Syntheses, structure, and tribological study of 1-phenyl-3-methyl-4- dodecyliminomethylenepyrazol-5-one and its complexes with copper(II)

Full text of DOI:10.1134/S1070363212110217

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 11, pp. 1846–1854. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © A.S. Burlov, A.S. Antsyshkina, G.G. Sadikov, V.S. Sergienko, A.I. Uraev, E.V. Korshunova, D.A. Garnovskii, T.V. Lifintseva,
G.S. Borodkin, A.G. Ponomarenko, G.G. Chigarenko, I.L. Eremenko, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 11, pp. 1856–1864.
Syntheses, Structure, and Tribological Study
of 1-Phenyl-3-methyl-4-dodecyliminomethylenepyrazol-5-one
and Its Complexes with Copper(II)
A. S. Burlova, A. S. Antsyshkinab, G. G. Sadikovb, V. S. Sergienkob, A. I. Uraeva,
E. V. Korshunovaa, D. A. Garnovskiic, T. V. Lifintsevad, G. S. Borodkina,
A. G. Ponomarenkoe, G. G. Chigarenkoe, and I. L. Eremenkob
a Research Institute of Physical and Organic Chemistry, Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
e-mail: garn@ipoc.rsu.ru
b Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
c Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
d Pedagogical Institute of Southern Federal University, Rostov-on-Don, Russia
e Scientific Industrial and Commercial Company “Don-Invek,” Rostov-on-Don, Russia
Received August 18, 2011
DOI: 10.1134/S1070363212110217
The metal complexes of azomethine compounds
occupy an important place in modern coordination
chemistry [1–5] and are used as fluorescent [6–9],
magnetic [10–14], catalytic [15] and optical materials
[16–18]. They are used also as effective additives to
lubricants [19–30]. The development of the latter is an
important and urgent task.
of the complex on the friction surface reach minimum
when the complex has a square structure. Thus, at the
selection of effective additives for lubricants the
knowledge of the structure and properties of metal
complexes is an important issue.
In extension of the work on the synthesis of new
effective additives for lubricants we have prepared
1-phenyl-3-methyl-4-dodecyliminomethylenepyrazol-
5-one (HL) and its copper complex CuL2 (I).
At the metal friction in an environment with
complex-forming additives both chemical and
tribochemical interactions occur, giving rise to the
appearance on the surface of complex compounds
formed from the contacting metal and ligand-additives
[19–28]. Further a tribochemical processes of the
complex exchange proceed: on both the rubbing
surfaces a thin polymer film is formed of copper or
other complex-forming transition metal. Therewith a
process occurs of selective transfer, which leads to a
significant improvement of tribochemical charac-
teristics [31]. The effectiveness of the additives is
determined by their solubility in oils, structure of the
metal complexes formed, and the stability of the latter
[19, 20]. To fix the metal complex on the rubbing
surface, the complex coordination sphere should have
a structure that minimizes the steric strains at the
location of the complex in the active points of
frictional contact. The steric hindrances at the location
In the compound HL the equilibrium of the A–D
tautomers can be realized [32–34]. The IR spectrum of
the HL solution in hexachlorobutadiene includes the
following absorption bands: a broad band at 3420 cm–1
(νNH) and a strong band at 1668 cm–1 (νC=O).
The presence of a broad signal of the protons of NH
1
group in the H NMR spectrum of HL in CDCl3 at
09.07 ppm and a doublet signal at 7.43 ppm of the
(CH–NH) protons in combination with the IR spectral
studies and published data [32–34] indicate the
existence of HL in aminomethylene tautomeric form B
with the intramolecular hydrogen bond with the
oxygen atom of the pyrazole fragment.
In the IR spectrum of the Cu(I) complex the
absorption bands of HL at 3420 and 1668 cm–1 dis-
1846

SYNTHESES, STRUCTURE, AND TRIBOLOGICAL STUDY
1847
H
N
H3C
N
(CH2)11CH3
Cu/2
H3C
(CH2)11CH3
Cu(CH3COO)2 H2O
CH3OH
N
N
O
O
N
N
I
HL
(CH2)11CH3
(CH2)11CH3
H3C
N
H3C
N
H
H
N
N
O
O
N
N
A
B
(CH2)11CH3
(CH2)11CH3
H
H3C
HN
N
H3C
N
N
O
O
N
N
C
D
appear, but a stretching vibration band appears at
1622 cm–1 (νC=N). The value of μeff = 1.98 MB at 295 K
of the complex I does not change with temperature,
indicating its mononuclear structure. According to
elemental analysis, complex I has the composition of
CuL2, which together with spectral studies indicates
the formation of the chelate structure.
