Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств
Based on the porphyrin concentrate extracted from oil, a cobalt (II) porphyrin complex and its dioxygen adduct have been synthesized. The structure of resulting complexes has been established by studying their electronic and IR spectra. The molecular weight of the oil cobalt (II) porphyrin complex,...
Saved in:
| Date: | 2019 |
|---|---|
| Main Authors: | , , |
| Format: | Article |
| Language: | English |
| Published: |
V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine
2019
|
| Online Access: | https://kataliz.org.ua/index.php/journal/article/view/49 |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| Journal Title: | Catalysis and petrochemistry |
| Download file: |  |
Institution
Catalysis and petrochemistry| _version_ | 1872009005241466880 |
|---|---|
| author | Aghaguseynova, M.M. Amanullayeva, G.I. Bayramova, Z.E. |
| author_facet | Aghaguseynova, M.M. Amanullayeva, G.I. Bayramova, Z.E. |
| author_institution_txt_mv | [
{
"author": "M.M. Aghaguseynova",
"institution": "Azerbaijan State Oil and Industry University"
},
{
"author": "G.I. Amanullayeva",
"institution": "Azerbaijan State Oil and Industry University"
},
{
"author": "Z.E. Bayramova",
"institution": "Azerbaijan State Oil and Industry University"
}
] |
| author_sort | Aghaguseynova, M.M. |
| baseUrl_str | https://kataliz.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2021-12-10T12:30:42Z |
| description | Based on the porphyrin concentrate extracted from oil, a cobalt (II) porphyrin complex and its dioxygen adduct have been synthesized. The structure of resulting complexes has been established by studying their electronic and IR spectra. The molecular weight of the oil cobalt (II) porphyrin complex, determined by the mass spectroscopic method, was 456. The molar ratio of cobalt (II) porphyrin complex and molecular oxygen is 2 : 1. It has been established that the dioxygen adduct of cobalt (II) porphyrin complex possesses the ability to epoxidize alkenes. A possible mechanism for epoxidation of alkenes has been considered. |
| doi_str_mv | 10.15407/kataliz2019.28.069 |
| first_indexed | 2026-03-12T15:50:03Z |
| format | Article |
| fulltext |
Каталіз та нафтохімія, 2019, № 28
69
UDC 665.65.546.73 2019
https://doi.org/10.15407/kataliz2019.28.069
Synthesis of the dioxygen complex
of oil cobalt (II) porphyrin complex
and study of its oxygenating properties
M.M. Aghaguseynova, G.I. Amanullayeva, Z.E. Bayramova
Azerbaijan State Oil and Industry University,
20, Azadliq Avenue, Baku, AZ 1010, quliyevazehra@mail.ru
Based on the porphyrin concentrate extracted from oil, a cobalt (II) porphyrin complex and its di-
oxygen adduct have been synthesized. The structure of resulting complexes has been established
by studying their electronic and IR spectra. The molecular weight of the oil cobalt (II) porphyrin
complex, determined by the mass spectroscopic method, was 456. The molar ratio of cobalt (II)
porphyrin complex and molecular oxygen is 2 : 1. It has been established that the dioxygen adduct
of cobalt (II) porphyrin complex possesses the ability to epoxidize alkenes. A possible mechanism
for epoxidation of alkenes has been considered.
Key words: dioxygen complex, cobalt, porphyrin complex
Introduction
Over the past 25 years, various properties of synthetic
metalloporphyrins have been established and studied. It has
been shown that synthetic metalloporphyrins in their cata-
lytic properties are not inferior to natural metalloporphyrins.
However, synthetic metal porphyrins are practically insolu-
ble in hydrocarbons. In this regard, there are serious tech-
nical difficulties in using them as a homogeneous catalyst
or for other purposes.
Unlike synthetic metal porphyrin complexes, metal
porphyrins isolated from heavy oils are quite soluble in
hydrocarbons and hydrocarbon fractions of oil. The result-
ing porphyrin complexes of transition metals are of great
interest as carriers of molecular oxygen.
