Palladium(II) chloro complexes with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol

Article abstract of DOI:10.1134/S0036023615050101

Palladium(II) chloro complexes with (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-tria-zol-1-ylmethyl)pentan-3-ol (L), such as trans-[PdCl₂L₂], cis-[PdCl₂L₂], and trans-[Pd₂(μ-Cl)₂Cl₂L₂], were synthesized. The structures of their coordination cores and the coordination modes of the reagent to the metal ion via the N(4) atom of the triazole ring were established by electronic, IR, and ¹H and ¹³C NMR spectroscopy. The ratio of RS- and RR(SS)-diastereomers in the complexes was determined from the complete assignment of signals in their ¹H and ¹³C NMR spectra.

Full text of DOI:10.1134/S0036023615050101

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2015, Vol. 60, No. 5, pp. 638–646. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.A. Khisamutdinov, O.V. Shitikova, G.R. Anpilogova, L.G. Golubyatnikova, R.F. Mulagaleev, Yu.I. Murinov, 2015, published in Zhurnal Neorganicheskoi
Khimii, 2015, Vol. 60, No. 5, pp. 710–718.
PHYSICAL CHEMISTRY
OF SOLUTIONS
Palladium(II) Chloro Complexes with (RS)ꢀ1ꢀ(4ꢀchlorophenyl)ꢀ
4
,4ꢀdimethylꢀ3ꢀ(1Hꢀ1,2,4ꢀtriazolꢀ1ꢀylmethyl)pentanꢀ3ꢀol
a
a
a
R. A. Khisamutdinov , O. V. Shitikova , G. R. Anpilogova ,
a
b
a
L. G. Golubyatnikova , R. F. Mulagaleev , and Yu. I. Murinov
a
Ufa Institute of Chemistry, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, Bashkortostan, 450054, Russia
Institute of Chemistry and Chemical Engineering, Siberian Branch, Russian Academy of Sciences,
ul. Karla Marksa 42, Krasnoyarsk, 660049 Russia
b
eꢀmail: hisam@anrb.ru
Received August 15, 2014
Abstract—Palladium(II) chloro complexes with (RS)ꢀ1ꢀ(4ꢀchlorophenyl)ꢀ4,4ꢀdimethylꢀ3ꢀ(1Hꢀ1,2,4ꢀtriaꢀ
zolꢀ1ꢀylmethyl)pentanꢀ3ꢀol (L), such as transꢀ[PdCl L ], cisꢀ[PdCl L ], and transꢀ[Pd2( ꢀCl) Cl L ], were
µ
2
2
2
2
2
2 2
synthesized. The structures of their coordination cores and the coordination modes of the reagent to the
1
13
metal ion via the N(4) atom of the triazole ring were established by electronic, IR, and H and C NMR
spectroscopy. The ratio of RSꢀ and1RR SS)1ꢀ3diastereomers in the complexes was determined from the comꢀ
(
plete assignment of signals in their H and C NMR spectra.
DOI: 10.1134/S0036023615050101
(RS)ꢀ1ꢀ(4ꢀchlorophenyl)ꢀ4,4ꢀdimethylꢀ3ꢀ(1Hꢀ1,2,4ꢀ
and other pharmacological activities, is of certain
triazolꢀ1ꢀylmethyl)pentanꢀ3ꢀol (tebuconazole) is known practical interest.
as a systemic fungicide and widely applied in agriculꢀ
The objective of this work is to synthesize pallaꢀ
tural industry. Being a 1Hꢀ1,2,4ꢀtriazole derivative,
this compound has antibacterial and insecticide propꢀ
erties [1]. We have shown earlier that the compound is
an efficient and selective agent for the extraction of
copper(II) and gold(III) from hydrochloric acid soluꢀ
tions and for the extraction of palladium(II) from
hydrochloric and nitric acid solutions [2–4]. Some
zinc(II) and copper(II) complexes with tebuconazole
are known [5]. Similar propiconazole complexes with
higher antifungal activity than the reagent itself were
proposed for application in wood preserving formulaꢀ
tions [6].
dium(II) chloro complexes with (RS)ꢀ1ꢀ(4ꢀchloꢀ
rophenyl)ꢀ4,4ꢀdimethylꢀ3ꢀ(1Hꢀ1,2,4ꢀtriazolꢀ1ꢀylmeꢀ
thyl)pentanꢀ3ꢀol and to establish its structure.
