Competitive coordination of 2-[(diorganylphosphinoyl)-hydroxymethyl)]-1- organylimidazoles with metal chlorides

Article abstract of DOI:10.1007/s11176-005-0198-x

The structure of complexes of bivalent cobalt, copper, zinc, cadmium, and palladium chloride and tetravalent tin chlorides with 1-organyl-2- [(diorganylphosphinoyl)hydroxymethyl]imidazoles, synthesized for the first time, was studied by ¹H NMR

Full text of DOI:10.1007/s11176-005-0198-x

Russian Journal of General Chemistry, Vol. 75, No. 2, 2005, pp. 200 206. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005,
pp. 226 232.
Original Russian Text Copyright 2005 by Baikalova, Zyryanova, Chipanina, Sinegovskaya, Ivanova, Mamaseva, Gusarova, Afonin, Trofimov.
Competitive Coordination of 2-[(Diorganylphosphinoyl)-
hydroxymethyl)]-1-organylimidazoles with Metal Chlorides
L. V. Baikalova, I. A. Zyryanova, N. N. Chipanina, L. M. Sinegovskaya,
N. I. Ivanova, T. V. Mamaseva, N. K. Gusarova, A. V. Afonin, and B. V. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Received May 13, 2003
Abstract The structure of complexes of bivalent cobalt, copper, zinc, cadmium, and palladium chloride
and tetravalent tin chlorides with 1-organyl-2- [(diorganylphosphinoyl)hydroxymethyl]imidazoles, synthesized
1
for the first time, was studied by H NMR and IR spectroscopy. The formation of two types of metal com-
plexes, molecular (Zn, Cd, Pd, Sn) and chelate (Co, Cu), was established. For crystalline 1: 1 complexes, the
structures with imidazolylphosphine oxide playing the role of an N3,O-bidentate ligand were proposed. In
2L:1 complexes, these ligands are monodentate and coordinate by the P=O oxygen atom. In DMSO solutions,
the molecular complexes undergo dissociation to form coordination compounds in which, depending of the
nature of the ligand, either M N3 or M O donor acceptor bond takes place.
Functionalyzed imidazoles with phosphine oxide
and hydroxyl substituents are convenient objects for
research into the competitive coordination of metals,
associated with the ability of polydentate ligand
systems to react by different potential donor centers,
depending on the nature of the attacking reagent and
the reaction conditions [1]. Synthesis of metal com-
plexes on the basis of polyfunctional tertiary phos-
phine oxides of the azole series opens up possibilities
for widely varying the coordination site of the metal
(=N, O=P, HO, and CH2=CH). Polysubstituted chiral
phosphorus- and oxygen-containing polydentate azole
ligands play an important role in asymmetric metal-
complex catalysis [2]. Metal complexes of such com-
pounds hold much practical promise primarily because
azoles and organophosphorus compounds exhibit a
strong physiological activity [3 6]. Development of
convenient methods of regioselective synthesis of
complexes on the basis of imidazolylphosphine oxides
is also important for searching among them of ef-
fective sorbents, flotation agents, insecticides, and
other materials with useful properties [7, 8].
zole (VI), and 1-ethyl-2-[[ethyl(phenyl)phosphinoyl]-
hydroxymethyl]benzimidazole (VII) with Co2+, Cu2+,
Zn2+, Cd2+, Pd2+, and Sn4+ chlorides, with the aim to
synthesize new metal complexes with phosphorus-
and oxygen-containing azole ligands and to correlate
the structure of the resulting complexes with the struc-
ture of the ligand, the nature of the metal, and reaction
conditions.
R3
R4
N
P
R2
CH
OH
C6H5
N
R1
O
I VII
I, R1 = CH3; R2 = R3 = H; R4 = C6H5. II, R1 = CH=CH2;
R2 = R3 = H; R4 = C6H5. III, R1 = C2H5; (R2 + R3) =
(CH)4; R4 = C6H5. IV, R1 = CH=CH2; (R2 + R3) = (CH)4;
R4 = C6H5. V, R1 = CH3; R2 = R3 = H; R4 = C2H5. VI,
R1 = C2H5; R2 = R3 = H; R4 = C2H5. VII, R1 = C2H5;
(R2 + R3) = (CH)4; R4 = C2H5.