In all metal porphyrin complexes, a regularity was es-
tablished in the formation of the peroxide structure of diox-
ygen adducts, which was confirmed by the presence in the
IR spectra of specific absorption bands of 1135–1140 cm–1
characteristic of the fragment.
The study of the catalytic activity of transition metal
complexes with porphyrins revealed their ability to oxidize
unsaturated organic compounds and alkenes, and their
dioxygen adducts had proved effective in epoxidation of
alkenes to oxiranes.
The object of this paper was to synthesize dioxygen ad-
ducts of metalloporphyrin complexes and to investigate
their structure by spectral methods.
Experimental part
The oil cobalt (II) porphyrin complex was obtained
from the oil porphyrin concentrate [3] according to our
method [4]. The obtained cobalt (II) porphyrin complex is a
solid material of cinnamon-violet color, which dissolves in
toluene and xylene. A sample of the obtained cobalt (II)
porphyrin complex was analyzed for cobalt content by the
spectrophotometric method [7–10]. The content of cobalt in
the sample was 12.65 %.
Preparation of the dioxygen adduct
2.28 g of petroleum cobalt (II) of the porphyrin complex
and 40 ml of carbon tetrachloride were placed in the metal
ampoule with a capacity of 100 ml, the ampoule was con-
nected to the oxygen cylinder under a pressure of 5.0 mPa
and the rocking chair was turned on. The reaction was car-
ried out at room temperature for 3 hours. The end of the
reaction was established based on completion of oxygen
absorption. At the end of the reaction, the contents in a
metal ampoule were cooled at normal pressure, and the
precipitated sediment was filtered through the glass filter.
1.52 g (62.3 %) of a solid precipitate of cinnamon color was
obtained, a solid precipitate, which, after washing from
petroleum ether and drying at room temperature, was ana-
lyzed for cobalt content by a spectrophotometric method
[7]. The cobalt content in the sample of the dioxygen ad-
duct was 6.25 %.
Epoxidation of alkenes with a dioxygen adduct
0.45 g of the dioxygen adduct (5) and 35 g (0.5 mol) of
1-pentene were placed in the metal ampoule and heated at
600 °C for 3 hours; then the reaction mixture was filtered
through the glass filter; yield of 1,2-oxidopentane deter-
mined in the filtrate by GC/LC was 65 % (based on the
olefin reacted).
IR spectroscopic studies were carried out on the
SPECORD-M80 spectrometer in the 4000–400 cm–1 re-
gion in KBr tablets.
Electronic spectra were recorded on the SF-4A instrument.
Каталіз та нафтохімія, 2019, № 28
70
Gas-liquid chromatographic analyzes were performed
on the LXM-8MD chromatograph, column dimensions:
5×2.5 m, carrier gas – helium, absorbent PEG-1000.
Results and discussion
The possibility of electroreduction of the dioxygen-
containing anion to water [1] or peroxide has been shown
before [2]. These studies are important for the creation of
combustible elements and air batteries [3–5]. The essence
of this method lies in the fact that the organometallic che-
late complexes LCo2+ (1) possess extremely high molecular
oxygen restoring abilities due to electron transfer, which
leads to the formation of a dioxygen adduct (2).
LCo2+ + O2 LCo3+ O... O... Co3+L LCo3+ Co3+L
O O
O
(1) (2) (3)
L – is an organic ligand.
The latter, oxidizing the hydrogen ion to H2O, turns into
a complex of LCo3 + (3). At the cathode, it is again reconsti-
tuted to LCo2+ (1), which then easily recovers molecular
oxygen. As a result of this combination of chemical and
electrochemical processes, a large amount of energy is
produced. Considering the great scientific and practical
significance of the dioxides complexes, we have developed
a method for obtaining such complexes based on petroleum
cobalt (2) porphyrin.
We synthesized oil cobalt (II) porphyrin complex PCo2 +
on the basis of the oil porphyrin concentrate [3] according
to the method developed earlier [4] and characterized by the
study of its electronic and IR spectra (table).