The final conclusion on the structure of I was made
on the basis of XRD data at low temperature (173 K).
Crystals of I are dark-brown needles. Figure 1 shows a
molecular structure of the complex. The Cu atom is
coordinated by two ligands L, which contain aromatic
and aliphatic fragments. Both ligands are of the same
composition and have close parameters.
In molecule I the Cu atom is coordinated by two N
atoms and two O atoms of two bidentate chelate
ligands L with the formation of highly distorted trans-
planar configuration. The dihedral angle between the
planes O1Cu1N3 and O2Cu1N6 is 33.5°. The molecule
contains a C2 pseudo-axis. The metallocycles formed
at the coordination of the metal with the ligands have a
9.0° distortion along the N3···O1 line in the Cu1···N3
ring and an 11° distortion along the N6···O2 line in the
Cu1···N6 metallocycle. The five-membered rings
C1N1N2C2C3 and C24N4N5C25C26 are almost planar, the
first is fused with the phenyl ring C4···C9, the second
with the ring C27···C32, the corresponding dihedral
angles are 11.4° and 6.3°. The bonds involving the N1
and N6 atoms are in the gauche conformation, the C–C
bonds of both hydrocarbon chains are in the anti
conformation. In both chains the amplitude of thermal
vibrations increases insignificantly with increasing
distance from the corresponding nitrogen atom. The
average planes of the hydrocarbon chains are almost
perpendicular to each other, the dihedral angle between
them is 85°. The chains are directed to one side, their
planes form the following dihedral angles with the cor-
responding aromatic fragments: C12C23/O1C1C3C11N3,
76°; C35C46/O2C24C26C34N6, 85°. The average bond
lengths in the coordination square of the central atom
are as follows: Cu1–O 1.927(2), Cu1–N 1.973(2) Å.
The specific hydrogen bond C28–H28b···O2 involves
a hydrogen atom of the phenyl ring, and the distances
are as follows: C28···O2 2.911, C28–H28b 0.93, H28b···O2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

1848
BURLOV et al.
Fig. 1. Molecular structure of complex I.
2.27 Å, the C28H28bO2 angle is 124°. The hydrogen bond
closes a six-membered H-ring O2C24N4C27C28H28b
,
which together with the phenyl and coordination rings
also is involved in the π–π stacking interaction.
Fig. 2. π–π-Stacking interaction between the molecules
(two mutually orthogonal projection).
The influence of π–π stacking interactions between
the individual planar fragments (associated through the
inversion center) leads to formation of dimers (Fig. 2).
The distance between parallel planes in the dimer is
3.24 Å, which is consistent with the usually observed
range (3.3–3.8 Å) and indicates indirectly the strength
of π–π stacking interactions. Within the dimer an
intermolecular interaction occurs in the direction of the
central atom of the complex, Cu1···C31A 3.35 Å, which
can be considered as a supplement converting the
coordination square into the elongated tetragonal
pyramid (4+1).
(associated with the complexing metal atom), or only
aliphatic fragments that run through the entire structure
(Fig. 3a). The layers differ by the packing density: in
the aromatic region there are numerous intermolecular
contacts and the π–π stacking interaction is realized,
while in the aliphatic region the contacts between the
atoms of the hydrocarbon chains are absent and the
packing is loose.
The packing of the molecules in structure I is
similar the packing characteristic of extended organic
molecules containing alternating aromatic and
aliphatic region. Compare the projection of the unit
cells of the crystals of I and 4-(3-acryloyloxy)
octyloxy-4'-cyanobisphenol (II) (Figs. 3a and 3b) [35].
Specific interest attracts in the structure I the
packing of the rather symmetrical molecular dimers in
the unit cell. A feature of the packing is the formation
of alternating layers containing only aromatic
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SYNTHESES, STRUCTURE, AND TRIBOLOGICAL STUDY
(a) (b)
1849
Fig. 3. Packing of molecules in supramolecular assemblies within the structures of (a) I and (b) II.
