Electrochemical synthesis, structure, magnetic and tribochemical properties of metallochelates of new azomethine ligands, bis-[2-(N- tosylaminobenzylidenealkyl(aryl)]disulfides

Article abstract of DOI:10.1134/S1070363209030128

On the basis of new ligand systems, bis-azomethines of N- tosylaminobenzaldehyde and alkyl(aryl) diaminodisulfides, mono- and binuclear chelates with 4N- and 2N2S-ligand arrangement were chemically (from metal acetates) or electrochemically (from metals i

Full text of DOI:10.1134/S1070363209030128

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 3, pp. 401–407. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.S. Burlov, S.A. Mashchenko, O.A. Ivashchenko, D.A. Garnovskii, A.I. Uraev, M.S. Korobov, I.G. Borodkina, G.G. Chigarenko,
A.G. Ponomarenko, A.D. Garnovskii, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 3, pp. 412–418.
Electrochemical Synthesis, Structure, Magnetic
and Tribochemical Properties of Metallochelates
of New Azomethine Ligands,
Bis-[2-(N-tosylaminobenzylidenealkyl(aryl)]disulfides
A. S. Burlova, S. A. Mashchenkoa, O. A. Ivashchenkoa, D. A. Garnovskiib,
A. I. Uraeva, M. S. Korobova, I. G. Borodkinaa, G. G. Chigarenkoc,
A. G. Ponomarenkoc, and A. D. Garnovskiia
a Research Institute of Physical and Organic Chemistry, South State University,
Prosp. Stachki 194/2, Rostov on Don, 344090 Russia
e-mail: garn@ipoc.rsu.ru
b South Scientific Center of Russian Academy of Sciences, Rostov on Don, Russia
c Invek RD Ltd., Rostov on Don, Russia
Received October 13, 2008
Abstract―On the basis of new ligand systems, bis-azomethines of N-tosylaminobenzaldehyde and alkyl(aryl)
diaminodisulfides, mono- and binuclear chelates with 4N- and 2N2S-ligand arrangement were chemically
(from metal acetates) or electrochemically (from metals in the zero oxidation state) first synthesized and
characterized. Mononuclear chelates have a tetrahedral structure. In binuclear copper complexes the magnetic
exchange interaction of the antiferromagnetic type was observed. Bisazomethines of disulfides were used as
additives to lubricant oils.
DOI: 10.1134/S1070363209030128
Electrochemical synthesis based on the anode
dissolution of the complex-forming metals in the zero
oxidation state is an important method of preparation
of coordination compounds [1–15]. In summary, the
process of electrolysis of proton-donor ligating com-
pounds can be represented as follows:
important place in this research occupies electro-
synthesis of coordination compounds of azomethines
containing in the coordnation sphere the chalcogene
atoms, for example [10, 16–20].
In the development of research in this field we have
first synthesized and studied the ligating azomethines:
bis[2-(N-tosylaminobenzylidenealkyl(aryl))]disulfides
I, their mono- II and binuclear III complexes.
Cathode (Pt): n LH + n e → n L– + n/2 Н2,
Anode (M0): M – n e → Mn+,
Solution: nL– + Mn+ → [MLn].
The synthesis of bisazomethine disulfide I was
performed by classical method for preparation of the
Schiff bases [21] by the reaction of о-tosylamino-
benzaldehyde (IV) [22] with 2,2'-dithiodianiline (V )
[23].
Advantages of electrosynthesis over conventional
chemical synthesis of coordination compounds consist
in the possibility of the purposeful preparation of metal
complexes containing no anions and in carrying out
synthetic reactions under mild conditions (usually at
room temperature) with a high yield of final products
[10, 15].
