SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE
Synthetic approach have been developed, and different-metal coordination compounds [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O (H4Edta is ethylenediaminetetraacetic acid, bipy is 2,2’-bipyridine, M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5)) have been prepared, their...
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Ukrainian Chemistry Journal| _version_ | 1871466187885379584 |
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| author | Pechinka , Dmytro Martsynko , Оlena |
| author_facet | Pechinka , Dmytro Martsynko , Оlena |
| author_institution_txt_mv | [
{
"author": "Dmytro Pechinka ",
"institution": "Odesa I.I. Mechnikov National University, Vsevolod Zmienko St., 2, Odesa, 65082, Ukraine "
},
{
"author": "Оlena Martsynko ",
"institution": "Odesa I.I. Mechnikov National University, Vsevolod Zmienko St., 2, Odesa, 65082, Ukraine."
}
] |
| author_sort | Pechinka , Dmytro |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:56Z |
| description | Synthetic approach have been developed, and different-metal coordination compounds [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O (H4Edta is ethylenediaminetetraacetic acid, bipy is 2,2’-bipyridine, M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5)) have been prepared, their comprehensive characterization has been carried out using modern physicochemical methods (elemental analysis, IR spectroscopy, mass spectrometry, and thermogravimetry), and structural features of new complexes have been determined. The synthesised complexes were found to be heteronuclear. The coordination polyhedron of the germanium(IV) remains analogous to that in the structurally characterized ethylenediaminetetraacetatogermanic acid, [Ge(OH)(HEdta)]·H₂O, adopting a distorted octahedral geometry formed by coordination to one hydroxyl group, three carboxylate oxygen atoms, and two nitrogen atoms of the Edta-ligand. The 3d metal center exhibits a coordination number of six, and it is bonded to two oxygen atoms of the carboxylate groups from two germanium-containing complex anions and four nitrogen atoms from two bipyridine molecules. |
| doi_str_mv | 10.33609/2708-129X.91.12.2025.3-13 |
| first_indexed | 2026-03-19T02:00:18Z |
| format | Article |
| fulltext |
3
UDC 541.49+546.289 doi: 10.33609/2708-129X.91.12.2025.3-13
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR
Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINE-
TETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.
D.M. Pechinka, O.E. Martsynko
Odesa I.I. Mechnikov National University,
2 Vsevolod Zmienko St., 65082 Odesa,Ukraine
e-mail: lborn@ukr.net
Synthetic approach have been developed, and different-metal coordination compounds
[M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O (H4Edta is ethylenediaminetetraacetic acid, bipy is 2,2’-bi-
pyridine, M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5))
have been prepared, their comprehensive characterization has been carried out using modern
physicochemical methods (elemental analysis, IR spectroscopy, mass spectrometry, and thermo-
gravimetry), and structural features of new complexes have been determined. The synthesised
complexes were found to be heteronuclear. The coordination polyhedron of the germanium(IV)
remains analogous to that in the structurally characterized ethylenediaminetetraacetatogermanic
acid, [Ge(OH)(HEdta)]·H₂O, adopting a distorted octahedral geometry formed by coordination
to one hydroxyl group, three carboxylate oxygen atoms, and two nitrogen atoms of the Edta-li-
gand. The 3d metal center exhibits a coordination number of six, and it is bonded to two oxygen
atoms of the carboxylate groups from two germanium-containing complex anions and four nitro-
gen atoms from two bipyridine molecules.
Keywords: germanium(IV), ethylenediaminetetraacetic acid, heterocyclic amines, coordina-
tion compounds, IR spectroscopy, thermogravimetry, mass spectrometry.
INTRODUCTION. Metal compounds with
aminopolycarboxylate complexones have long
been the subject of intensive research and
practical application in agriculture, analytical
chemistry, materials science, and environmen-
tal chemistry due to their unique structural,
spectroscopic, catalytic, and biological pro
perties [1, 2]. The most extensively studied sys-
tems are complexes based on ethylenediamine-
tetraacetic acid (H4Edta) and its structural
analogues, including heterometallic comp
lexes [3–9]. Significant attention has been paid
to the widespread application of such coordi-
nation compounds in crop production. In par-
ticular, soil amendment or foliar fertilization
with solutions of ethylenediaminetetraacetates
of 3d metals has been shown to increase the
yield of grain crops (buckwheat, oats, barley,
rye, flax) and to accelerate seed germination
and vegetative growth processes [1].