EXPERIMENTAL
The reagent in this work was (RS)ꢀ1ꢀ(4ꢀchloropheꢀ
nyl)ꢀ4,4ꢀdimethylꢀ3ꢀ(1Hꢀ1,2,4ꢀtriazolꢀ1ꢀylmethyl)penꢀ
tanꢀ3ꢀol (L)
OH
Cl
CH2 CH2 C C(CH3)3
The weakly basic and complexing properties of
tebuconazole are due to the presence of a 1Hꢀ1,2,4ꢀ
triazole ring in its structure [3, 5, 7]. According to
quantumꢀchemical calculations, the N(4) atom has
the highest electron density among the electronꢀ
donating atoms in the ring [8]. The bulk alkyl substitꢀ
uent at the N(1) atom in substituted 1Hꢀ1,2,4ꢀtriazꢀ
oles creates sterical hindrances for the participation of
the N(2) atom in the coordination to transition metal
ions and promotes the formation of an electronꢀ
donating bond only via the N(4) atom [9]. The coorꢀ
CH2
N
HC
N
N CH
The purity of the reagent established by elemental
analysis (Table 1), NMR spectroscopy, and highꢀperꢀ
formance liquid chromatography was no less than
8%. The physicochemical characteristics of the
reagent correspond to the literature data [10].
9
The complexes were synthesized using palladium(II)
dination of tebuconazole to the central metal ion via chloride of pure grade and potassium tetrachloropallaꢀ
the N(4) atom was established by Xꢀray diffraction for date(II) K [PdCl ] [11] and transꢀ(bisꢀacetonitrile)dichloꢀ
2
4
[
Zn(OAc) L ], [Cu(OAc) L2], and [CuCl L ] ⋅ 4EtOH ropalladium [PdCl (CH CN)2] [12] synthesized by known
2 2 2 2 4
2 3
1
13
15
[
5] and by Н, С, and
N
NMR for AuCl3L [3]. The methods. Sodium cisꢀdichloromalonatopalladate(II)
cis PdCl {CH (COO) }] 2H O was synꢀ
tebuconazole, which can potentially have anticancer thesized at 20
synthesis of platinum group metals complexes with dihydrate Na2
[
ꢀ
⋅
2
2
2
2
°
C from transꢀ[PdCl (CH CN)2] and
2 3
638

PALLADIUM(II) CHLORO COMPLEXES
639
Table 1. Physicochemical characteristics of reagent L and its chloro complexes with palladium(II)
Elemental analysis results, calcd/found, %
Predetermined Composiꢀ
Compound
Λ
,
Tm, C
°
2
Pd(II) : L ratio
tion
(S cm )/mol
C
H
N
Cl
Pd
L
L
103–104
153
6
6
2.44
2.30
7.20
ꢀꢀꢀꢀꢀꢀꢀ
13.65
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
11.52
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
7.26
13.53
10.82
1
1
: 2 (method A) PdCl2L2
: 1 (method B) PdCl2L2
0.5
0.5
–
48.47
5.59
ꢀꢀꢀꢀꢀꢀꢀ
10.60
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
17.89
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
13.42
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀ
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
4
8.42
5.32
10.55
17.99
14.00
I
153
48.47
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
5.59
ꢀꢀꢀꢀꢀꢀꢀ
10.60
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
17.89
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
13.42
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀ
4
8.31
5.33
10.54
18.25
14.16
II
1 : 2
1 : 1
PdCl2L2
197
48.47
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
5.59
ꢀꢀꢀꢀꢀꢀꢀ
10.60
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
17.89
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
13.42
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀ
4
8.57
5.77
10.57
18.65
13.22
III
Pd Cl L
135–137
3.3
2
4
2
39.61
ꢀꢀꢀꢀꢀꢀꢀꢀꢀ
4.58
ꢀꢀꢀꢀꢀꢀꢀ
8.66
ꢀꢀꢀꢀꢀꢀꢀ
21.92
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
21.93
ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ
ꢀ
4
0.45
4.41
8.72
20.50
21.12
disodium malonate of pure grade at a molar ratio of tate was filtered out, washed with water and then hexꢀ
reagents of 1 : 1 by mixing their saturated aqueous soluꢀ ane, and dried. The yield was 92%.
tions. The yield was 82%.