Electrosynthesis of chelates II and III was per-
formed from bisazomethine ligating compounds under
standard conditions [10, 12, 15] upon anodic dissolu-
tion of the complex-forming metals (Co0, Ni0, Cu0,
Zn0, Cd0) with a platinum cathode in acetonitrile at 20°С
with [Et4N]ClO4 as a conducting additive. Charac-
The method of electrochemical synthesis was
widely used for preparation of metal chelates, in
particular, the Schiff bases complexes [9–13, 15]. An
401

402
BURLOV et al.
Table 1. Data of elemental analysis of azomethines Ia–Ic and their complexes
Found, %
mp,
Calculated, %
R
X
M
Composition
Formula
°С
С
Н
N
M
–
С
Н
N
M
–
(СН2)2 Ts
Н
90–91
57.93 5.32 8.62
52.45 4.32 7.90
С32Н34N4O4S4
57.63 5.14 8.40
Iа
(СН2)2 Ts Cu CuL
IIаа (СН2)2 Ts Cu CuLа
229–230
9.32 С32Н32N4O4S4Сu
9.10 С32Н32N4O4S4Cu
52.76 4.42 7.69 8.72
52.76 4.42 7.69 8.72
IIа
229–230
52.43 4.12 7.80
(СН2)2 Ts Ni
IIbа (СН2)2 Ts Ni
NiL
265–266
245–246
>250
53.11 4.25 7.63
53.25 4.32 7.56
8.21 С32Н32N4O4S4Ni
8.30 С32Н32N4O4S4Ni
53.15 4.45 7.74 8.11
53.15 4.45 7.74 8.11
52.44 4.80 7.42 16.97
52.63 4.41 7.67 8.59
52.63 4.41 7.63 8.95
49.44 4.14 7.20 14.46
IIb
NiLа
(СН2)2 Ts Со CoL·MeOH
52.45 4.17 7.70 17.00 C33H36N4O5S4Co
IIc
IId
(СН2)2 Ts Zn
IIdа (СН2)2 Ts Zn
ZnL
ZnLа
220–221
215–216
205–207
79–80
52.38 4.36 7.28
52.45 4.52 7.83
8.89 С35Н35N4O4S4Сu
9.10 С32Н32N4O4S4Zn
(СН2)2 Ts Cd CdL
50.12 4.24 7.32 14.76 С32Н32N4O4S4Сd
59.29 5.85 7.23 С18Н20N2O2S2
51.70 4.67 6.40 14.86 С18Н18N2O2S2Сu
51.43 4.42 6.70 15.5 С18Н18N2O2S2Сu
IIe
Ib
(СН2)2
(СН2)2
IIfа (СН2)2
(СН2)2
IIgа (СН2)2
O
O
Н
Н2L
–
59.97 5.59 7.77
–
Cu CuL
Cu CuLа
175
51.23 4.29 6.64 15.05
IIf
O
O
O
O
169
193
51.23 4.29 6.64 15.05
51.79 4.35 6.71 14.07
51.79 4.35 6.71 14.07
51.79 4.34 6.71 14.12
Ni
Ni
NiL
NiLа
51.43 4.10 6.32 14.58 С18Н18N2O2S2Ni
52.21 4.55 6.32 14.58 С18Н18N2O2S2Ni
51.70 4.16 7.10 14.62 С18Н18N2O2S2Сo
IIg
180–181
190–191
(СН2)2
Со CoL
IIh
(СН2)2
O
O
O
Ts
Zn
Zn
ZnL
230–231
220–221
210–211
155–156
>250
51.12 4.41 6.56 15.58 С18Н18N2O2S2Zn
51.32 4.18 6.84 15.12 С18Н18N2O2S2Zn
45.31 3.82 5.34 24.10 С18Н18N2O2S2Сd
51.00 4.28 6.61 15.42
51.00 4.28 6.61 15.42
45.91 3.85 5.95 23.87
IIi
IIiа (СН2)2
ZnLа
Cd CdLа
IIjа
(СН2)2
Ph
Н
Н2L
62.67 4.31 7.42
57.32 4.25 6.84
–
С40Н34N4O4S4
62.97 4.49 7.30
–
Ic
Ph
IIkа Ph
Ts Cu CuL·H2O
Ts Cu CuLа·H2O
8.20 С40Н34N4O5S4Сu
57.02 4.06 6.64 7.54
54.10 3.64 6.31 14.4
57.36 4.09 6.69 7.00
IIk
>250
54.68 4.28 6.94 14.76 С40Н34N4O5S4Сu
Ph
Ts Ni
NiLа·H2O
>250
56.85 3.88 6.26 7.61 С40Н34N4O5S4Ni
IIl
a Complex compounds prepared by the electrochemical synthesis.