Such a structure containing the regions contrasting by
the strength of intermolecular interactions is charac-
teristic of compounds capable to exhibit mesogenic
(liquid crystalline) properties. It can be assumed that
the structure I or its analogs also may be able to
exhibit specific physical properties.
The electron absorption spectra (EAS) of solution
of compound HL in methylene chloride include a
system of overlapping diffuse bands (Table 1). A
shoulder located in the vicinity of 329 nm in the long-
wavelength wing of the intense asymmetric broad band
at 298 nm can be attributed, by analogy with the
spectra of the previously investigated pyrazolone
aminomethylene derivatives [36, 37], to the n→π
transitions. The absorption in the range of 264–298 nm
is probably associated with the transitions in the
pyrazolone, 1-phenylpyrazolone, and aminomethylene-
pyrazol-5-one fragments [36, 37].
As a result of the complex formation of the
aminomethylene derivative of pyrazol-5-one with
copper acetate monohydrate, in the EAS a slight blue
shift (~6.7 nm) of the maxima of the envelopes of the
intraligand bands is observed with a decrease and
redistribution of their intensity (Fig. 5). The shoulder
at 329 nm clearly expressed in the spectra of the ligand
is not seen in the spectrum of the complex, apparently
due to the merging with a strong band in the region of
291 nm. Along with the intraligand transitions, in the
EAS of the complex a low-intensity band occurs at
473 nm, which can be associated with the transitions
either at the ligand–metal O→Cu charge transfer [38–
41], or at the metal–ligand Cu→O charge transfer [42–
45]. In the range of 600–900 nm a poorly expressed
shoulder is observed with the poorly resolved
structure, which is attributed to the d–d transitions.
Judging from the position of these bands it can be
assumed that the complex has, like other similar
compounds with bidentate ligands, a distorted pseudo-
tetrahedral configuration of the chelate site [37, 45].
As noted above, the structure of coordination
compounds formed at the friction is an important
factor in determining their effectiveness as additives to
oils. In this regard, the square structure of I and its
high solubility in oil was expected to give the desired
effect. We tested compounds HL and I as additives to
lubricating oils. At adding HL and I in the M-10DM
oil in amount 4% by weight the friction coefficient in a
steel–steel pair decreases from 0.043 for pure M-
10DM oil to 0.0037, that is, approximately by an order
of magnitude. The maximum load Pmax increases by
Table 1. Parametes of EAS of compounds HL and I
Compound
HL
λmax CH2Cl2, nm
ε, g mol–1 cm–1
264
29839
298
41887
329 sh
9518
258
291
473
675
28364
25702
1163
145
I
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1850
BURLOV et al.
times and the wear resistance, 7 times. The compounds
D
HL and I may be promising additives for the deve-
lopment of new motor and other industrial oils.
EXPERIMENTAL
IR spectra were obtained on a Varian 1000-FT-IR
spectrometer from mulls in hexachlorobutadiene and
1
mineral oil. H NMR spectra were taken on a Varian
Unity-300 instrument, the internal stabilization mode
2
using the CDCl3 polar-resonance H line. The electron
absorption spectra (EAS) of the methylene chloride
solutions of studied substances were measured on a
Helios Unicam instrument in the range 195–1100 nm.
λ, nm
The tribochemical measurements were performed
on the machine for the mechanical friction (AE-5). The
samples and rider were made of steel-45. The load was
varied in the range of 10-150 MPa with increments
0.5–10 MPa. Sliding speed was 0.8 m s–1. The seizure
load Pmax and the friction coefficient were controlled.
Wear was determined gravimetrically, from these data
the rate of wear of the samples were calculated. The
test duration was 5 h.
Fig. 4. Electron absorption spectra of solution of
compound HL in methylene chloride at a concentration c =
5×10–5 M.
11.3 and 34.2 MPa for the HL and I, respectively, and
the wear rate decreases from 7.8 μm km–1 for the M-
10DM to 0.88 and 1.1 μm km–1 at the adding HL and I,
respectively.