Complex [Pd Cl L ] (III) was synthesized at a preꢀ
2
4 2
Acetone (pure for analysis), acetonitrile (high
purity), hexane (pure), and chloroform (chemically
pure) were used in the work.
determined ratio Pd(II) : L = 1 : 1. To palladium(II)
chloride (0.20 g, 1.13 mmol) placed into a 25ꢀmL
pearꢀshaped flask with a reflux condenser, acetonitrile
The palladium(II) chloro complexes were syntheꢀ
sized via the innerꢀsphere substitution of acido or neuꢀ
tral ligands by reagent L.
(
10 mL) was added, and the resulting mixture was
refluxed on a sand bath until the salt was completely
dissolved. The formed yellowꢀbrown transꢀ(bisꢀacetoꢀ
nitrile)dichloropalladium solution was cooled to
Complex transꢀ[PdCl L ] (I) was prepared at 20°С
2 2
by methods A and B at different predetermined 60
°С, thereupon reagent L (0.35 g, 1.13 mmol) was
Pd(II):L molar ratios.
added. The color of the solution changed to light yelꢀ
low. Acetonitrile was removed on a rotary evaporator,
Method A: The batch ratio was Pd(II) : L = 1 : 2.
To a magnetically stirred aqueous solution (3 mL) and the separated substance was washed with hexane
containing K [PdCl ] (0.30 g, 0.92 mmol), the reagent and dried. The yield was 95%.
2
4
L (0.57 g, 1.84 mmol) dissolved in acetone (6.5 mL)
was added. The brown color of the solution quickly
changed to orange. The bulky yellow precipitate was
formed in 5 h; in 16 h after the evaporation of acetone,
Electronic absorption spectra (EAS) of acetonitrile
solutions of the reagent and complexes were recorded
on a Specord M40 spectrophotometer. The IR spectra
the precipitate was filtered out, washed with water and of the compounds were taken on a Specord M80 specꢀ
–1
then hexane, and dried in air. The yield was 97%.
trophotometer in the region of 4000–250 cm (Nujol
mulls, KRSꢀ5), and their NMR spectra were recorded
on a Bruker Avance III spectrometer (at a working freꢀ
Method B: The predetermined ratio was Pd(II) : L =
: 1. To an aqueous solution (3 mL) containing
1
1
13
quency of 500 MHz for H and 125 MHz for C) using
.92 mmol) dissolved in acetone (6.5 mL) was added CDCl and DMFꢀ as solvents. The melting temperꢀ
K [PdCl ] (0.30 g, 0.92 mmol), the reagent (0.28 g,
0
2
4
d
7
3
under stirring. A yellow precipitate was formed in few atures of the compounds were determined on a Boetꢀ
minutes. After stirring for 24 h the precipitate was filꢀ ius heating table, and the electrical conductivity of
tered out, washed with water and hexane, and dried.
The yield was 81% based on the reagent.
0
.001 mol/L complexes solutions in dry acetone was
measured on an OK 102/1 conductometer with an
OPꢀ907/3 electrode.
Complex cisꢀ[PdCl L ] (II) was prepared at 20°С
2 2
and the predetermined ratio Pd(II) : L = 1 : 2. To an
aqueous solution (1 mL) of cisꢀsodium dichloromaꢀ
lonatopalladate(II) dihydrate (0.063 g, 0.17 mmol), a
solution (1 mL) of the reagent (0.102 g, 0.33 mmol) in
The NMR spectra were recorded and the elemental
analysis of the compounds was performed on the
equipment of the Shared Facility Center “Chemistry”
chloroform was added under stirring. A yellow precipꢀ of the Institute of Organic Chemistry of the Ufa Sciꢀ
itate was formed for 3 h. On the next day, the precipiꢀ entific Center of the Russian Academy of Sciences.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 5 2015

640
KHISAMUTDINOV et al.