Anions of polyaminopolycarboxylic acids,
acting as bridging ligands, can form one-, two-,
4 ISSN 2708-129X. Укр. хім. журн., 2025
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES
WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.INORGANIC CHEMISTRY
and three-dimensional polymeric chains and
networks, in some cases featuring large cavi
ties. Such structures are classified as me
tal-organic frameworks (MOFs) and are
characterized by high thermal stability and
durability. An illustrative example is the meso
porous three-dimensional polymeric complex
{[ZrIVO-μ3-(Edta)FeIIIOH]·H2O}n [5]. The in-
corporation of heteroaromatic amines, such
as 2,2’-bipyridine (bipy), into carboxylate
complexes contributes to their stabilization
through noncovalent interactions, including
hydrogen bonding, π–π stacking, and C–H···π
interactions [10].
It has been demonstrated that Cu(II) comp
lexes with amino acids and 2,2′-bipyridine
can promote the generation of reactive oxygen
species and induce DNA and RNA degrada-
tion. The heterocyclic amine intercalates into
the DNA helix, while copper ions catalyze the
in situ formation of hydroxyl radicals, which
subsequently cause oxidative DNA damage.
This property is of interest for therapeutic
and biotechnological research [10]. Moreover,
copper(II)-bipyridine complexes with amino
acids exhibit cytotoxic activity even against
cisplatin-resistant tumor cell lines [11].
Among the least studied systems are hete
rometallic multiligand complexes of p- and
d-block metals. Representative examples in-
clude Co(II)–Bi(III) cation–anion compounds
such as [Co(NH3)5NCS](Bi(Edta)]2·4H2O,
[Co(NH3)4(NO2)2][Bi(Edta)(H2O)]·2H2O,
[Co(NH3)4(CO3)][Bi(Edta)]·3H2O [6], and
[Co(NxH)2(An)2]2[Bi(Edta)(H2O)]2·7H2O,
[Co(NxH)2(p-Tol)2][Bi(Edta)]·4H2O (where
An is aniline, p-Tol is p-toluidine, NxH is
1,2-cyclohexanedione dioximate) [7].
Aminopolycarboxylate complexes of ger-
manium(IV) have attracted considerable in-
terest due to their intriguing structural fea-
tures and plant growth-stimulating properties.
These compounds have been systematically
investigated for many years at the Faculty of
Chemistry and Pharmacy of Odesa I.I. Mech-
nikov National University within the scien-
tific school led by I.I. Seifullina [12–14]. The
complex acid [Ge(OH)(HEdta)]×Н2О was
synthesized, and heteronuclear complexes
with various 3d metals were obtained using
this compound as a structural building block.
It was shown that, in the presence of Cu²⁺ ions,
a heteronuclear complex [Cu(H2O)4{Ge(OH)
(μ-Edta)}2] is formed, in which the copper
ion is coordinated by two nitrogen atoms of
the fully deprotonated ligand and four water
molecules [12]. A polymeric heteronuclear
Ge(IV)-Cu(II) compound based on the H4Edta
derivative 3-diamino-2-hydroxypropanetetra
acetic acid (H5Hpdta) and 2,2’-bipyridine,
{[Ge2(OH)2(μ3-hpdta)2Cu2(bipy)2]×2Н2О}n,
was also obtained [15]. However, mixed-ligand
complexes of Ge(IV) – 3d metals with H4Edta
and heterocyclic amines have not yet been sys-
tematically investigated.
The aim of this work is to develop synthe
tic approaches for coordination compounds
of Ge(IV)–Mn(II)/Co(II), Ni(II), Cu(II), and
Zn(II) with ethylenediaminetetraacetic acid
and 2,2′-bipyridine, to perform their compre-
hensive characterization using modern phy
sicochemical methods, and to establish their
structural features.
EXPERIMENT AND DISCUSSION OF THE
RESULTS. As starting reagents for the synthe-
sis of new complexes, were used ready-made
reagents (Sigma-Aldrich) without additional
purification: germanium(IV) oxide (GeO2,
99.99%), ethylenediaminetetraacetic acid
(H4Edta, CAS 60-00-4, ³98%), 2,2’-bipyridine
5https://ucj.org.ua
D.M. Pechinka, O.E. Martsynko UCJ № 12 / Vol. 91
(bipy, CAS 366-18-7, 99.5%), and metal salts
Mn(CH3COO)2∙4H2O, Co(CH3COO)2∙4H2O,
Ni(CH3COO)2∙4H2O, Cu(CH3COO)2∙H2O,
Zn(CH3COO)2∙2H2O (98-99%).