Thus, the introduction of compounds HL and I in
the motor oil M-10DM leads to a significant increase
in the oil characteristics: the load capacity increases 3
The XRD experiment: The structure was solved by
the direct method (SHELXS-86) [46] and refined by
the full matrix least-squares method (SHELXS-97)
(a)
(b)
(c)
D
D
D
λ, nm
λ, nm
λ, nm
Fig. 5. Electron absorption spectra of I in methylene chloride solutions at the following concentrations: (a) 5×10–5, (b) 5×10–4, and
(c) 5×10–3 M.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

SYNTHESES, STRUCTURE, AND TRIBOLOGICAL STUDY
1851
[37] with respect to F2. The hydrogen atoms were
placed in calculated positions and refined isotropically
within the rider model. The crystallographic data and
characteristics of the experiment are given in Table 2,
the main bond lengths and bond angles in the
coordination polyhedron are given in Tables 3 and 4.
The experimental data are deposited in the Cambridge
Structural Database (CCDC 831652).
Table 2. Crystallographic parameters and experimental data
for compound I
Parameter
Empirical formula
Value
C45H66CuN6O2
786.58
М
Synthesis of 1-phenyl-3-methyl-4-dodecylimino-
methylenepyrazol-5-one (HL). To a solution of 2.2 g
(0.01 mol) of 1-phenyl-3-methyl-4-formylpyrazole-5-
one in 10 ml of benzene was added a solution of 1.85 g
(0.01 mol) of dodecylimine in 10 ml of benzene. The
mixture was boiled with a Dean–Stark trap for 1 h to
complete separation of water, then 2/3 of the benzene
volume was distilled off on a rotary evaporator. The
precipitate was filtered off and HL was recrystallized
from hexane. Yellow powder, yield 96%, mp 49–50°C.
IR spectrum, hexachlorobutadiene (ν, cm–1): 3240 br
(NH), 2926, 2854 (C12H25), 1668 (C=O). 1H NMR spec-
trum (δ, ppm): 0.86 t [3H, J = 6.6 Hz, (CH2)11CH3],
1.17–1.35 m (18H, CH2), 1.66 m [2H, (CH2)11CH3],
2.22 s (3H, CH3), 3.40 q [2H, 3J = 6.5 Hz, NH (CH2)],
7.01–7.14 m (1H, CArH), 7.33–7.38 m (2H, CArH),
Color, habitus
Sample size, mm
Temperature, K
Crystal system
Space group
Unit cell parameters:
a, Å
Black, a prism
0.20×0.35×0.55
293
Triclinic
Р-1
9.344(3)
10.092(3)
24.298(5)
91.83(2)
91.43(2)
93.63(3)
2284.6(4)
2
b, Å
c, Å
α, deg
3
β, deg
7.43 (2H, d, J = 13.4 Hz, CHNH, CArH), 9.71 br.s
(1H, NH). Found, %: C 74.80, H 9.61; N 11.40.
C23H35N3O. Calculated, %: C 74.75, H 9.55; N 11.37.
γ, deg
V, Å3
Synthesis of copper bis[1-phenyl-3-methyl-4-do-
decyliminomethylenepyrazol-5-onate] (I). To a solu-
tion of 0.74 g (0.002 mol) of HL in 10 ml of methanol
was added 0.2 g (0.001 mol) of copper acetate
monohydrate in 10 ml of ethanol. The mixture was
refluxed for 2 h. The complex precipitated at cooling
was filtered off, washed with 5 ml of methanol, and
recrystallized from ethanol:hexane (2:1). Brown crys-
tals, yield 75%, mp 119–120°C.
Z
d
calc, g cm–3
1.143
μ, cm–1
0.518
F(000)
846
Scan interval θ, deg
Indices interval
1.68–44.11
–11 ≤ h ≤ 11, –11 ≤ k ≤ 11,
–2 ≤ l ≤ 27
Electrochemical synthesis of I was performed by
the usual method through the interaction of HL with
the copper cations formed at dissolving the copper
anode during the electrolysis. Methanol solution
(10 ml) contained 0.002 mol of HL and 0.01 g of
[Et4N]ClO4 as a conductive additive. Electrosynthesis
was performed at a 40 mA current at 15 V voltage for
1 h. The precipitated complex was filtered off,
recrystallized from ethanol–hexane (2:1) mixture, and
dried in a vacuum drying cabinet. Yield 91%. The
melting point and spectral characteristics of complex I
obtained by chemical and electrochemical method are
identical. IR spectrum (hexachlorobutaniene, ν, cm–1):
Total number of measured reflections
Number of independent reflections
Number of reflections with I > 2σ(I)
Correction for extinction
GOOF with respect to F2
R [I > 2σ(I)]
13373
12980 (Rint 0.0226)
2978
487
1.143
R1 0.0512, wR2 0.1294
R1 0.2400, wR2 0.3473
0.330–0.441
R (all reflections)
Δρmax and Δρmin, e Å–3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

1852
BURLOV et al.