RESULTS AND DISCUSSION
The chemical compositions of the synthesized
complexes were established by elemental analysis
Table 1). The obtained complexes represent powderꢀ
like yellow waterꢀinsoluble substances. Complexes
and III are well soluble in acetone, acetonitrile, toluꢀ
ene, and chloroform. In contrast to them, complex II
is soluble only in DMF. The low molar electrical conꢀ
ductivities of the solutions (Table 1) indicate that
Δ
takes place for the hydrogen and carbon atoms
located in the immediate proximity to the N(4'') atom
of the triazole ring and is ~0.8 ppm for the H(5'') atom
in CDCl3 (0.4–0.5 ppm in DMFꢀd7), ~0.5 ppm for
the H(3'') atom in CDCl3 (0.3–0.4 ppm in DMFꢀd7),
and 1.2–1.5 ppm for the C(1'), C(3''), and C(5'')
atoms. The change in chemical shifts for the other sigꢀ
(
I
1
nals does not exceed 0.1 and 0.5 ppm in the H and
13
C NMR spectra, respectively. We should note that
the redistribution of electron density in the conjugated
system of the triazole ring in the complexes leads to the
upfield shift of the C(3'') atom signal and the downꢀ
field shift of the C(5''), C(1'), H(3''), and H(5'') atoms
signals.
complexes I and III are neutral [13].
To establish the coordination mode of the ligand to
palladium(II) and the structure of coordination cores,
we compared the NMR, IR, and electronic absorption
spectra of the reagent and the complexes.
Despite that the change in the chemical shift of the
The complete assignment of signals in the NMR
spectra of reagent L and the complexes is given in
1
hydroxyl group proton signal in the H NMR spectra
attains 2 ppm, there is obviously no coordination of
the reagent via the oxygen atom; if otherwise a set of
signals from the C(2), C(3), C(4), and H(2) atoms,
which are closest to the oxygen atom, would have been
observed, but it is missing. The location of the signal
from this proton seems to change due to its participaꢀ
tion in exchange processes.
13
Tables 2 and 3. The C NMR spectra contain lowꢀ
2
field signals from the sp ꢀhybridized carbon atoms of
the triazole and aromatic rings in the regions of 140–
1
50 and 128–140 ppm, respectively, and a highꢀfield
signal from methyl groups of the tertꢀbutyl moiety
Table 2). The signals from the C(3) atom linked to the
(
oxygen atom and the C(1') atom at the nitrogen atom
lie at 75 and 55 ppm, respectively. The signals from
The reagent coordination mode established by
protons of the triazole ring and the tertꢀbutyl moiety in NMR spectroscopy is confirmed by IR spectroscopic
1
the H NMR spectra of the reagent and the complexes data. In the IR spectra of all the complexes, the
(
Table 3) are located at 8.0–9.2 and 1.00 ppm, respecꢀ absorption band of the stretching and bending vibraꢀ
–1
tively. The chemical shifts of the signals from the НА tions of the triazole ring
νring shifts by 16–32 cm
and НВ protons of methylene groups differ from each towards higher frequencies with respect to its location
other due to the different effects produced on these in the reagent spectrum (Table 4), thus indicating that
protons by the substituents at the chiral C(3) carbon the reagent is coordinated via a pyridineꢀtype nitrogen
atom. The vicinal constants of spin–spin coupling atom, probably, the N(4) atom [14–16].
(
CSSC)
В
J = 12.5 and J = 5.0 Hz between the Н (1),
А
The reaction between reagent L and potassium tetꢀ
rachloropalladate(II) in water–acetone media to the
Н (1), Н (2), and Н (2) protons indicate the retarꢀ
dation of free rotation around the C(1)–C(2)
bond in the preferred conformation, in which the benꢀ
zene ring and the C(3) atom are in transꢀposition as
shown in the Newman projection
А
В
σ
ꢀ
formation of complex
the predetermined Pd(II) : L ratio (Table 1). The presꢀ
ence of one strong absorption band assigned to (Pd–
Cl) in the farꢀIR spectrum of the complex at 357 cm
Table 4) indicates the transꢀconfiguration of its coorꢀ
I [PdCl2L2] independently of
ν
–1
(
H H
C(3)
H
(
CH ) C
3 3
dination core with symmetry D2h [17–19]. The
C(1)
–1
N
mediumꢀintensity absorption band at 323 cm can be
Cl
N
assigned to
configuration of complex
its solution containing two overlapping absorption
bands, which have maxima at 362 nm ( = 110) and 391
nm ( ~ 100) and correspond to spinꢀallowed
transitions in the palladium(II) ion incorporated into
planar complexes like trans PdCl L (D2h [17, 20,
1]. There are no absorption bands in the visible
ν(Pd–N) [14, 16, 18]. The squareꢀplanar
N
O
H H
I
is confirmed by an EAS of
H
H
ε
In the case of such an arrangement, the Н (1) and
А
ε
d–d
Н (1) protons are spatially close to the bulk substituꢀ
В
ents at the chiral C(3) atom, so the chemical shifts of
the protons at the C(1) atom have a greater difference
between each other (0.64–0.51 ppm) than ones of the
protons at the C(2) and C(1') atoms (0.07–0.00 and
ꢀ
)
2
2
2
region of an EAS of reagent L solution, and but its
ultraviolet region contains a set of strong absorption
0
.10–0.02 ppm, respectively).