Synthesis of compounds 1–5. An equimolar
amount of GeO2 (0.05 mol, 5.23 g) was added to
an aqueous solution of H4Edta (0.05 mol, 14.6 g
in 1 L of water at 100°C), and the mixture was
evaporated for 2 hours at 80 °C to a volume of
500 mL and cooled at room temperature 20–
25 °C (working solution). The working solu-
tion was divided into 5 parts. Solutions con-
taining 0.005 mol of the corresponding metal
salt and bipy, in a 1:2 ratio, were separately pre-
pared in 10 mL of 95% ethanol. These solutions
were added to part of the working solution and
mixed. After 24 h, crystalline precipitates of
light pink (complexes 1 – with Mn, 5 – with
Zn), yellow (complex 2 – with Co), burgundy
(complex 3 – with Ni), and blue (complex 4 –
with Cu) were formed in the reaction medium.
Yields ranged between 63–70%.
Elemental analysis was performed on
C,N,H-analyzer Elemental Analyzer CE-440.
The metal content in the complexes was mea
sured by inductively coupled plasma atomic
emission spectroscopy using a PerkinElmer
Optima 8000.
Thermogravimetric analysis (TGA) was per-
formed on a Q-1500D device at a heating rate
of 10°C/min in air, over the temperature range
20–1000°C.
The IR spectra in the range of 4000–400 cm-1
were recorded as potassium bromide pellets
on a Frontier spectrometer (PerkinElmer). IR
spectra were interpreted based on literature
data on the characteristic absorption bands of
organic molecules and complex compounds of
germanium(IV) and other metals [12, 16, 17].
ESI-mass spectra were taken on a TSQ
Fortis Triple Quadrupole Mass Spectrome-
ter (ThermoFisher Scientific, USA). The sam-
ple was infused with a Chemyx Fusion 100T2
syringe pump at a flow rate of 20 mL/min.
Water-methanol solutions of the complexes
(at about 10 µg/mL) were introduced using a
500 µL Hamilton gas-tight syringe. The electric
potential used to initiate ESI was 3.0 to 3.5 kV
in positive ionization mode and 2.0 to 2.5 kV
in negative ionization mode. Mass spectra were
collected in centroid mode over the m/z range
of 50–1500 Da.
The main results of the study of complexes
are presented below.
Elem. Anal. Calculated (%) for
C40H52Ge2MnN8O23 (1, Mr = 1212): C 39.60,
H 4.29, Ge 11.96, Mn 4.54, N 9.24; found
(%): C 39.37, H 4.20, Ge 11.87, Mn 4.48,
N 9.16. IR spectrum (KBr, ν сm-1): 3422 ν(ОН),
3058 ν(C–Hbipy), 2996 ν(C–H), 1712 νas(COO),
1592, 1173 ν(C–Cbipy), 1472 δas(CH2), 1437
νs(COO), 1402 δs(CH2), 1312 ν(С–Nbipy), 1079
ν(С–N), 1012 ν(C–O), 934, 873 δ(C–Hbipy),
773, 736 γ(C–Hbipy), 818 δ(GeOH), 652
ν(Ge–O), 509 ν(Mn–N), 428 ν(Mn–O). TGA
data (weight losses): 50-170 °C (7.5%); 170–
320 °C (25.5%); 320–700 °C (46.0%); residue
21.0%. ESI-mass spectrum ESI(-): [Ge(OH)
(Edta)]- (m/z = 375.16, 376.88, 379.08); ESI(+):
Hbipy+ (m/z = 157.10), [Mn(bipy)2]
2+ (m/z =
183.61).
Elem. Anal. Calculated (%) for
C40H56CoGe2N8O25 (2, Mr = 1252): C 38.34,
H 4.47, Co 4.71, Ge 11.58, N 8.85; found (%):
C 38.21, H 4.30, Co 4.58, Ge 11.45, N 8.72.