Previously we found [9, 10] that the reactions of
2-[[bis(phenylethyl)phosphinoyl]hydroxymethyl]-1-
vinylimidazole (VIII) with methyl iodide and 1-ethyl-
2-[(diphenylphosphinoyl)hydroxymethyl]imidazole
(IX) with camphorsulfonic acid involve the heteroring
N3 atom and gives rise to complex compounds of the
ionic type. At the same time, ambident imidazoles
I VII can act as monodentate ligands coordinating
In the present work we have studied for the first
time reactions of 2-[(diphenylphosphinoyl)hydroxy-
methyl]-1-methylimidazole (I), 2-[(diphenylphosphi-
noyl)hydroxymethyl]-1-vinylimidazole (II), 1-ethyl-
2-[(diphenylphosphinoyl)hydroxymethyl]benzimida-
zole (III), 2-[(diphenylphosphinoyl)hydroxymethyl]-
1-vinylbenzimidazole (IV), 2-[[ethyl(phenyl)phosphi-
noyl]hydroxymethyl]-1-methylimidazole (V), 1-ethyl-
2-[[ethyl(phenyl)phosphinoyl]hydroxymethyl]imida-
via the P=O oxygen atom or via the heteroring N3
1070-3632/05/7502-0200 2005 Pleiades Publishing, Inc.

COMPETITIVE COORDINATION OF 2-[(DIORGANYLPHOSPHINOYL)-...
Table 1. Complexes of 2-[(diorganylphosphinoyl)hydroxymethyl)-1-organylimidazoles I VII
Found, %
201
Calculated, %
H Cl
Comp.
no.
Yield,
%
mp,
C
Formula
C
H
Cl
C
ZnCl2 II
ZnCl2 III
ZnCl2 IV
74
73
17
53
39
33
48
80
80
59
64
55
71
42
80
87
160(decomp.) 47.15
3.97
4.16
3.76
4.56
5.35
4.16
3.53
4.70
4.08
4.17
4.28
4.15
3.09
4.05
4.10
4.95
15.22 C18H17Cl2N2O2PZn
13.23 C22H21Cl2N2O2PZn
14.20 C22H19Cl2N2O2PZn
17.39 C13H17Cl2N2O2PZn
10.66 C28H38Cl2N4O4P2Zn
8.54 C34H34CdCl2N4O4P2 50.53
13.73 C18H17CdCl2N2O2P 42.60
7.40 C44H42CdCl2N4O4P2 56.15
7.75 C44H38CdCl2N4O4P2 56.71
15.76 C13H17CdCl2N2O2P
14.16 C18H21CdCl2N2O2P
8.76 C17H16ClCuN2O2P
14.43 C36H34Cl4N4O4P2Sn
7.45 C22H18ClCoN2O2P
15.84 C13H17Cl2N2O2PPd
8.96 C36H42Cl2N4O4P2Pd
46.94
51.52
51.76
38.96
48.55
3.72
4.10
3.73
4.25
5.49
4.21
3.33
4.49
4.08
3.83
4.11
3.90
3.40
3.85
3.85
5.04
15.39
13.36
13.92
17.73
10.26
8.79
14.00
7.59
7.62
15.58
13.89
8.66
14.22
7.59
192 195
210 212
51.28
51.48
ZnCl2
V
128(decomp.) 39.31
110(decomp.) 48.05
170(decomp.) 50.07
ZnCl2 2VI
CdCl2 2I
CdCl2 II
CdCl2 2III
CdCl2 2IV
123 125
185 187
43.01
55.87
190(decomp.) 56.50
CdCl2
V
158 160
175 177
122 124
144 147
117 119
162 163
149 151
35.03
41.92
49.57
43.26
56.57
35.23
51.54
34.89
42.27
49.76
43.26
56.47
35.37
51.86
CdCl2 VII
CuCl2 (I-H)
SnCl4 2II
CoCl2 (IV-H)
PdCl2
V
16.10
8.52
PdCl2 2VII
atom, depending on the nature of the acceptor.
