N-carbomodithiolate (DTC) was
studied in light-protected thermostatic cell of volume of
650 ml with DTC concentration range of 2.7 9 10-3
–
8.3 9 10-3 mol L-1 under the temperatures of 20–40 °C.
The experiments were carried out in water-alkali solutions
under the pH values 8–10. The construction consisting
thermostat, thermostatic cell with possibility of controlling
the temperature and sampling, and an oxygen feeder was
used in the work. The method of analytical determination
of current DTC concentration by spectrophotometric
method is described in works [27, 28]. The oxidation of
DTC proceeds according to the general Scheme 1.
H5
H5
S
S
C2H5
C2H5
C2
C2
S
S
H5
H5
C2
2
C2
S
S
O2
,
catalyst
-2Na
N
N
C
C
N
C
Na
Scheme 1 Reaction of oxidation of DTC
O
O O
S
O
[O]
[O]
[O]
2RSH
R
RS-SR
S
SR
R
R
S
-2H
O
O
Solid catalyst was triturated and then added to the
substrate solution. The mixture was stirring during the
Scheme 2 Scheme of mercaptans oxidation
123

J Incl Phenom Macrocycl Chem
RSÀ þ COIIPc ꢀ RSÁ Á CoIPc
ð4Þ
ð5Þ
4
3
0.60
0.45
0.30
0.15
0.00
RSÁ Á CoIPc + O2 ꢀ RSÁ Á CoIIPc Á OÀ2
slowly
RSÁ Á CoIIPc Á O2À ꢁ RSÁ + CoIIIPc Á O2À
2
H2O
! CoIIIPc Á O2À ꢁ CoIIPc + OHÀ + H2O2
instantaneous
ð6Þ
ð7Þ
2RSÁ
ꢁ
RSSR
1
It has been determined that the step of triple complex
destruction (6) is limiting. This scheme suggests that cat-
alytic activity of tetrapyrrolic macroheterocycles is affec-
ted significantly by the state of catalyst active center, which
is presented in particular case by cobalt cation.
0
1000
2000
3000
τ, s
Fig. 3 Kinetic curves of DTC oxidation (c 5 9 10-3 mol/L) in
presence of macroheterocyclic catalysts: 1 Co(II)Pz, 2 Co(II)Pc, 3
Co(II)P, 4 Co(II)TPz, under 25 °C, pH 11.4
Given that the cobalt is located in the conformationally
rigid macrocyclic ligand environment, it is obvious that the
nature of the ligand will have a significant effect on the
active center of catalysis. That influence is caused mainly
by the effects of conjugated p-system and as a result by its
impact on the central cobalt cation.
the LUMO pÃ1 and HOMO p1, and energy degeneration pÃ1;2
(e.g.). Increase of the conjugated system of the macrocycle
leads to the enhancement of these effects and appearance of
new symmetry levels of macromolecule active center
[36, 37, 40], which is involved in catalysis.
The change of conjugation circuit of porphyrin macro-
cycle occurs during the benzo-annulation and aza-substi-
tution in accordance with the Fig. 2 [32–34].
Kinetic curves of DTC oxidation in presence of
macrocyclic catalysts are presented in Fig. 3.
As it can be seen from Fig. 3 the oxidation rate of the
DTC in the presence of all the catalysts at a constant
oxygen concentration obeys the kinetic equation of the first
order. Obviously, conventional porosity of the investigated
catalysts is of the same order in terms of macro kinetic
approach, so we can assume that the diffusion processes
proceed at the same speed. In this case, it becomes apparent
that the reaction rate will depend not only on the adsorption
processes (coordination) of the substrate on the active
center of the catalyst, but also on a similar process of the
reaction product.
The decrease of macrocyclic molecule conjugation cir-
cuit leads to the change of central metal cation state [35].
Tetraaza-substitution of porphyrin macrocycle leads to the
change of symmetry and energy LUMO and HOMO of
Co(II)Pz molecule according to the quantum-chemical
calculations data [36–39]. Only two HOMO p2 (au)
undergoes no change, while p1 (b1u) has a significant
reduction of energy due to the high orbital coefficients of
pyrrolic and meso- nitrogen atoms, which reflects the state
of the entire macrocyclic systems. The orbitals p1 (b1u) and
pÃ1 (b2g) comparing to p2 (au) and p2Ã (b3g) are destabilized
in metal complexes of tetrapyrrolic compounds. It leads to
the increase of LUMO pÃ1 and HOMO p1 energy, while
LUMO pÃ2 and HOMO p2 remain virtually unchanged.
Such action on the metal cation of aza-substituted macro-
cycle leads to a change in the symmetry of the molecule to
D4h caused by decrease of the energy difference between
There are only RS- anions in the solution at initial time.