IR spectrum (KBr, ν, сm-1): 3421 ν(ОН), 3079
ν(C–Hbipy), 2990 ν(C–H), 1713 νas(COO),
1598, 1158 ν(C–Cbipy), 1473 δas(CH2), 1442
νs(COO), 1399 δs(CH2), 1314 ν(С–Nbipy), 1078
ν(С–N), 1018 ν(C–O), 935, 872 δ(C–Hbipy),
6 ISSN 2708-129X. Укр. хім. журн., 2025
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES
WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.INORGANIC CHEMISTRY
776, 737 γ(C–Hbipy), 816 δ(GeOH), 652
ν(Ge–O), 510 ν(Co–N), 419 ν(Co–O). TGA data
(weight losses): 50-190 °C (10.0%); 190–340 °C
(24.0%); 340–550 °C (44.0%); residue 22.0%.
ESI-mass spectrum ESI(-): [Ge(OH)(Edta)]-
(m/z = 375.23, 376.87, 379.07), other fragments
(m/z = 393.36, 403.39); ESI(+): Hbipy+ (m/z =
157.10), [Co(bipy)2]
2+ (m/z = 185.59, 186.33).
Elem. Anal. Calculated (%) for
C40H56Ge2N8NiO25 (3, Mr = 1252): C 38.34,
H 4.47, Ge 11.58, N 8.85, Ni 4.71; found (%):
C 38.09, H 4.36, Ge 11.50, N 8.79, Ni 4.67.
IR spectrum (KBr, ν, сm-1): 3416 ν(ОН), 3076
ν(C–Hbipy), 2986 ν(C–H), 1711 νas(COO),
1599, 1159 ν(C–Cbipy), 1473 δas(CH2), 1444
νs(COO), 1396 δs(CH2), 1312 ν(С–Nbipy), 1078
ν(С–N), 1021 ν(C–O), 933, 871 δ(C–Hbipy),
776, 738 γ(C–Hbipy), 818 δ(GeOH), 654
ν(Ge–O), 536 ν(Ni–N), 427 ν(Ni–O). TGA data
(weight losses): 50-180 °C (10.0%); 180–340 °C
(24.0%); 340–550 °C (47.5%); residue 18.5%.
ESI-mass spectrum ESI(-): [Ge(OH)(Edta)]-
(m/z = 375.00, 376.97, 378.95); ESI(+): Hbipy+
(m/z = 157.09), [Ni(bipy)2]
2+ (m/z = 185.08,
186.03).
Elem. Anal. Calculated (%) for
C40H50CuGe2N8O22 (4, Mr = 1203): C 39.90,
H 4.16, Cu 5.32, Ge 12.05, N 9.31; found (%): C
39.81, H 4.10, Cu 5.24, Ge 12.15, N 9.26. IR spec-
trum (KBr, ν, сm-1): 3415 ν(ОН), 3095 ν(C–Hbipy),
2993 ν(C–H), 1714 νas(COO), 1600, 1159
ν(C–Cbipy), 1473 δas(CH2), 1444 νs(COO),
1394 δs(CH2), 1312 ν(С–Nbipy), 1079 ν(С–N),
1014 ν(C–O), 964, 872 δ(C–Hbipy), 773, 732
γ(C–Hbipy), 816 δ(GeOH), 658 ν(Ge–O), 512
ν(Cu–N), 425 ν(Cu–O). TGA data (weight
losses): 50-170 °C (6.0%); 170–280 °C
(26.0%); 280–550 °C (46.0%); residue 22.0%.
ESI-mass spectrum ESI(-): [Ge(OH)(Edta)]-
(m/z = 375.19, 376.76, 379.12), other fragments
(m/z = 393.42, 403.43); ESI(+): Hbipy+ (m/z =
157.14), [Cu(bipy)2]
2+ (m/z = 187.63, 188.55).
Elem. Anal. Calculated (%) for
C40H52Ge2N8O23Zn (5, Mr = 1222): C 39.28,
H 4.26, Ge 11.87, N 9.17, Zn 5.32; found (%):
C 39.19, H 4.30, Ge 11.78, N 9.10, Zn 5.37.
IR spectrum (KBr, ν, сm-1): 3420 ν(ОН), 3075
ν(C–Hbipy), 2994 ν(C–H), 1711 νas(COO),
1589, 1160 ν(C–Cbipy), 1472 δas(CH2), 1440
νs(COO), 1395 δs(CH2), 1313 ν(С–Nbipy), 1078
ν(С–N), 1020 ν(C–O), 932, 873 δ(C–Hbipy),
775, 736 γ(C–Hbipy), 814 δ(GeOH), 651
ν(Ge–O), 515 ν(Zn–N), 434 ν(Zn–O). TGA data
(weight losses): 60-190 °C (7.0%); 190-330 °C
(26.0%); 330–800 °C (46.0%); residue 21.0%.