Moreover, bidentate ligation, as well as chelate forma-
tion are also possible.
NMR spectra of free and coordinated ligands I VII.
1
In [10], by means of IR and H and 31P NMR
spectroscopy we showed that compounds I IV
contain both intra- and intermolecular hydrogen bonds,
mainly of the OH O=P type.
The reactions of imidazoles I VII with metal
chlorides were carried out at room temperature or at
70 C in ethanol or acetone at 1:1 and 1:2 salt:ligand
ratios (Table 1). As a result, complexes with the com-
position corresponding mostly to the starting reagent
ratio were isolated, except for the adducts ZnCl2 L
(L = III V), CdCl2 II, and CoCl2 IV, in which the
salt:ligand ratio is higher than that taken in reaction
(1:2). The complex PdCl2 2VII was obtained at an
equimolar salt:ligand ratio in the reaction mixture
(Table 1). The preferred site of coordination of metals
to polydentate imidazolylphosphine oxides was de-
In the present work, to establish the mutual loca-
tion of electron-donor centers in ligands I VII, we
performed quantum-chemical calculations of the
model 2-[(dimethoxyphosphinoyl)hydroxymethyl]-1-
methylimidazole (X) at the HF/6-31G* level with full
geometry optimization. As a result, it was established
that imidazolylphosphine oxide X has three energe-
tically stable forms with intramolecular hydrogen
bonds OH O=P (Xa) and OH N (Xb), and with a
free OH group (Xc) (see scheme bellow).
1
termined by comparative analysis of the IR and H
O
H3C
H3C
CH3
P
H3C
H3C
^
2
N
1 N
N
CH
P
HO
O
H
)
)
/
/
O
CH
CH
.
.
2
N
N
N
^
.
1
O
H
H3C P=O
H3C
CH3
CH3
Xa
Xb
Xc
1 113
83
2 177
134
1 132 , 2 71
130
4.99 D
E 21.4 kJ mol
1.09 D
E 0 kJ mol
2.11 D
E 19.3 kJ mol
1
1
1
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

202
The
BAIKALOVA et al.
1
2
and
dihedral angles in structures Xa Xc
chelate complexes most frequently produces a red
shift of the stretching vibration frequencies of the
heteroring [15].
relate to rotation of the azole ring or the phosphine
oxide group with respect to the plane defined by the
C OH group. The
angle determines the mutual
In the IR spectra of the complexes of ZnCl2, CdCl2,
PdCl2, and SnCl4 with imidazolylphosphine oxides
I VII, there are stretching vibration bands of the
position of the planes defined by the P=O group and
the heteroring. The calculations show that these planes
are almost orthogonal to each other: The angle is
83 in form Xa and 134 and 130 in forms Xb and
Xc, respectively. Under real conditions, the effects of
the medium and coordinating agent can shift the equi-
librium between forms Xa Xc that have much dif-
ferent calculated dipole moments (see scheme).
1
hydroxymethyl group: C O (1030 1050 cm ) and
1
OH (3070 3300 cm ), implying intramolecular
hydrogen bonding of the coordinated ligands. The
absorption band of the associated OH group of the
1
free ligands ( 3000 3100 cm ) in the spectra of the
corresponding complexes increases to 3250
1
1
3300 cm for MCln L and to 3070 3180 cm for
MCln 2L (Table 2). Such a blue shift of the (OH)
band may be associated both with the weakening of
intramolecular hydrogen bonding due to formation of
an additional O M bond [16, 18] and with a change
in the type of association [10]. Thus, analysis of the
IR spectra of coordinated and free ligands I VII, as
well as the ortogonal mutual location of the donor
centers in the ligands in hand (trans conformation),
proposed on the basis of calculations, allows the 1:1
complexes to be assigned the structure of polymeric
chains with both heteroatoms being coordination
centers and the ligand playing the role of a bridge
between the central atoms of complex A. We do not
also exclude formation of an OH OH hydrogen bond
in complexes A. Evidence for this suggestion is
provided by a considerable shift of the (OH) band
In the IR spectra of the metal complexes of imida-
zoles I VII, the P=O bands are shifted red by 30
1
50 cm compared with the respective bands of the
free ligands, unlike what is observed with ionic com-
plexes of imidazolylphosphine oxides VIII and IX
[9, 10] whose P=O absorption band is in the same
place as in the spectra of the free ligands (Table 2).