teristics of the products of the electrochemical reaction
are presented in Table 1.
the formation of mono- (ML–II) or binuclear (M2L2–
III) complexes [12, 13, 26–28]. The chelate type of the
described structures II and III follows from com-
parison of the data of IR and 1Н NMR spectra.
To compare the characteristics of the previously
unknown complexes, their chemical synthesis was
performed by direct reaction [12, 13] of ligand I with
acetates of the aforementioned d-metals in boiling
methanol.
The C=N bond stretching vibration frequencies in
the IR spectra decrease on going from ligands I to
complexes II, III (1630–1640 cm-1 for ligands, 1620–
1630 cm–1 for complexes) (Table 2), which, according
to the data of [27] and references therein proves
participation of the azomethine nitrogen atom in the
coordination.
It is known [10, 16–20] that under the conditions of
electrosynthesis based on disulfide ligands (I, Х = О)
complex compounds with both retention and rupture of
the S–S bond can be obtained. The latter result is based
on the data of the Tuck’s studies [23–25]. Judged from
1
Comparison of the H NMR spectra of ligands I
1
the H NMR spectra, the ligand systems of the type I
and zinc complexes II (Table 2) shows the disap-
pearance in the products of complex formation the
signals of protons of the HNTs fragments and a
downfield shift of the signals of the HC=N group
(8.50–8.60 ppm), which is in compliance with the
formation of metallocycles including 4N (II) or 2N2S
(III) donor centers.
display the amino–imine tautomerism: the signals of
the НС=N (8.40–8.50 ppm) and HNTs (12.80–12.90
ppm) groups are observed.
According to the elemental analysis (Table 1), all
prepared compounds have ML composition regardless
of the method of their synthesis. This can result from
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 3 2009

ELECTROCHEMICAL SYNTHESIS
403
X
X
M
HC N
R
N CH
X
e/s, M0
X
S
S R
20oC, CH3CN
II
HC N
R
N CH
S R
M = Co, Ni, Cu, Zn, Cd
S
R
I
N CH
X
S
Ia, X = Ts, R = (CH2)2; Ib, X = O, R = (CH2)2;
Ic, X = Ts, R = Ph
M
M
R
S
X
HC N
III
NHTs
NHTs
NH2
H2N
NHTs +
N
S
S
N
S
S
CHO
IV
V
I
The choice between mono- II and binuclear III struc-
tures has been made on the basis of the ESR and magne-
tochemical studies at variable temperature (295–77 K).
the signals g1 = 2.268; g2 = 2.131; g3 = 2.086 are super-
imposed on the wide signal g = 2.1. These results can
be explained by the formation upon electrosynthesis of
a mixture of the mononuclear II and binuclear III
structures with the rupture of the disulfide groups.
The electrochemically synthesized copper com-
plexes of the type (II, X = O, NTs) have the following
parameters of the ESR spectra taken in CHCl3: g|| =
2.229; g┴ = 2.069; A = 167.4 E. [II, R = (СН2)4, Х =
О]; g1 = 2.219; g2 = 2.134; g3 = 2.080 [II, R = (CН2)4,
X = NTs]. A notable increase in the degree of tetra-
hedral distortion in complexes [II, R = (СН2)4, X =
NTs] is due to steric hindrances caused by the tosyl
fragment. Replacement of the hydroxyl oxygen by the
NTs group results in an increase in the anisotropy of g-
factors and to such a sharp decrease in the hyperfine
splitting constant (HSC) on copper that in complex (II,
X = NTs) it practically cannot be seen.