The characteristic bands with maxima in the electron
spectrum at 521, 572, and 533 nm confirm the existence of
a coordination bond between the cobalt ions and the nitro-
gen atoms in the porphyrin ring. Spectrum area of the syn-
thesized oil cobalt (II) porphyrin complex has been ob-
served in the IR absorption bands confirming the presence
of a macrocyclic porphyrin ring. The pyrrole cycles are
characterized by absorption bands at vibrational frequencies
ν 1508, 1525 and 1605 cm–1. The absorption bands at ν 857
cm–1 correspond to non-flat deformation vibrations of the
methine bridges (= CH). Plane deformation vibrations at ν
1030, 1046 and 1076 cm–1 characterize the presence of CH
bonds of the pyrrole ring. The absorption band at ν 634 cm–1
is a characteristic signal of the nonplanar deformation vi-
bration of the groups = NH in the complex PCo3+. The
absorption bands at ν 1380 and 1451 cm–1 correspond to
–C–N and –C = N groups in the petroleum cobalt (II) com-
plex. Absorption bands, characterizing the presence of the
functional groups: C = O, –OH, –NH2, –COOR, etc. in
the lateral branches of the porphyrin molecule, appear in the
areas, respectively, at 1705–1712, 3360–3475, 3214–3247
and 1736–1740 cm–1. It should be noted that the PCo2+
petroleum metalloporphyrin complex synthesized by us
dissolves rather well in aromatic and aliphatic hydrocar-
bons. The infrared spectrum (figure) of the sample of the
complex obtained by us completely coincides with the data
of the spectrum given in [3].
The molecular weight of the oil cobalt-porphyrin com-
plex PCo2+ (4), determined by the mass spectroscopic
method, is 466 carbon units.
For the first time, we obtained a dioxygen adduct of an
oil complex (5) by oxygenation of PCo2 + (2) [5].
2 PCo2+ + O2 PCo3+ ...O
O... Co3+P
(4) (5)
The purity of the obtained sample (5) was confirmed by
repeated elemental analyses, the study of IR spectra and
measurement of magnetic susceptibility. The IR spectrum
of the dioxygen complex (5) exhibits a characteristic ab-
sorption band at = 1127 cm–1, confirming the presence of
dioxygen in the complex (5). The presence of O2
2– in the
dioxygen adduct is also established by the determination of
its magnetic moment of 1.5 mV (23 C). The IR spectral
data and the magnetic characteristics of the dioxygen anion
(O2
2–) in the complex (5) also agree well with the reference
data [6]. When comparing the contents of cobalt in the
Some characteristics of cobalt porphyrine complex
Complex
Electron spectrum,
nm
IR spectrum,
cm-1
Absorption of molecular
oxygen at 25 C, g/cm3
CoIIP 521, 533, 572
1508, 1525, 1605 (pyrrole ring), 857 (CH2), 634 (=NH),
1030,1046,1076 (CH-pyrrole), 1380 (–C–N),
1451 (–C=N)
18,7
Infrared spectrum of complex compounds a) PCo2+ com-
plex; b) the dioxygen adduct PCo2+
Каталіз та нафтохімія, 2019, № 28
71
complex compound (4) and dioxygen adduct (5), it can be
seen that in the dioxygen adduct (5), the molar ratio of
complex (4) and molecular oxygen is 2 : 1.
Our results show that although the transfer of an elec-
tron from Co (II) to dioxygen is complete, the resultant
dioxide adduct (5) can not be represented as a complex in
which the cobalt (II) ion is connected to singlet oxygen.
A remarkable feature of the diacid adduct of the petro-
leum cobalt (II) of the porphyrin complex (5) is the fact that
such dioxygen adducts undergo epoxidation of olefins.