That is why the linearized kinetic Langmuir–Hinshelwood-
Schwab equation takes the form:
À
À
PRS
W
1
CRS
CRSSR
À
¼
þ
PRS
þ
PRSSR
ð8Þ
kobs
kobs
kobs
Fig. 2 Scheme of conjugation
circuit of macrocycles p-system
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
Co
N
N
Co
N
Co
N
N
N
N
Co(II)Pc
Co(II)P
Co(II)PPz
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J Incl Phenom Macrocycl Chem
Table 1 Parameters of DTC oxidation in presence of macrocyclic catalysts (pH 11.4)
Catalyst
kobs 9 102 (s 9 g-1
)
W 9 104 (25 °C)
Ea (kJ mol-1
)
TON
T ( °C)
20
25
7.5 0.8
30
35
40
Co(II)P
6.9 0.3
–
9.3 0.6
–
11 0.4
16 0.4
13 0.4
–
4
30
29
54
40
30
1
1
2
1
1
72
83
Co(II)Pz
Co(II)Pc
Co(II)PPz
Co(II)BP
11
37
1
1
5.5
18.5
7
28
1
49
21
1
1
74
1
100
1
112
64
12 0.9
–
14 0.9
10 0.4
26 0.7
15 0.4
29 0.8
–
12 0.6
5
76
becomes excessively electronic under coordination of the
substrates and oxygen. This leads to lability of the formed
complexes. The joint combination of aza-substitution and
benzo-annulation (Co(II)Pc) leads to significant increase of
macrocycle aromaticity [42, 43] and alignment of the
charge density on central metal cation, which causes fast
coordination exchange between the substrate and the
reaction product. Acceleration of the desorption processes
of the reaction product from catalyst active center leads to
significant increasing of the general process rate. This
acceleration is caused by thermodynamic instability of
formed triple complex due to increasing of the tetrapyrrole
macrocycle aromaticity. Structural criterion of the aro-
maticity calculated for the phthalocyanine is 0.204, for the
porphyrin it in turn is lower 0.179 [44]. Under aza-sub-
stitution of annulated benzene fragments their weak con-
jugation with eighteen central p-electrons of the
macrocycle is disturbed (Fig. 2) that leads to increase of
uncompensated charge on central metal cation and pro-
motes decrease of catalytic activity.
where PRS—partial pressure of thiolate, PRSSR—partial
pressure of reaction product, kobs—observed constant of
reaction rate.
Kinetic curves obtained by this equation are in good
agreement with experiment. DTC oxidation rate constants
are shown in Table 1.
Obtained values of process activation energy (Table 1)
allows to conclude that the reaction takes place in kinetic
region. Processes of adsorption can be taken as quasi-
equilibrium for this region [41]. The first kinetic order of
the reaction according to substrate indicates the weak
adsorption of DTC on the surface of the catalyst. Wherein,
it is obvious that disulfide formed during the oxidation will
also have weak adsorption, which determines the limiting
state of the entire process as desorption from active centers
of the catalyst. Concerning investigated compounds this
process is directly linked to the destruction of the triple
oxygen-catalyst-substrate complex in the reaction step
recorded by Eq. 1.
Thereat, the rate of the process is determined by Eq. 9:
À
W ¼ kobsCRS
ð9Þ
Conclusion
This corresponds to equation of the reaction order con-
cerning the volume and surface concentrations of thiolate-
ion and indicates that observed activation energy of the
process will be determined by the difference between the
true activation energy and the absolute value of the heat of
adsorption. The observed positive values of activation
energy let us to conclude that the adsorption heat is lower
than the true value of energy barrier of the reaction.
The results obtained in present work demonstrates the
strategy of evolution of the macrocyclic ligand structure
coordinated by metal and its physical and chemical prop-
erties on the example of catalytic properties for oxidation
of DTC. It was established that the oxidation of DTC by air
oxygen in presence of b-octaphenylporphyrin and its aza-
and benzo-annulated analogues proceeds in kinetic region,
wherein diffusion braking of the process is not observed.
This allows to conclude that aza-substitution has a greater
effect on catalytic activity of tetrapyrrolic macroheterocy-
cles compared to benzo-annulation. Removal of annulated
benzene fragments from the p-conjugated system by aza-
substitution leads to decrease in catalytic activity. Consis-
tent combination of benzo-annulation and aza-substitution
on the periphery of tetrapyrrolic macromolecule, for
Catalytic activity of investigated compounds changes in
the series from porphyrin to phthalocyanine Co(II)P \
Co(II)BP B Co(II)Pz \ Co(II)PPz ꢀ Co(II)Pc. The regu-
larity of change of catalytic activity under modification of
macrocycle p-system is pretty clearly traced. Increase of
the porphyrin aromatic conjugated p-system under benzo-
annulation (Co(II)BP) or aza-substitution (Co(II)Pz) leads
to increasing of catalytic activity due to decreasing of the
charge density of central metal cation. Metal cation
123

J Incl Phenom Macrocycl Chem
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Acknowledgements The synthesis, extraction and purification of
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