This conclusion is definitely proved by the
magnetochemical data (Table 3). For copper com-
plexes II [X = O, NTs, R = (CH2)2], irrespective of the
method of preparation, metallochelates are formed
whose magnetic properties practically do not vary with
temperature [μeff =2.09 (294.5 K) – 1.94 (82.9 K), 1.89
(295 K) – 1.86 (82.3 K) BM]. This is indicative of
their monomeric structure of the type (II, L = Сu) with
retention of the S–S bond. A similar magnetochemical
result was obtained for the synthesized from copper
acetate complex (II, L = Сu, X = NTs, R = C6H4). The
value of its μeff = 1.82 BM does not change when
measured even at 77 K, which points to the formation
of mononuclear complex.
Similar data have been obtained by ESR study of
the copper complexes synthesized by chemical method
from ligand I (X = NTs, R = C6H4). In the ESR
spectrum of this complex one unresolved signal with
g = 2.1 is observed. This can be due to the formation
of a substantially distorted tetrahedral structure of the
monomer complex [29, 30]. In this case the signals g1,
g2, g3, cannot be seen, as in complex II (X = NTs, R =
C6H4) because of a large width of the line.
For the copper complex prepared under the condi-
tions of electrosynthesis from the ligand (I, X = NTs,
R = C6H4), as distinct from the chemically synthesized
copper chelate, a temperature dependence of μeff
=
1.92 MB (295 K) and 1.59 MB (82.2 K) was observed,
suggesting the presence of magnetic exchange of
antiferromagnetic type. This result, according to the
literature data [31, 32], can be related to the formation
It is interesting to note that in the ESR spectrum of
the same complex prepared by electrochemical method
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 3 2009

404
BURLOV et al.
Table 2. Magnetic moments, IR and 1H NMR spectra of compounds Ia–Ic and their complexes IIa–IIl
IR spectrum, ν, cm–1
Comp
1H NMR spectrum (DMSO-d6), δ, ppm
μeff., BM
. no.
M
ОН
С=N
SO2, as SO2, s
Ph–O
–
–
Н
–
1620
1320
vs
1146
vs
2.21 s (6Н, 2СН3), 3.13 t (4Н, 2СН2), 3.93 t
(4Н, 2СН2), 7.07–7.67 m (16Н, Нarom), 8.48 s
(2Н, СН=N), 12.88 br.s (2Н, 2NH)
Iа
o. с
2.09–1.94
(294–82.9 K)
1.76–1.71
Cu
Cuа
Ni
–
–
–
–
–
–
1617
vs
1288
vs
1121
vs
–
–
–
–
–
–
IIа
IIаа
IIb
IIbа
IIc
1617
vs
1286
vs
1126
vs
(293–83 K)
3.12 (296 K)
1613
vs
1300
vs
1116
vs
3.2 (296 K)
Niа
Со
Zn
1613
vs
1300
vs
1116
vs
1606
vs
1286
vs
1120
vs
dia
1620
vs
1288
vs
1126
vs
2.55 s (6Н, 2СН3), 3.80 br.s (2Н, СН2), 4.30
br.s (2Н, СН2), 6.68–7.94 m (16Н, Нarom), 8.56
s (2Н, 2CН=N)
IId
IIdа
IIe
Ib
dia
dia
–
Znа
Cd
Н
–
–
–
–
–
–
–
–
–
–
–
1620
vs
1288
vs
1126
vs
–
–
1609
vs
1286
vs
1126
vs
1620
vs
–
–
1275
s
1.89–1.86
(295–82.3 K)
1.90–1.89
Cu
Cuа
Ni
1606
vs
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
1340
IIf
s
IIfа
IIg
IIg*
IIh
IIi
1600
vs
1340
(295–82 K)
1.76 (296 K)
s
1606
vs
1342
s
1.76 (296 K)
0.76 (296 K)
Ni*
Со
Zn
Znа
Cdа
Н
1606
vs
1342
s
1607
vs
1333
s
1622
vs
1332
s
IIiа
IIjа
Ic
1622
vs
1333
s
1330
s
1608
vs
–
3433
br
1600
s
1326
1142
vs
–
s
1296
s
1.82–1.82
(295–82 K)
1.91–1.59
Cu
Cuа
Ni
–
1600
s
1142
vs
–
–
–
IIk
IIkа
IIl
3340
br
1600
s
1296
s
1124
vs
(295–82 K)
3.11 (296 K)
–
1593
s
1296
s
1120
vs
a Complex compounds prepared by the electrochemical synthesis.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 3 2009

ELECTROCHEMICAL SYNTHESIS
405
Table 3. Temperature dependence of magnetic properties of
complexes IIa, IIf, and IIe
of binuclear complexes of the type III formed upon
electrochemical rupture of the S–S bond of the ligand
system (I, X = NTs, R = C6H4).