Thus, the preprepared adduct (5) epoxidizes 1-pentene to
form 1,2-oxidopentane. It should be noted that the dioxy-
gen anion (O2
2–) in the complex compound (5) can not
directly epoxidize the olefin, the O2
2–-anion is not electro-
philic [3]. An alternative mechanism of epoxidation of
alkenes with a dioxygen adduct (5) allows the occurrence
of oxenoid resonance structures A and B formed as a result
of decomposition of the dioxygen complex of cobalt (II)
porphyrin (5):
PCo PCo3+ ...O
O... Co3+P
(A)(5)
O PCo+O-
(B)
The formation of 1,2-oxidopentane is quite possible by
the interaction of 1-pentene with the oxenoid-resonance
structure A, which has electrophilic oxygen according to
the scheme:
+
PCo=O + CH2=CH C3H7
CH2 C3H7
CH
O
CoP
CH2 C3H7
CH
O
PCo3++
The resulting 1,2-oxidopentane is identified by gas-liquid
chromatography.
Conclusion
The ability of the synthesized petroleum cobaltporphy-
rin complex to epoxidize 1-pentene to 1,2-oxidopentane has
been revealed.
The mechanism of alkene epoxidation has been pro-
posed. It is shown that alkene epoxidation with an oxygen
adduct occurs with the appearance of intermediate oxenoid
resonant structures formed during the decomposition of the
dioxygen complex.
Литература
1. Мираламов Г.Ф. Получение металлопорфири-
новых комплексов на основе нефтяных концентратов
и применение их в нефтехимических процессах и пере-
работке природного газа: дис… Баку. 2006. с. 225.
2. C. Floriani, F. Calderazzo Oxygen adducts of
Schiff’s base complexes of cobalt prepared in solution // J.
Am. Chem. Soc. A. 946(1969).
3. Тарасевич Б.Н. ИК спектры основных классов
органических соединений. Справочные материалы.
Химический факультет МГУ, Москва, 2012, с. 54.
4. Маравин Г.Б., Авдеев М.В., Багрий Е.И. Окис-
лительная функционализация насыщенных углеводо-
родов на металлокомплексных катализаторах порфи-
ринового ряда. Нефтехимия. 2000. 40 (1). 1–21.
5. Сулимов А.В., Федосов А.Е. Методы получения
катализаторов жидкофазного окисления органических
соединений пероксидом водорода. Катализ в про-
мышленности. 2007. (2). 33–36.
6. Кузнецова Л.И. Каталитические свойства ге-
терополисоединений, содержащих переходные метал-
лы в реакциях жидкофазного окисления. Докт. дисс.,
ИК СО РАН, Новосибирск, 2001, 245.
7. Авласевич Ю.С. Водорастворимые порфирин-
полимеры. Успехи химии порфиринов. Т. 4. Под ред.
О.А. Голубчикова. Изд. НИИ Химии, СПб ГУ. С.-
Петербург. 2004. 304.
8. Агагусейнова М.М., Абдуллаева Г.Н. Синтез и
свойства металлокомплексных катализаторов на осно-
ве нефтяных металлопорфиринов. Доклады НАНА,
2009. (5). 53–57.
9. Агагусейнова М.М., Амануллаева Г.И., Байра-
мова З.Э. Нефтяные металлопорфирины – катализато-
ры селективного оксигенирования непредельных угле-
водородов. НефтеГазоХимия. Москва. 2018. (1).
29–32.
10. Агагусейнова М.М., Абдуллаева Г.Н., Адыгеза-
лова М.Б. Получение дикислородных аддуктов метал-
лопорфириновых комплексов в полости рецепторов.
НефтеГазоХимия, Москва. 2014. (1). 27–32.
References
1. Miralamov G.F. Polucheniye metalloporfirinovykh
kompleksov na osnove neftyanykh kontsentratov i prime-
neniye ikh v neftekhimicheskikh protsessakh i pererabotke
prirodnogo gaza: Dis… Baku. 2006. с. 225. [In Russian].
2. C. Floriani, F.Calderazzo Oxygen adducts of Schiff’s
base complexes of cobalt prepared in solution // J. Am.
Chem. Soc. A. 946 (1969). [In English].
3. Tarasevich B.N. IK spektry osnovnykh klassov or-
ganicheskikh soyedineniy. Spravochnyye materialy. –
Khimicheskiy fakul'tet MGU. Moskva. 2012. 54. [In Rus-
sian].