Table 3. Bond lengths (d) and bond angles (ω) of compound I
Bond
Cu1–O1
Cu1–O1'
Cu1–N1
Cu1–N1'
O1–C1
N1–C3
N1–C13
N2–C4
N2–N3
d, Å
Bond
C9–C10
C10–C11
O1'–C1'
N1'–C3'
N1'–C13'
N2'–C4'
N2'–N3'
N3'–C1'
N3'–C6'
C1'–C2'
Angle
d, Å
Bond
N3–C6
C1–C2
C2–C3
C2–C4
C4–C5
C6–C11
C6–C7
C7–C8
C8–C9
d, Å
Bond
d, Å
1.923(3)
1.931(3)
1.974(4)
1.983(4)
1.283(5)
1.297(6)
1.441(6)
1.316(6)
1.402(5)
1.377(6)
ω, deg
1.370(8)
1.377(7)
1.274(5)
1.287(6)
1.465(6)
1.308(7)
1.385(6)
1.368(6)
1.413(7)
1.402(7)
ω, deg
1.422(6)
1.407(6)
1.383(7)
1.405(7)
1.491(7)
1.381(7)
1.393(7)
1.370(7)
1.364(7)
C2'–C3'
C2'–C4'
C4'–C5'
C6'–C11'
C6'–C7'
C7'–C8'
C8'–C9'
C9'–C10'
C10'–C11'
1.402(7)
1.420(7)
1.494(7)
1.366(8)
1.368(7)
1.381(8)
1.344(9)
1.344(9)
1.387(9)
N3–C1
Angle
Angle
ω, deg
Angle
ω, deg
O1Cu1O1'
O1Cu1N1
O1'Cu1N1
O1Cu1N1'
O1'Cu1N1'
N1Cu1N1'
C1O1Cu1
C3N1C13
C3N1Cu1
C13N1Cu1
C4N2N3
C1N3N2
C1N3C6
N2N3C6
O1C1N3
151.65(14)
96.5(2)
O1C1C2
N3C1C2
C3C2C4
C3C2C1
C4C2C1
N1C3C2
N2C4C2
N2C4C5
C2C4C5
C11C6C7
C11C6N3
C7C6N3
C8C7C6
C9C8C7
130.3(5)
106.0(4)
130.7(5)
123.8(5)
105.5(5)
125.8(5)
112.4(4)
119.6(5)
128.0(5)
118.8(5)
119.4(5)
121.8(5)
120.2(5)
120.9(6)
C8C9C10
C9C10C11
C10C11C6
C1'O1'Cu1
C3'N1'C13'
C3'N1'Cu1
C13'N1'Cu1
C4'N2'N3'
C1'N3'N2'
C1'N3'C6'
N2'N3'C6'
O1'C1'N3'
O1'C1'C2'
N3'C1'C2'
C3'C2'C1'
119.3(6)
120.9(5)
119.9(5)
121.6(3)
117.9(4)
123.5(3)
118.5(3)
105.1(4)
111.8(4)
129.5(5)
118.6(4)
124.7(5)
129.4(5)
105.9(4)
124.3(5)
C3'C2'C4'
C1'C2'C4'
N1'C3'C2'
N2'C4'C2'
N2'C4'C5'
C2'C4'C5'
C11'C6'C7'
C11'C6'N3'
C7'C6'N3'
C6'C7'C8'
C9'C8'C7'
C10'C9'C8'
C9'C10'C11'
C6'C11'C10'
130.9(5)
104.8(5)
125.0(5)
112.4(5)
119.6(5)
128.0(6)
119.4(5)
118.2(5)
122.4(5)
119.8(6)
121.0(7)
119.2(6)
121.5(7)
119.1(6)
90.1(2)
89.9(2)
95.5(2)
155.5(2)
119.9(3)
117.7(4)
122.6(4)
119.6(3)
105.4(4)
110.7(4)
130.4(4)
118.7(4)
123.7(4)
Table 4. The shortest intermolecular contacts in structure I
2951, 2918, 2851 (C12H25), 1622 (C=N). Found, %: C
69.15, H 8.52, N 10.61, Cu 8.02 (chemical synthesis),
C 69.10, H 8.59, N 10.45, Cu 8.12. (electrochemical
synthesis). C46H68N6O2Cu. Calculated, %: C 69.09, H
8.56, N 10.50, Cu 7.94.