bands assigned to the π → π
*
transitions of the
pꢀsubꢀ
1
The change of the chemical shifts in the H and stituted aromatic and triazole rings: the aromatic ring
C NMR spectra of complexes in CDCl3 and/or Е2ꢀband at 205 nm (
13
ε
= 14500), the triazole ring I
ꢀband
DMFꢀd7 (Tables 2 and 3) in comparison with the specꢀ at 222 nm (
ε
= 10200), and the band at 269 nm (
tra of the reagent allows us to state that the reagent in 410) with shoulders at 263 and 276 nm due to the overꢀ
the complexes I–III is coordinated via the N(4'') lapping of the aromatic ring ꢀband and the triazole
nitrogen atom. The greatest change in chemical shifts ring band II corresponding to → π transitions [22, 23].
ε
=
B
n
*
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PALLADIUM(II) CHLORO COMPLEXES
641
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642
KHISAMUTDINOV et al.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 5 2015

PALLADIUM(II) CHLORO COMPLEXES
643
Table 4. Characteristic absorption bands in the IR spectra of reagent L and its chloro complexes with palladium(II)
Compound
L
Type of complex
ν
, cm–1
ν
(Pd–Cl), cm–1
ν
(Pd–N), cm–1
ring
1500 s
1
1
1
1
1
1
532 m
516 m
532 m
516 m
532 m
516 m
I
I
(
method A)
method B)
II
transꢀ[PdCl L ]
357 m
357 m
323 m
323 m
298 w
2
2
(
transꢀ[PdCl L ]
2
2
ν
ν
ν
ν
ν
361 m
as
cisꢀ[PdCl L ]
2
2
336 m
365 s
s
t
III
transꢀ[Pd Cl L ]
1520 m
304 w
326 w
2
4
2
br
br
277 w
The Cl
overlapped by the reagent’s bands, and their assignꢀ two diastereomers, namely, the transꢀ[PdCl (LR
) ]
(S) 2
→
Pd and L
→
Pd chargeꢀtransfer bands are should expect the formation of complex I as a mixture of
2
ment is hindered.
diastereomer consisting of a pair of enantiomers with
Using the racemic reagent L representing an an identical configuration of chiral moieties in ligands
equimolar mixture of
Rꢀ and
Sꢀenantiomers, we
(RRꢀ or SSꢀ)
Cl
OH
(CH2)2 C CH2
CH ) C
N
C(CH3)3
N CH2 C (CH2)2
Cl
Cl
N
N
Pd
N
Cl
(
N
OH
3
3
Cl
Cl
(
CH ) C
N
OH
3
3
(CH2)2 C CH2
OH
N
N
Pd
N
N CH2 C (CH2)2
C(CH3)3
Cl
,
N
Cl
and the transꢀ[PdCl (L )(L )] diastereomer with an inverse configuration of chiral moieties in ligand molecules
2
R
S
(
SRꢀ or RSꢀ)
Cl
Pd
Cl
OH
(CH2)2 C CH2
CH ) C
N
N
OH
.
Cl
Cl
N
N
N
N CH2 C (CH2)2
C(CH3)3
(
3
3
1
3
1
The C NMR spectra of complex
I
in CDCl3 and
The H NMR spectrum of complex
I
in CDCl3
DMFꢀd7 contain a set of 12 signals from the carbon (Table 3) allows us to distinguish the signals from the
atoms of the reagent. The number of signals from a protons at the C(1), C(1'), C(3''), C(5''), C(9), and
molecule of each stereomer in a spectrum is twice
lower than the number of atoms corresponding to
them, as molecules have a secondꢀorder symmetry
C(13) atoms of two diastereomers (
dias). Despite the
Δ
difference between the chemical shifts of signals is
only 0.01–0.02 ppm, it indicates the formation of
diastereomers, and equal integral intensities point to
their equimolar ratio. We should note that the specꢀ
trum of this complex in DMFꢀd7 contains only one set
of proton signals.