4. Maravin G.B., Avdeyev M.V., Bagriy Ye.I. Okis-
litel'naya funktsionalizatsiya nasyshchennykh uglevodo-
rodov na metalokompleksnykh katalizatorakh porfiri-
novogo ryada. Neftekhimiya. 2000. 40 (1). 1–21. [In Rus-
sian].
5. Sulimov A.V., Fedosov A.Ye. Metody polucheniya
katalizatorov zhidkofaznogo okisleniya organicheskikh
soyedineniy peroksidom vodoroda. Kataliz v
promyshlennosti. 2007. (2). 33–36. [In Russian].
6. Kuznetsova L.I. Kataliticheskiye svoystva geteropoli-
Каталіз та нафтохімія, 2019, № 28
72
soyedineniy, soderzhashchikh perekhodnyye metally v reak-
tsiyakh zhidkofaznogo okisleniya. Dokt. diss… IK SO
RAN. Novosibirsk. 2001. 245. [In Russian].
7. Avlasevich YU.S. Vodorastvorimyye porfirinpoli-
mery. Uspekhi khimii porfirinov. T. 4. Pod red. O.A.
Golubchikova. NII Khimii, SPb GU. S.-Peterburg. 2004.
304. [In Russian].
8. Agaguseynova M.M., Abdullayeva G.N. Sintez i
svoystva metallokompleksnykh katalizatorov na osnove
neftyanykh metalloporfirinov. Doklady NAN A. 2009. (5).
53–57. [In Russian].
9. Agaguseynova M.M., Amanullayeva G.I.,
Bayramova Z.E. Neftyanyye metalloporfiriny –
katalizatory selektivnogo oksigenirovaniya nepredelnykh
uglevodorodov. NefteGazoKhimiya. Moskva. 2018. (1).
29–32. [In Russian].
10. Agaguseynova M.M., Abdullayeva G.N.,
Adygezalova M.B. Polucheniye dikislorodnykh adduktov
metalloporfirinovykh kompleksov v polosti retseptorov.
NefteGazoKhimiya, Moskva. 2014. (1). 27–32. [In
Russian].
Received to the editor 28.11.2017
Синтез дикислородного комплекса
нефтяного кобальт(II) порфиринового комплекса
и изучение его оксигенирующих свойств
М.М. Агагусейнова, Г.И. Амануллаева, З.Э. Байрамова
Азербайджанский государственный университет нефти и промышленности,
AZ 1010, Баку, просп. Азадлыг, 20, quliyevazehra@mail.ru
На основе порфиринового концентрата, выделенного из нефти, синтезированы кобальт (II)
порфириновый комплекс и его дикислородный аддукт. Строение полученных комплексов
установлено с помощью их электронных и ИК-спектров. Молекулярная масса нефтяного
кобальт (II) порфиринового комплекса, определенная масспектропическим методом, соста-
вила 456. Мольное соотношение кобальт (II) порфиринового комплекса и молекулярного
кислорода составляет 2 : 1. Установлено, что дикислородный аддукт кобальт (II) порфири-
нового комплекса обладает способностью эпоксидировать алкены. Рассмотрен возможный
механизм эпоксидирования алкенов.
Ключевые слова: диоксидный комплекс, кобальт, порфириновый комплекс
Синтез дикисневого комплексу
нафтового кобальт(II) порфіринового комплексу
і вивчення його оксигенуючих властивостей
М.М. Агагусейнова, Г.І. Амануллаєва, З.Е. Байрамова
Азербайджанський державний університет нафти та промисловості,
AZ 1010, Баку, просп. Азадлыг, 20, quliyevazehra@mail.ru
На основі порфірінового концентрату, виділеного з нафти, синтезовані кобальт (II) порфірі-
новий комплекс і його дикисневий аддукт. Будову отриманих комплексів встановлено за
допомогою їх електронних і ІЧ-спектрів. Молекулярна маса нафтового кобальт (II) порфі-
рінового комплексу, визначена масспектропічеським методом, склала 456. Мольне співвід-
ношення кобальт (II) порфірінового комплексу і молекулярного кисню складає 2 : 1. Вста-
новлено, що дикисневий аддукт кобальт (II) порфіринового комплексу має здатність епок-
сидувати алкени. Розглянуто можливий механізм епоксидування алкенов.