Comp.
T, K
82.9
χMexp×106, cm3 mol–1
Μeff, exp, BM
no.
A similar situation was earlier observed in com-
plexes of the ligand (X = O) prepared from zero-valent
metals under the conditions of electrosynthesis [8].
5682.4
4685.4
3978.1
3381.7
3126.0
2819.3
2444.3
2103.5
1847.9
4382.8
3646.7
2997.2
2564.2
2239.5
2077.1
1914.7
1671.2
1319.4
5249
1.94
1.94
1.94
1.95
2.01
2.05
2.06
2.08
2.09
1.71
1.71
1.70
1.71
1.71
1.74
1.76
1.76
1.76
1.86
1.84
1.83
1.85
1.86
1.88
1.86
1.87
1.89
1.82
1.81
1.79
1.78
1.77
1.81
1.80
1.78
1.82
1.66
1.66
1.69
1.75
1.74
1.85
1.93
1.93
1.98
IIа
100
118
140
162
186
217
256
294.5
83.1
100
120
142
164
181.5
203
232
293
82.3
100.5
120
148.5
164
188
222
245
295
82.1
99.6
119
144
156
183
226
253
295
82.9
99.6
120
143
162
188
241
258
259
Effective magnetic moments for nickel and cobalt
complexes of the type (II, X = O, R = C6H4) with
tetradentate ligands lacking a tosyl fragment are equal
at room temperature to 1.77 and 0.76 MB, respec-
tively. They are in agreement with the structure of
four-coordinated low-spin metallochelates with planar
coordination node for the cobalt and tetrahedrally
distorted nickel complex [34]. Thus, planar chelate
node CKС Со(2+) was proved by X-ray analysis for
the earlier studied [N,N'-ethylenebis(2-amino-5-chloro-
benzylideneiminate)]cobalt(2+) [2].
IIаа
Introduction of the tosyl group into the molecule of
ligand (X = NTs) substantially affects the distortion of
the planar chelate node and favors the formation of
nonplanar structures. For the nickel chelate of this
type, μeff = 3.12 (296 K); 3.20 (296 K) BM, and for the
cobalt chelate it is 4.34 (296 K) BM, which is
indicative of a distorted tetrahedral structure of the
coordination node [34, 35].
IIf
4195.9
3478.8
2873.8
2649.8
2358.5
1955.1
1787.1
1507.0
5044.3
4133.3
3384.3
2745.8
2522.3
2235.0
1788.1
1564.1
1405.0
8299.8
6902.3
5903.9
5305.6
4905.6
4506.4
3841.5
3574.2
3306.0
Therefore, when studying the complex formation of
bis[2-N-tosylaminobenzimidene-2'-aminoalkyl(aryl)]-
disulfides (I, X = NTs, R = (CH2)4, C6H4) with metals
it was established that both ligand systems irrespective
of the method of synthesis are capable of formation of
metallochelates (with Cu, Co, Zn, Ni, Cd). Bis[2-(N-
tosylaminobenzimidene)-2'-aminophenyl]disulfide
under the conditions of electrosynthesis with the use of
copper anode suffers the rupture of the disulfide bond
and, as a result, the metallochelates on its basis have
binuclear structure with spin-spin antiferromagnetic
interaction between the copper atoms.