The bands of stretching vibrations of the azole ring
1
(1410 1510 cm ) of free ligands I VII are shifted
slightly blue in going to the 1:1 complexes and
remain unchanged in going to the 2L:1 complexes
(Table 2). Note that the monodentate coordination of a
ligand to an electron acceptor, involving the oxygen
atom in phosphine oxides [11, 12] or the pyridine
nitrogen atom in azole derivatives [9, 10, 13, 14]
(Table 2) is accompanied by a stronger shift of the
P=O and heteroring absorption bands (by 80 100 and
1
(to 3250 3300 cm ) compared with the free ligand
(Table 2).
1
10 30 cm , respectively), whereas formation of
R2 R3
R2 R3
Ph
R
O
CH
H
N
N
M
O=P
N
N M
R1
R1
CH
CH
R1
M
O=P
R
N
N
O=P
R
O
H
O
H
Ph
Ph
R3
R2
A
M = Zn, Cd, Pd, Sn.
Note that the complex formation gives rise to
additional interactions and may be attended with a
transition of the imidazolylphosphine oxides to the
cisoid conformation. At such a location of the N and
O centers, molecules I VII can, playing the role of a
double bridge between the metal atoms, form dimeric
2:2 complexes B. For example, by X-ray diffraction
we revealed a similar structure in bis( -1,1 -divinyl-
2,2 -biimidazolyl)tetrachlorodicobalt; therewith, the
coordinated 1,1 -divinyl-2,2 -biimidazolyl ligand had
the same cisoid conformation as the free ligand
[18, 19].
In the 2L:1 complexes, imidazolylphosphine
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

COMPETITIVE COORDINATION OF 2-[(DIORGANYLPHOSPHINOYL)-...
203
Table 2. IR (KBr) and 1H NMRa (DMSO-d6) spectral parameters of free and coordinated 2-[diorganylphosphinoyl)-
hydroxymethyl]-1-organylimidazoles I IX
1
Compound
IR, , cm
P=O OH
NMR, , ppm
CHOH, d
heteroring
HA (d.d)b
HB (d.d)b
H4, d
H5, d
6.70
I
1180 3100 1485, 1440, 1405
5.78
7.04
CdCl2 2I 1150 3180 1485, 1440
5.99( 0.21)
7.10( 0.06)
6.87( 0.17)
CuCl2
II
I
1130
1200 3000
1495, 1440, 1415
1480, 1435
4.74
5.33
5.91
7.44
6.80
ZnCl2 II
CdCl2 II
1150 3300 1485, 1438
1150 3250 1485, 1435
4.81( 0.07) 5.37( 0.04) 6.05( 0.14)
4.81( 0.07) 5.34( 0.01) 6.01( 0.10)
4.92( 0.18) 5.49( 0.16) 6.14( 0.23)
7.45( 0.01)
7.45( 0.01) 6.87( 0.07)
7.47( 0.03) 7.17( 0.37)
6.90( 0.10)
SnCl4 2II 1160 3120 1480, 1435
III 1200 3000 1475, 1435, 1410
ZnCl2 III 1145 3300 1485, 1440, 1435
CdCl2 2III 1170 3120 1475, 1437, 1410
6.05
6.08
6.19
IV
1190 3080 1470, 1450, 1430
5.13
5.16
5.56
5.55
6.10
ZnCl2 IV 1140 3280 1480, 1465, 1435
CdCl2 2IV 1165 3100 1470, 1450, 1430
6.14
CoCl2 IV 1135
1485, 1460, 1430
V