element: the transꢀ[PdCl (LR(
symmetry axis, and the transꢀ[PdCl (L )(L )] stereꢀ
) ] diastereomer has a
S) 2
2
2
R
S
omer has a symmetry plane. For this reason, the numꢀ
bering of atoms is given in Tables 2 and 3 only for one
coordinated reagent L molecule, and the numbering
of atoms in the second molecule is omitted for simꢀ
plicity. The spectrometer resolution has not allowed us
Complex II prepared from the precursor with a cis
configuration of its coordination core has the same
elemental composition as transꢀcomplex . However,
by its physical
from the carbon atoms of diastereomers and to prove characteristics, namely, by the melting temperature
their formation.
(Table 1) and, as mentioned above, by its solubility in
ꢀ
I
to detect the nonequivalency of corresponding signals it considerably differs from complex
I
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 5 2015

644
KHISAMUTDINOV et al.
–1
organic solvents. In contrast to the spectrum of comꢀ [24, 25]. A weak absorption band at 298 cm seems to
plex
, the farꢀIR spectrum of complex II contains two belong to (Pd–N) [18, 24].
mediumꢀintensity absorption bands at 361 and 336 cm
Table 4), which belong to as(Pd–Cl) and
respectively, and are typical for the complexes like cis
I
ν
–1
The coordination of racemic reagent molecules to
(
ν
ν
s(Pd–Cl)
,
palladium(II) enables the formation of complex II in
ꢀ
the same fashion as for complex
I
in the form of two
PdCl2L2 with the C2 symmetry of coordination core diastereomers, namely,
ν
cisꢀ[PdCl (LR
) ]
) 2
2
(S
Cl
Cl
OH
N
Pd
C(CH3)3
Cl
Cl
(CH2)2 C CH2
N
N
N
N CH2 C (CH2)2
Cl
Cl
(
CH ) C
N
OH
3
3
(
CH ) C
N
OH
3
3
(CH2)2 C CH2
OH
N
N
N
N CH2 C (CH2)2
C(CH3)3
N
Pd
Pd
Cl
Cl
and cisꢀ
[
PdCl (L )(L )
2
]
R
S
Cl
Cl
OH
N
N
OH
N CH2 C (CH2)2
C(CH3)3
.
Cl
Cl
(CH2)2 C CH2
N
N
N
(
CH ) C
3 3
The mutual spatial arrangement of coordinated dinated to palladium(II) ions via the N(2) and N(4)
reagent molecules in the cisꢀ and transꢀisomers is difꢀ atoms [26]. Since reagent L in complex III is monoꢀ
ferent, so the chemical shifts of signals from some dentate coordinated via the N(4) atom according to
atoms in the IR spectra of complexes
from each other by the value I– (Tables 2 and 3) for binuclear chloro bridge and to have the composition
the methylene carbon atoms C(1) (0.82 ppm), C(2)
0.64 ppm), C(1') (0.23 ppm), which are the most mobile
I
and II differ NMR spectroscopic data, it may be supposed to be a
δ
δ
II
[
Pd Cl L2]. This is also indicated by the presence of
2
4
(
two overlapping broad bands in EASs with maxima at
63 nm ( = 280) and 395 nm ( = 240), which can be
moieties in a molecule, the atoms C(3'') (0.13 ppm) and
H(3'') (0.12 ppm) of the methyne group, which is closꢀ
est to the N(4'') atom, and also for the H(5'') atom of
the triazole ring (0.14 ppm). The smaller number of
signals in the spectra in comparison with the number
of atoms in the molecules of complex is caused by the
3
ε
ε
assigned to the d–d transitions in palladium(II) ions
incorporated into the [Pd Cl L2]ꢀtype chloro bridged
2
4
complex with a squareꢀplanar configuration of coordiꢀ
nation cores [24]. The band at 236 nm ( = 41100) in
the spectrum of complex III is produced by the σ → dσ*
charge transfer from the bridging chloride ion to the
metal [27] and is absent in the spectra of the reagent
and mononuclear complex
complex III contains a set of three
tion bands (Table 4), which are typical for the spectra
of planar transꢀ[Pd2( ꢀCl) Cl L2]ꢀtype complexes
with С2h symmetry, namely, the strong band assigned to
the
the weak band belonging to the
of the bridging bond in the transꢀposition to the termiꢀ
ε
1
3
Cl
same reasons as for complex I. The C NMR specꢀ
trum of complex II contains one set of signals, i.e.,
does not provide any information about diastereꢀ
omers. The presence of two equally intense Н(1B) proꢀ
I
. The IR spectrum of
1
ν(Pd–Cl) absorpꢀ
ton signals in the H NMR spectrum with chemical
shifts differing from each other by
indicates the equimolar ratio between RR
RSꢀdiastereomers.