Ключові слова: діоксидный комплекс, кобальт, порфіриновий комплекс
|
| id | oai:katalizorgua:article-49 |
| institution | Catalysis and petrochemistry |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T15:50:03Z |
| publishDate | 2019 |
| publisher | V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | katalizorgua/5a/34f4a039d9fec529bc45b63d5872b25a.pdf |
| spelling | oai:katalizorgua:article-492021-12-10T12:30:42Z Synthesis of the dioxygen complex of oil cobalt (II) porphyrin complex and study of its oxygenating properties Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств Aghaguseynova, M.M. Amanullayeva, G.I. Bayramova, Z.E. Based on the porphyrin concentrate extracted from oil, a cobalt (II) porphyrin complex and its dioxygen adduct have been synthesized. The structure of resulting complexes has been established by studying their electronic and IR spectra. The molecular weight of the oil cobalt (II) porphyrin complex, determined by the mass spectroscopic method, was 456. The molar ratio of cobalt (II) porphyrin complex and molecular oxygen is 2 : 1. It has been established that the dioxygen adduct of cobalt (II) porphyrin complex possesses the ability to epoxidize alkenes. A possible mechanism for epoxidation of alkenes has been considered. На основі порфірінового концентрату, виділеного з нафти, синтезовані кобальт (II) порфіріновий комплекс і його дикисневий аддукт. Будову отриманих комплексів встановлено за допомогою їх електронних і ІЧ-спектрів. Молекулярна маса нафтового кобальт (II) порфірінового комплексу, визначена масспектропічеським методом, склала 456. Мольне співвідношення кобальт (II) порфірінового комплексу і молекулярного кисню складає 2 : 1. Встановлено, що дикисневий аддукт кобальт (II) порфіринового комплексу має здатність епоксидувати алкени. Розглянуто можливий механізм епоксидування алкенов V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the National Academy of Sciences of Ukraine 2019-11-20 Article Article application/pdf https://kataliz.org.ua/index.php/journal/article/view/49 10.15407/kataliz2019.28.069 Catalysis and petrochemistry; No. 28 (2019): Catalysis and petrochemistry; 69-72 Каталіз та нафтохімія; № 28 (2019): Каталіз та нафтохімія; 69-72 2707-5796 2412-4176 10.15407/kataliz2020.28 en https://kataliz.org.ua/index.php/journal/article/view/49/39 |
| spellingShingle | Aghaguseynova, M.M. Amanullayeva, G.I. Bayramova, Z.E. Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title | Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title_alt | Synthesis of the dioxygen complex of oil cobalt (II) porphyrin complex and study of its oxygenating properties |
| title_full | Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title_fullStr | Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title_full_unstemmed | Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title_short | Синтез дикислородного комплекса нефтяного кобальт(II) порфиринового комплекса и изучение его оксигенирующих свойств |
| title_sort | синтез дикислородного комплекса нефтяного кобальт(ii) порфиринового комплекса и изучение его оксигенирующих свойств |
| url | https://kataliz.org.ua/index.php/journal/article/view/49 |
| work_keys_str_mv | AT aghaguseynovamm synthesisofthedioxygencomplexofoilcobaltiiporphyrincomplexandstudyofitsoxygenatingproperties AT amanullayevagi synthesisofthedioxygencomplexofoilcobaltiiporphyrincomplexandstudyofitsoxygenatingproperties AT bayramovaze synthesisofthedioxygencomplexofoilcobaltiiporphyrincomplexandstudyofitsoxygenatingproperties AT aghaguseynovamm sintezdikislorodnogokompleksaneftânogokobalʹtiiporfirinovogokompleksaiizučenieegooksigeniruûŝihsvojstv AT amanullayevagi sintezdikislorodnogokompleksaneftânogokobalʹtiiporfirinovogokompleksaiizučenieegooksigeniruûŝihsvojstv AT bayramovaze sintezdikislorodnogokompleksaneftânogokobalʹtiiporfirinovogokompleksaiizučenieegooksigeniruûŝihsvojstv |