А···B
N2···C8'
N3···C8
C1···C8
C3···N2'
C6···C7
C9···C1
d, Å
3.44
3.45
3.31
3.39
3.46
3.48
Matrix for atom B
1 – x, 1 – y, 1 – z
2 – x, 1 – y, 1 – z
2 – x, 1 – y, 1 – z
x, 1 + y, z
ACKNOWLEDGMENTS
This work was supported by the President of the
Russian Federation (grants MK-170.2011.3 and NSh-
3233.2010.3), Russian Foundation for Basic Research
2 – x, 1 – y, 1 – z
2 – x, 1 – y, 1 – z
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

SYNTHESES, STRUCTURE, AND TRIBOLOGICAL STUDY
1853
15. Gibson, V.S. and Spitzmesser, S.K., Chem. Rev., 2003,
(grants 11-03-00475a, 10-03-90735-mob_st) and the
program of the of the Presidium of Rissiasn Academy
of Sciences “Support for Innovation.”
vol. 103, no. 2, p. 283.
16. Bren’, V.A., Usp. Khim., 2001, vol. 70, no. 12, p. 1152.
17. Burgette, S.C., Lippard, S.J., Coord. Chem. Rev., 2001,
REFERENCES
vol. 216-217, p. 334.
1. Garnovskii, A.D., Nivorozhkin, A.L., and Minkin, V.I.,
18. Bren’, V.A., Dubonosov, A.D., Tsukanov, A.V., and
Minikn, V.I., Ross. Khim. Zh., 2009, vol. 53, no. 1, p. 42.
19. Chigarenko, G.G., Ponomarenko, A.G., Bolotnikov, V.S.,
Alekseev, V.A., Burlov, A.S., Garnovskii, A.D., and
Barchan, G.P., Trenie i Iznos, 1989, vol. 10, no. 6,
p. 1050.
Coord. Chem. Rev., 1993, vol. 126, no. 1, p. 1.
2. Garnovskii, A.D. and Vasil’chenko, I.S., Usp. Khim.,
2002, vol. 71, no. 11, p. 1064.
3. Hernandez-Molina, R. and Menderos, A., Com-
prehensive Coordination Chemistry, Lever, A.B.P., Ed.,
Amsterdam: Elsevier–Pergamon Press, 2003, vol. 1,
p. 411.
20. Kuzharov, A.S., Effect Beziznosnosti i Tribotekhnologii,
1992, no. 2, p. 3.
21. Kuzharov, A.S., Burlakova, A.E., Zadoshchenko, E.G.,
Kuzharov, A.A., Uraev, A.I., Burlov, A.S., Kravchik, K.,
and Garnovskii, A.D., Trenie i Iznos, 2005, vol. 26,
no. 6, p. 628.
22. Chigarenko, G.G., Ponomarenko, A.G., Burlov, A.S.,
Vasil’chenko, I.S., Uraev, A.I., and Garnovskii, A.D.,
Trenie i Iznos, 2006, vol. 27, no. 2, p. 225.
23. Chigarenko, G.G., Ponomarenko, A.G., Burlov, A.S.,
Chigarenko, A.G., Vasil’chenko, I.S., Uraev, A.I., and
Garnovskii, A.D., Trenie i Iznos, 2007, vol. 28, no. 4,
p. 397.
24. Garnovskii, A.D., Burlov, A.S., Lysenko, K.A.,
Garnovskii, D.A., Borodkina, I.G., Ponomarenko, A.G.,
Chigarenko, G.G., Nikolaevskii, S.A., and Minkin, V.I.,
Koord. Khim., 2009, vol. 35, no. 2, p. 122.
25. Ponomarenko, A.G., Chigarenko, G.G., Burlov, A.S.,
Bicherov, A.V., Shiryaeva, T.A., Konoplev, B.G.,
Ageev, O.A., Kolomiitsev, A.S., Zaichenko, S.B.,
Chetverikova, V.A., Garnovskii, A.D., and Minikn, V.I.,
Trenie i Iznos, 2010, vol. 31, no. 5, p. 353.