1180 3100 1480, 1460, 1435
1160 3300 1500, 1465, 1445
5.88
5.57(+0.31)
5.51, 5.39
5.55(+0.33)
5.46, 5.37
5.24(+0.64)
5.81, 5.80
5.57, 5.40
(+0.24),
7.58
7.39
ZnCl2
V
7.24(+0.34)
7.16, 7.11
7.15(+0.43)
7.10, 7.07
7.00(+0.39)
6.95, 6.92
7.00(+0.39)
6.94, 6.92
ZnCl2 Vc
CdCl2
V
1150 3250 1495, 1460, 1440
CdCl2 Vc
PdCl2
VI
V
1150 3250 1495, 1460, 1440
1180 3095 1490, 1460, 1440
7.53, 7.49
7.32, 7.12
(+0.21),
(+0.37)
7.27, 7.23
7.00, 6.92
(+0.27),
(+0.31)
ZnCl2 2VI 1155 3120 1490, 1460, 1440
(+0.40)
VII
1190 3070 1480, 1455, 1430
6.17, 5.97
5.87, 5.65
(+0.30),
CdCl2 VII 1150 3250 1485, 1460, 1435
(+0.32)
PdCl2
2VII
1160 3050
3150
1480, 1455, 1430
5.52, 5.40
(+0.65),
(+0.57)
VIII
1157 3105 1521, 1495, 1483
4.85
5.41
5.23
7.20
7.01
CH3I VIII 1155 3110 1542, 1517, 1496 5.33( 0.48) 5.63( 0.22) 6.19( 0.96)
7.23( 0.03) 7.12( 0.11)
IX
1200 3100 1490, 1445
5.70
6.52( 0.82)
6.83
7.29( 0.46)
6.83
7.01( 0.18)
CSAd IX 1200 3140 1518, 1445
a
Parenthesized are the direction and magnitude of the signal shift in going from the starting ligand to the complex: ( ) downfield
c
d
b
shift and (+) upfield shift. Signals of the vinyl group Het CH =CHAHB. At 80 C. CSA is camphorsulfonic acid.
x
oxides act as monodentate ligands coordinating via
the P=O oxygen atom. In complexes C, either an
OH N hydrogen bond may form or the OH O=P
hydrogen bond may be preserved with simultaneous
involvement of the oxygen atom in coordination with
metal, which is evidently confirmed by the smaller
R2 R3
Ph
R
O
CH
H
N
N
M
O=P
R1
R1
CH
HO
=O
P
M
N
N
1
blue shift (to 3070 3180 cm ) of the (OH) band
(Table 2).
Ph
R
R3
R2
B
M = Zn, Cd, Pd, Sn.
Abundant X-ray diffraction evidence is available
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

204
BAIKALOVA et al.
R2
R2
R2 R3
R2 R3
R1
R1
O
R3
R3
N
N
N
N
N
N
N
N
R1
R1
O
H
CH
HC
P
H
CH
CH
H
H
=O
R
M
=O
P
M
O
O=P
R
O=P
R
O
Ph
Ph
P
h
P
h
R
C
M = Zn, Cd, Pd, Sn.
for the simultaneous involvement of oxygen in an
intramolecular hydrogen bond and a donor acceptor
bond [1, 20, 21].
plexes. The adducts of ligands III and IV are an
exception, because the proton chemical shifts of the
free azoles and their complexes with ZnCl2 and CdCl2
are identical (Table 2). This fact suggests that the
latter complexes are completely dissociated in DMSO
solutions. The considerable downfield shifts of the
vinyl (HA and HB) and heteroring (H4 and H5) signals
The reactions of imidazolylphosphine oxides I and
IV with copper and cobalt dichlorides provide
chelates D.