ESI-mass spectrum ESI(-): [Ge(OH)(Edta)]-
(m/z = 375.05, 376.76, 379.01), other fragment
(m/z = 393.33); ESI(+): Hbipy+ (m/z = 157.09),
[Zn(bipy)2]
2+ (m/z = 188.56, 189.09).
IR spectra of 1–5 are similar in the re-
gion of vibrational bands (as an example,
fig. 1 shows the spectra of complexes Co(II),
and Ni(II)) characteristic of the coordination
polyhedron of germanium. The presence of
asymmetric and symmetric stretching vibra-
tions of the carboxylate groups νas(СOО) and
νs(СOО), clearly indicates coordination of
the carboxylate moieties to the Ge(IV) center.
The value of the Deacon–Phillips criterion
Δν = νas(COO) − νs(COO)~267–275 сm-1 in-
dicates monodentate coordination of all car-
boxylate groups of the ligand. In addition,
bands assigned to Ge–O and Ge–N stretching
vibrations, as well as deformation vibrations
δ(GeOH), are observed. The absence of bands
in the region around 1730 cm-1 confirms that
protonated carboxylic groups are not present.
In general, the spectra 1–5 in this region are
similar to the spectrum of complex ethylenedi-
aminetetraacetategermanic acid.
7https://ucj.org.ua
D.M. Pechinka, O.E. Martsynko UCJ № 12 / Vol. 91
a)
b)
Fig. 1. IR spectra of the complexes 2 (a) and 3 (b).
Overall, the spectra of complexes 1–5 in
this region closely resemble that of ethylene-
diaminetetraacetatogermanic acid. This in-
dicates that the coordination environment
of germanium remains analogous to that in
[Ge(OH)(HEdta)]×Н2О [12], adopting a dis-
torted octahedral polyhedron. The coordina-
tion number of six is achieved through coordi-
nation with one hydroxyl group, three oxygen
atoms of three carboxylate groups, and two
nitrogen atoms of the Edta-ligand.
A set of characteristic bands assigned to
ν(C–Hbipy), ν(С–Nbipy), δ(C–Hbipy), γ(C–Hbipy)
confirms the presence of 2,2’-bipyridine in the
complexes and its coordination to the 3d me
tal ions. This is further supported by the appea
rance of a band corresponding to M–N stretch-
ing vibrations. The absorption band attributed
to ν(M–O) stretching vibrations indicates the
coordination of the fourth carboxylate group
of Edta to the 3d metal ion. Based on the IR
spectral data and considering the +2 oxidation
8 ISSN 2708-129X. Укр. хім. журн., 2025
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES
WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.INORGANIC CHEMISTRY
a)
b)
Fig. 2. Thermogravigrams of the complexes 2 (a) and 5 (b).
state of the 3d metal ions, an octahedral co-
ordination polyhedron can be proposed for
these metal centers. It is formed due to valence
bonds with oxygen atoms of two carboxylate
groups of two fragments [Ge(OH)(Edta)] and
four coordination bonds with nitrogen atoms
of two bipyridine molecules.
Broad and intense absorption bands ob-
served at approximately ~3400 cm-1 in the IR
spectra of complexes 1–5 are assigned to O–H
stretching vibrations of crystallization water
molecules, which is consistent with the ther-
mogravimetric analysis data (fig. 2).
9https://ucj.org.ua
D.M. Pechinka, O.E. Martsynko UCJ № 12 / Vol. 91
a)
b)
Fig. 3. ESI(+) mass spectra of a water-methanol solution of complex 2 (a) and 4 (b).
The thermal decomposition behavior of the
studied compounds is generally similar (as an
example, fig. 2 shows the thermogravimetric
curves of complexes Co(II), and Zn(II)). Ther-
mogravimetric analysis confirms that they are
crystalline hydrates. In the temperature range
of 50–180 °C, the corresponding number of
crystallization water molecules is released into
the gas phase (5 for complexes 1 and 5, 7 for
complexes 2 and 3, and 4 for complex 4). Upon
further heating, in the interval of 180-340 °C,
the removal of two bipyridine molecules oc-
curs, as evidenced by the mass losses calcula
ted from the TG curves. Evaluation of the mass
loss from the thermogravimetric data at 800 °C
confirms that the final decomposition product
of compounds 1–5 is a mixture of GeO2 and
the oxide of the corresponding 3d metal.