26. Chigarenko, G.G., Ponomarenko, A.G., Burlov, A.S.,
Vasil’chenko, I.S., Garnovskii, A.D., and Minkin, V.I.,
RF Patent no. 2339682, 2007, Byul. Izobr., no. 33,
27.11.2008.
27. Chigarenko, G.G., Ponomarenko, A.G., Burlov, A.S.,
Vasil’chenko, I.S., Garnovskii, A.D., and Minkin, V.I.,
RF Patent no. 2339683, 2007, Byul. Izobr., no. 33,
27.11.2008.
28. Chigarenko, G.G., Ponomarenko, A.G., Burlov, A.S.,
Vasil’chenko, I.S., Uraev, A.I., Shiryaeva, T.A.,
Ostrovskaya, L.S., Garnovskii, A.D., and Minkin, V.I.,
RF Patent no. 2374309, 2009, Byul. Izobr., no. 33,
27.11.2009.
4. Garnovskii, A.D., Vasilchenko, I.S., Garnovskii, D.A.,
and Kharisov, B.I., J. Coord. Chem., 2009, vol. 62,
no. 2, p. 151.
5. Garnovskii, A.D., Sadimenko, A.P., Vasilchenko, I.S.,
Garnovskii, D.A., Sennikova, E.V., and Minkin, V.I.,
Adv. Heterocycl. Chem., 2009, vol. 93, p. 291.
6. Metelitsa, A.V., Burlov, A.S., Bezuglyi, S.O., Borod-
kina, I.G., Bren’, V.A., Garnovskii, A.D., and Min-
kin, V.I., Koord. Khim., 2006, vol. 32, no. 12, p. 894.
7. Metelitsa, A.V., Burlov, A.S., Bezuglyi, S.O., Borod-
kina, I.G., Vasil’chenko, I.S., Garnovskii, D.A.,
Mashchenko, S.A., Borodkin, G.S., Garnovskii, A.D.,
and Minkin, V.I., RF Patent, no. 2395512., 2010, Byul.
Izobr., no. 21, 27.07.2010.
8. You, Y. and Park, Y., J. Chem. Soc. Dalton Trans.,
2009, no. 8, p. 1267.
9. Zhang, L., Jiang, F., and Zhou, Y., J. Coord. Chem.,
2009, vol. 62, no. 9, p. 1476.
10. Burlov, A.S., Uraev, A.I., Ikorskii, V.N., Nikolaev-
skii, S.A., Koshchienko, Yu.V., Vasil’chenko, I.S.,
Garnovskii, D.A., Vlasenko, V.G., Zubavichus Ya.V.,
Divaeva, L.N., Borodkin, G.S., and Garnovskii, A.D.,
Zh. Obshch. Khim., 2008, vol. 78, no. 6, p. 1002.
11. Garnovskii, A.D., Vasil’chenko, I.S., Garnovskii, D.A.,
Burlov, A.S., Uraev, A.I., Ross. Khim. Zh., 2009,
vol. 53, no. 1, p. 100.
12. Burlov, A.S., Ikorskii, V.N., Nikolaevskii, S.A.,
Koshchienko, Yu.V., Vlasenko, V.G., Zubavichus, Ya.V.,
Uraev, A.I., Vasil’chenko, I.S., Garnovskii, D.A.,
Borodkin, G.S., and Garnovskii, A.D., Zh. Neorg.
Khim., 2008, vol. 53, no. 10, p. 1677.
13. Burlov, A.S., Nikolaevskii, S.A., Bogomyakov, A.S.,
Vasil’chenko, I.S., Koshchienko, Yu.V., Vlasenko, V.G.,
Uraev, A.I., Garnovskii, D.A., Sennikova, E.V.,
Ikorskii, V.G., Borodkin, G.S., Garnovskii, A.D., and
Minkin, V.I., Koord. Khim., 2009, vol. 35, no. 7, p. 495.
29. Ponomarenko, A.G., Chigarenko, G.G., Burlov, A.S.,
Nikolaevskii, S.A., Shiryaeva, T.A., Pavlyuk, O.V.,
Garnovskii, A.D., and Minkin, V.I., RF Patent
no. 2374310, 2009, Byul. Izobr., no. 33, 27.11.2009.