1
R2
in the H NMR spectra of the complexes of imida-
Ph
R
R1
zoles I and II compared to the respective signals of
the free ligands are indicative of donor acceptor inter-
action of the metals with, primarily, N3 [13, 14].
R3
P=O
N
M
N
CH
O
Appreciable shifts of these proton signals (
0.16
M
O
N
HC
0.37 ppm) are observed for the complex SnCl4 2II
R3
N
R1
P=O
that comprises the strongest acceptor in the series of
1
P
R
h
R2
metal chlorides in hand (Table 2). In the H NMR
D
spectra of stronger ionic complexes of imidazolyl-
phosphine oxides VIII and IX with CH3I and cam-
phorsulfonic acid, in which the acceptors are coor-
dinated in the monodentate fashion by the pyridine
nitrogen atom of the heteroring [9, 10], the downfield
shift of the respective signals reaches more significant
values than in the spectra of the adducts under study
(Table 2). Evidently, the electrostatic repulsion of the
phenyl system in compounds I and II and electrons
of the central metal atom renders the coordination
bond of the latter with the P=O oxygen atom in
DMSO solutions weaker than the N3 M bond and
makes it to dissociate.
M = Co, Cu.
The IR spectra of the CuCl2 and CoCl2 complexes
contain no absorption bands due to stretching and
deformation vibrations of the OH group. The largest
shift of the P=O band (50 55 cm ) is observed, and
the blue shift of the heteroring band reaches 15 cm
compared to free ligands I and IV (Table 2). Unlike
what is observed with mixed-ligand chelate com-
pounds on the basis of 2-(hydroxymethyl)-1-vinylimi-
dazoles [22], the evolving HCl enters into donor
acceptor interaction with the lone electron pair of the
N3 atom of the azole ring, which is confirmed by the
elemental analyses (Table 1) and IR spectra (lack of
the characteristic NH+ band in the range 2600
1
1
We found a strong upfield shift of the heteroring
1
and CH signals in the H NMR spectra of the com-
plexes of 2-(ethylphenylphosphinoyl)imidazoles V
VII compared with the respective signals of the free
ligands, which has never been observed in the case of
coordination by the nitrogen atom [23]. Such an up-
field shift is evidently produced by the shielding
effect of the aryl ring through space, which becomes
possible if the azole and aryl rings are strongly aco-
planar. In this case, the 1H NMR spectra of the
adducts with ligands V VII provide indirect evidence
for preservation of the coordination by the oxygen
atom, because on coordination by N3 substitution of
the phenyl substituent by ethyl should not such sig-
1
3000 cm ). Evidently, both in the Cu and in the Co
chelate compounds with ligands I and IV, the si-
multaneous coordination of two acoplanar donor
centers, P=O oxygen and heteroring N3, too, is re-
alized via formation of polymeric structures in which
the corresponding imidazolohosphine oxide plays the
role of a bridging N,O-bidentate ligand.
The 1H NMR spectra of imidazolylphosphine
oxides I, II, and V VII in DMSO differ considerably
from the spectra of their Zn, Cd, Sn, and Pd com-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 2 2005

COMPETITIVE COORDINATION OF 2-[(DIORGANYLPHOSPHINOYL)-...
205
nificantly affect the strength of the N3 M donor
acceptor bond. Note that in the H NMR spectra of
4. RU Patent 2038079, 1995; Byull. Izobret., 1995,
1
no. 18.
the complexes with ligands V VII, the signal of the
CH proton of the hydroxymethyl group is shifted
stongly upfield compared with the respective signal of
the free donors, which can be considered one more
evidence for coordination by the P=O oxygen atom.
5. Odareeva, E.V. and Baikalova, L.V., in Aktual’nye
voprosy onkologii (Actual Problems of Oncology),
Irkutsk, 1998, pp. 76 77.
6. Domnina, E.S., Baikalova, L.V., Voronkov, M.G.,
Veksler, I.G., and Balitskii, K.P., Abstracts of Papers,
Vsesoyuznyi seminar po khimii fiziologicheski aktiv-
nykh soedinenii (All-Union Seminar on Chemistry of
Physiologically Active Compounds), Chernogolovka,
1989, p. 88.