Analysis of the mass spectra of the newly
synthesized complexes revealed that the ESI(+)
mass spectra recorded in positive ion mode
exhibit a low-intensity signal corresponding to
protonated 2,2’-bipyridine Hbipy+, along with
signals attributable to doubly charged cations
[M(bipy)2]
2+ (where M denotes a 3d metal ion).
The presence of multiple peaks in this region
arises from the natural isotopic distribution of
the constituent elements that form these cati-
ons (as an example, fig. 3 shows the spectra of
heterometallic complexes Co(II), Cu(II)).
10 ISSN 2708-129X. Укр. хім. журн., 2025
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES
WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.INORGANIC CHEMISTRY
a)
b)
Fig. 4. ESI(-) mass spectra of a water-methanol solution of complex 2 (a) and 4 (b).
Fig. 5. The synthesis scheme and the supposed structure
of the compounds 1–5 (M = Mn, Co, Ni, Cu, Zn).
11https://ucj.org.ua
D.M. Pechinka, O.E. Martsynko UCJ № 12 / Vol. 91
In the negative ion mode (fig. 4), the mass
spectra display an intense signal at m/z ~ 379,
belonging to anion [Ge(OH)(Edta)]-, along
with several additional, unassigned signals that
are likely formed as a result of fragmentation
processes occurring for complexes 4, and 5.
On the basis of a comprehensive analysis of
the elemental composition, thermogravimetric
data, infrared spectral features, and mass spec-
trometric results, together with consideration of
the characteristic coordination number of six for
Ge(IV) and comparison with previously struc-
turally characterized germanium compounds,
formulas for the synthesized complexes were
proposed: [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O
(M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II),
n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5)).
The synthesis scheme and the supposed
structure of the compounds, excluding crystal-
lization water molecules, can be presented as
follows (fig. 5).
CONCLUSIONS. Thus, five new different-
metall mixed-ligand coordination compounds
were synthesized. It was shown that the li-
gand-complexon is a bridge between the Ge
and Cu atoms. The octahedral coordination
polyhedron of Ge(IV) is formed through coor-
dination with one hydroxyl group, three oxy
gen atoms of three carboxylate groups, and
two nitrogen atoms of the Edta. An octahe-
dral polyhedron of 3d-metal is realized due to
two bonds with oxygen atoms of carboxylate
groups of two fragments [Ge(OH)(Edta)] and
four bonds with nitrogen atoms of two 2,2’-bi-
pyridine molecules.
This work was performed within the
theme “Chemical construction of orga-
no-inorganic ensembles of coordinat-
ing, supramolecular, polymeric nature for
use as new materials and pharmaceuticals”,
state registration number: 0122U201403.
СИНТЕЗ ТА КОМПЛЕКСНЕ ДОСЛІДЖЕННЯ
ГЕТЕРОЯДЕРНИХ Ge(IV) – 3d-МЕТАЛОКОМП
ЛЕКСІВ З ЕТИЛЕНДІАМІНТЕТРАОЦТОВОЮ
КИСЛОТОЮ ТА 2,2ʼ-БІПІРИДИНОМ
Д. М. Печінка, О. Е. Марцинко
Одеський національний університет імені
І. І. Мечникова,
вул. Всеволода Змієнка, 2, Одеса 65082,
Україна
e-mail: lborn@ukr.net
Розроблено синтетичний підхід та от-
римано різнометальні координаційні спо-
луки [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O
(H4Edta – етилендіамінтетраоцтова кисло-
та, bipy – 2,2’-біпіридин, M = Mn(II), n=5
(1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II),
n=4 (4); Zn(II), n=5 (5)). Проведено їхнє
комплексне дослідження з використан-
ням сучасних фізико-хімічних методів
(елементний аналіз, ІЧ-спектрометрія,
мас-спектрометрія, термогравіметрія) та
встановлено структурні особливості. По-
казано, що всі синтезовані комплекси є
гетероядерними. Координаційний поліедр
германію(IV) є аналогічним до такого в
раніше структурно охарактеризованій ети
лендіамінтетраацетатогерманатній кислоті
[Ge(OH)(HEdta)]·H₂O: несиметричний ок
таедр, що утворений в результаті коорди-
нації гідроксильної групи, трьох атомів
Оксигену трьох карбоксилатних груп та
12 ISSN 2708-129X. Укр. хім. журн., 2025
SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES
WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE.INORGANIC CHEMISTRY
двома атомами Нітрогену Edta-ліганду.