30. Garnovskii, A.D., Ponomarenko, A.G., Chigarenko, G.G.,
Burlov, A.S., Vakulenko, E.V., Bicherov, A.V.,
Chetverikova, V.A., and Minkin, V.I., RF Patent
no. 2374311, 2009, Byul. Izobr., no. 33, 27.11.2009.
14. Garnovskii, A.D., Burlov, A.S., Starikov, A.G.,
Metelitsa, A.V., Vasil’chenko, I.S., Bezuglyi, S.O.,
Nikolaevskii, S.A., Borodkina, I.G., and Minkin, V.I.,
Koord. Khim., 2010, vol. 36, no. 7, p. 483.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012

1854
BURLOV et al.
31. Garkunov, D.A., Tribotekhnika (iznos i bezyznosnost’)
Tribotecknique (Wear and Wearless), Moscow:
MSKhA, 2001.
39. Li, P., Solanki, N., K., Ehrenberg, H., Feeder, N.,
Davies, J.E., Rawson, J.M., and Halcrow, M.A.,
J. Chem. Soc., Dalton Trans., 2000, p. 1559.
32. Kurkovskaya, L.N., Shapet’ko, N.N., Kvitko, I.Ya.,
Koshelev, Yu.N., and Samartseva, E.D., Zh. Org.
Khim., 1974, vol. 10, no. 10, p. 2210.
33. Minkin, V.I., Garnovskii, A.D., Elguero, J., Katritz-
ky, A.R., and Denisko, O.V., Adv. Het. Chem., 2000,
vol. 76, p. 157.
34. Antsyshkina, A.S., Sadikov, G.G., Uraev, A.I., Kor-
shunov, O.Yu., Nivorozhkin, A.L., and Garnovskii, A.D.,
Kristallograf., 2000, vol. 45, no. 5, p. 850.
35. Antsyshkina, A.S., Sadikov, G.G., Syrbu, S.A.,
Rodnikova, M.N., Kiselev, M.R., Burmistrov, V.A.,
Kuvshinova, S.A., and Syrbu, A.A., Zh. Neorg. Khim.,
2011, vol. 56, no. 11, p. 1883.
36. Rtishchev, N.I., El’tsov, A.V., Kvitko, I.Ya., and
Allam, L.V., Zh. Obshch. Khim., 1980, vol. 50, no. 9,
p. 2070.
37. Kvitko, I.Ya., Alam, L.V., Bobrovnikov, M.N.,
Avetikyan, G.B., and Panasyuk, S.L., Zh. Obshch.
Khim., 1994, vol. 64, no. 4, p. 657.
38. John, R.P., Sreekanth, A., Rajakannan, V., Ajith, T.A.,
and Kurup, M.R.P., Polyhedron, 2004, vol. 23, no. 16,
p. 2549.
40. Jazdzewski, B.A., Holland, P.L., Pink, M., Young, V.G.,
Spencer, Jr., D.J.E., and Tolman, W.B., Inorg. Chem.,
2001, vol. 40, no. 5, p. 6097.
41. Sreenivasulu, B., Zhao, F., Gao, S., and Vittal, J.J., Eur.
J. Inorg. Chem., 2006, p. 2656.
42. Losada, J., del Peso, I., and Beyer, L., Inorg. Chim.
Acta., 2001, vol. 321, nos. 1–2, p. 107.
43. Subramanian, P.S., Suresh, E., and Dastidar, P.,
Polyhedron, 2004, vol. 23, no. 16, p. 2515.
44. Correia, I., Dornyei, A., Jakusch, T., Avecilla, F., Kiss, T.,
and Pessoa, J.C., Eur. J. Inorg. Chem., 2006, no. 14,
p. 2819.
45. Liver, E., Elektronnaya spektroskopiya neorga-
nicheskikh soedinenii (Electronic Spectroscopy of
Inorganic Compounds), Tsivadze, A.Yu., Ed., Moscow:
Mir, 1987, vol. 1.
46. Sheldrick, G.M., SHELXS-86, Gottingen (Germany):
Univ. of Gottingen, 1986.
47. Sheldrick, G.M., SHELXS-97, Gottingen (Germany):
Univ. of Gottingen, 1986.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 11 2012