1
According to H and 31P NMR data in [9], phos-
phine oxides with two asymmetric centers (carbon and
phosphorus) exhibit diastereomerism. In the spectra
of their complexes, most signals are split, which is
explained by preservation of two diastereomers of
ligands V VII in the molecules of the corresponding
metal complexes (Table 2).
7. Medvedeva, E.N., Neverova, I.A., Babkin, V.A.,
Reutskaya, A.M., and Zyryanova, I.A., Abstracts of
Papers, 2 Vserossiiskaya konferentsiya Khimiya i
tekhnologiya rastitel’nykh veshchestv (2nd Russian
Conf. Chemistry Technology of Plant Substances,
Kazan, 2002, p. 151.
In conclusion it may be said that unambiguous
conclusions as to the structure of the synthesized
complexes and their coordination centers may be
made by means of X-ray analysis.
8. Reutskaya, A.M., Cand. Sci. (Chem.) Dissertation,
Irkutsk, 2001.
EXPERIMENTAL
9. Gusarova, N.K., Arbuzova, S.N., Reutskaya, A.M.,
Ivanova, N.I., Baikalova, L.V., Sinegovskaya, L.M.,
Chipanina, N.N., Afonin, A.V., and Zyryanova, I.A.,
Khim. Geterotsikl. Soedin., 2002, no. 1, pp. 71 77.
The IR spectra were recorded on a Bruker IFS-25
instrument in KBr pellets. The NMR spectra were
obtained on a Bruker DPX-400 instrument in DMSO-
d6 solutions at room temperature and at 80 C against
internal HMDS. Quantum-chemical calculations with
full geometry optimization were carried out using the
GAUSSIAN-98 program package [24].
10. Chipanina, N.N., Baikalova, L.V., Sinegovskaya, L.M.,
Kanitskaya, L.V., Fedorov, S.V., Zyryanova, I.A.,
Reutskaya, A.M., Tiunov, M.P., Gusarova, N.K.,
and Trofimov, B.A., Zh. Obshch. Khim., 2004, vol. 74,
no. 4, p. 591.
The complexes of metal chlorides with ligands I,
II, and IV VII were obtained by stirring ligand
and metal salt in absolute ethanol at 60 C for 8 15 h
and subsequent precipitation of the products with
ether and drying. The complexes of CdCl2 with ligand
I and of metal chlorides with ligand III were obtained
at room temperature.
11. Skopenko, V.V. and Zub, Yu.L., Ukr. Khim. Zh., 1978,
vol. 44, no. 12, pp. 1235 1241.
12. Skopenko, V.V., Zub, Yu.L., and Matishinets, I.M.,
Ukr. Khim. Zh., 1984, vol. 50, no. 7, pp. 675 680.
13. Baikalova, L.M., Domnina, E.S., Chipanina, N.N.,
Khamaganova, L.D., Afonin, A.V., and Gavrilo-
va, G.A., Koord. Khim., 1997, vol. 23, no. 2,
pp. 95 101.
The complexes of PdCl2 with ligands III, V, and
VII were obtained by adding ligands in aqueous
K2[PdCl4]. The precipitates that formed were filtered
off, washed with acetone, and dried in a vacuum.
14. Baikalova, L.V., Domnina, E.S., Kashik, T.V., Gav-
rilova, G.A., Kukhareva, V.A., Afonin, A.V., and
Mamaseva, T.V., Zh. Obshch. Khim., 1998, vol. 68,
no. 5, pp. 842 847.
The complex of PdCl2 with ligand IV was ob-
tained in acetone at 56 C for 21 h. The product was
then filtered off, washed with acetone, and dried.
15. Garnovskii, A.D., Osipov, O.A., and Sheiker, V.N.,
Koord. Khim., 1980, vol. 6, no. 1, pp. 3 26.
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