Координаційне число 3d-металу дорів-
нює шести та реалізується за рахунок двох
зв’язків з Оксигенами карбоксилатних груп
двох германієвмісних комплексних аніонів
та чотирьох зв’язків з атомами Нітрогену
двох молекул 2,2ʼ-біпіридину.
Ключові слова: германій(IV), етиленді-
амінтетраоцтова кислота, гетероциклічний
амін, координаційні сполуки, ІЧ-спектро
скопія, термогравіметрія, мас-спектро
метрія.
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Стаття надійшла 15.11.2025.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-759 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:13:57Z |
| publishDate | 2026 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/42/867681072385ef44fa08937e0e0a4b42.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-7592026-07-22T08:23:56Z SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE Pechinka , Dmytro Martsynko , Оlena germanium(IV), ethylenediaminetetraacetic acid, heterocyclic amines, coordination compounds, IR spectroscopy, thermogravimetry, mass spectrometry. Synthetic approach have been developed, and different-metal coordination compounds [M(bipy)2{Ge(OH)(μ-Edta)}2]×nH2O (H4Edta is ethylenediaminetetraacetic acid, bipy is 2,2’-bipyridine, M = Mn(II), n=5 (1); Co(II), n=7 (2); Ni(II), n=7 (3); Cu(II), n=4 (4); Zn(II), n=5 (5)) have been prepared, their comprehensive characterization has been carried out using modern physicochemical methods (elemental analysis, IR spectroscopy, mass spectrometry, and thermogravimetry), and structural features of new complexes have been determined. The synthesised complexes were found to be heteronuclear. The coordination polyhedron of the germanium(IV) remains analogous to that in the structurally characterized ethylenediaminetetraacetatogermanic acid, [Ge(OH)(HEdta)]·H₂O, adopting a distorted octahedral geometry formed by coordination to one hydroxyl group, three carboxylate oxygen atoms, and two nitrogen atoms of the Edta-ligand. The 3d metal center exhibits a coordination number of six, and it is bonded to two oxygen atoms of the carboxylate groups from two germanium-containing complex anions and four nitrogen atoms from two bipyridine molecules. V.I.Vernadsky Institute of General and Inorganic Chemistry 2026-01-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/759 10.33609/2708-129X.91.12.2025.3-13 Ukrainian Chemistry Journal; Vol. 91 No. 12 (2025): Ukrainian Chemistry Journal; 3-13 Украинский химический журнал; ##issue.vol## 91 ##issue.no## 12 (2025): Ukrainian Chemistry Journal; 3-13 Український хімічний журнал; Том 91 № 12 (2025): Ukrainian Chemistry Journal; 3-13 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/759/394 Copyright (c) 2026 Dmytro Pechinka , Оlena Martsynko https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Pechinka , Dmytro Martsynko , Оlena SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title | SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title_full | SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title_fullStr | SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title_full_unstemmed | SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title_short | SYNTHESIS AND COMPREHENSIVE STUDY OF HETERONUCLEAR Ge(IV) – 3d METAL COMPLEXES WITH ETHYLENEDIAMINETETRAACETIC ACID AND 2,2ʼ-BIPYRIDINE |
| title_sort | synthesis and comprehensive study of heteronuclear ge(iv) – 3d metal complexes with ethylenediaminetetraacetic acid and 2,2ʼ-bipyridine |
| topic_facet | germanium(IV) ethylenediaminetetraacetic acid heterocyclic amines coordination compounds IR spectroscopy thermogravimetry mass spectrometry. |
| url | https://ucj.org.ua/index.php/journal/article/view/759 |
| work_keys_str_mv | AT pechinkadmytro synthesisandcomprehensivestudyofheteronucleargeiv3dmetalcomplexeswithethylenediaminetetraaceticacidand22ʼbipyridine AT martsynkoolena synthesisandcomprehensivestudyofheteronucleargeiv3dmetalcomplexeswithethylenediaminetetraaceticacidand22ʼbipyridine |