IIe
Azomethine compounds and complexes on their
basis are effective additives to lubricant oils [36–40].
In this connection, we have studied compounds I as
additives to lubricant oils. Lubricant properties of
different oils can be improved by addition into the
lubricant composition 0.1–0.5 wt % of I. With this, the
maximum loading increases as compared to other
compositions by 20–40%, the weight wear intensity
decreases by 15–30% for bronze and by 40–95% for
steel, and the friction coefficient decreases by 40–70%.
Therefore, the obtained and studied in the present work
azomethines and their complexes can be practical
IIeа
a Complex compounds prepared by the electrochemical synthesis.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 3 2009

406
BURLOV et al.
additives to lubricant oils and used for development of
new effective lubricant compositions for different
machines and mechanisms.
ACKNOWLEDGMENTS
This work was performed under the financial
support from the Grants of the President RF (projects
NSh-363.2008.3, MK-3351-2007.3), Russian Founda-
tion for Basic Research (grants nos. 07-03-00256, 08-
03-00154, 07-03-00710) and Program of Presidium
RAS “Support of innovations (development of high-
temperature lubricants on the basis of polyorganyl-
siloxanes modified with azomethine metal complexes).”
EXPERIMENTAL
IR spectra were taken on a Specord IR 72 in-
strument, samples prepared as pastes in mineral oil. 1Н
NMR spectra were registered on a Varian Unity 300
instrument (300 MHz) in the regime of internal
2
stabilization of the polar resonance line of Н in
CDCl3. ESR spectra were recorded on a FR 9 (Zeiss)
instrument from powders. Magnetic susceptibilities in
solid phase were measured by the Faraday method in
the range 80–300 K using the device made in the
Rostov State University [41].
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praktika sinteza koordinatsionnykh soedinenii (Theory
and Practic of Synthesis of Coordination Compounds),
Leningrad: Nauka, 1990.
The azomethine compounds Ia–Ic were prepared
by the following general procedure: To the solution of
1.22 g of salicylaldehyde or 2.75 g of 2-(N-tosyl-
aminobenzal-dehyde) [22] in 50 ml of methanol the
filtered solution of 1.12 g of bis(aminoethyl)disulfide-
hydrochloride and 1.36 g of anhydrous sodium acetate
in 30 ml of methanol or 1.24 g of 2,2'-dithioaniline in
20 ml of methanol was added. The mixture was
refluxed for 1 h, the precipitated azomethines were
filtered off and washed with methanol (2×5 ml),
crystallized from the mixture chloroform−methanol
(1:2), and dried under a vacuum. Yield 85–87%.
6. Davies, Y.A., Hockensmith, C.M., Kukushkin, V.Yu.,
and Kukushkin, Yu.N., Syhtetic Coordination Chem-
istry: Principles and Practice, Singapor-London: World
Scientific, 1992.
7. Chakravorty, M.C. and Subrahmanyam, G.V.P., Coord.
Chem. Rev., 1994, vols. 135–136, p. 65.
Metal complexes IIa–IIl were prepared by the
reaction of equimolar amounts of the corresponding
azomethines Ia–Ic and acetates of the corresponding
metals in methanol (chemical method). The mixture
was refluxed for 1 h. The complexes precipitated after
cooling were filtered off, washed with methanol,
crystallized from the mixture chloroform−methanol
(2:1), and dried under a vacuum. Yield 80–85%.
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Electrochemical synthesis of complex compounds
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the methanol solution of the ligand by the routine
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