Δ
dias
= 0.02 ppm
μ
(
SS)ꢀ and
2
2
–1
ν
t(Pd–Cl) terminal bond vibrations at 365 cm ,
According to elemental analysis (Table 1), the
Pd(II) : L ratio in complex III corresponds to the preꢀ
determined value, and its composition with allowance
for the palladium(II) coordination number of 4 correꢀ
sponds to the polynuclear [PdCl L] chloro complex.
νbr(Pd–Cl) vibrations
–1
nal chloride ion at 304 cm , and the weak bond proꢀ
duced by the br(Pd–Cl) vibrations of the bridging
ν
2
n
–1
The reaction between transꢀ[PdCl (CH CN)2] and bond in transꢀposition to L at 277 cm [18, 19, 24].
2
3
–1
1
Hꢀ1,2,4ꢀtriazole in the molar ratio of 1 : 1 in an aqueꢀ The weak band in the spectrum at 326 cm correꢀ
ous medium is known to give the [PdCl2(
ꢀL)]n coorꢀ sponds to the (M–N) vibrations in the trans
dination polymer with a bridging triazole ligand coorꢀ
Pd Cl ]ꢀtype chloro bridged binuclear pallaꢀ
μ
ν
ꢀ
[
L
4 2
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 60 No. 5 2015

PALLADIUM(II) CHLORO COMPLEXES
645
1
dium(II) complexes with nitrogenꢀcontaining heteroꢀ The two sets of signals in the H NMR spectrum with
13
cyclic ligands [18, 24]. The C NMR spectrum of equal intensities and the difference between chemical
complex III, as well as the spectrum of complex shifts of 0.01–0.02 ppm indicate that this complex is
contains only one set of signals from carbon atoms. an equimolar mixture of two diastereomers:
I,
OH
N
Cl
Cl
(CH2)2 C CH2
N
N
Cl
Cl
(
CH ) C
Pd
Pd
Pd
Pd
3
3
C(CH3)3
Cl
Cl
Cl
N
N CH2 C (CH2)2
Cl
(
CH ) C
3
3
N
OH
(CH2)2 C CH2
OH
N
N
Cl
N
N
OH
Cl
,
Cl
Cl
N
N CH2 C (CH2)2
C(CH3)3
and
OH
N
Cl
(CH2)2 C CH2
N
N
Cl
Cl
Cl
(
CH ) C
Pd
Pd
N
OH
N CH2 C (CH2)2
C(CH3)3
3
3
Cl
N
.
Cl
The similar values of chemical shifts of correꢀ
sponding signals in the spectra of complexes III and
also argue for the transꢀconfiguration of coordination ladium(II) via the N(4) atom of the triazole ring.
cores: the difference does not exceed 0.06
[Pd Cl L LS] = 1 : 1) have been synthesized and charꢀ
acterized. Reagent molecules are coordinated to palꢀ
2 4 R
I
δ
–
δ
III
I
1
ppm in the H NMR spectrum and 0.12 ppm in the
C NMR spectrum.
13
ACKNOWLEDGMENTS
The synthesis of the transꢀ[Pd Cl L2] binuclear
chloro bridged complex can be described by the folꢀ Chemistry of Materials Science of the Russian Acadꢀ
lowing scheme:
This work was supported by the Department of
2
4
emy of Sciences (Program OKhNMꢀ5). The authors
are grateful to the Russian Foundation for Basic
Research (grant no. 13ꢀ00ꢀ14056 IR) for the financial
support of access to the information resources of forꢀ
eign publishers.
(
1) The formation of the transꢀ[PdCl (CH CN)2]
2
3
complex upon the dissolution of PdCl2 in acetonitrile
80
(
°
С)
PdCl + 2CH CN
2
→
transꢀ[PdCl (CH CN) ].
2 3 2
3
(
2) The innerꢀsphere substitution of acetonitrile by
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Translated by E. Glushachenkova
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