Chiral palladium complexes with monoterpenoids oximes

Article abstract of DOI:10.1134/S1070363214010216

Oximes of cis-caran-4-one, 3α- and 3β-hydroxycaran-4-ones, cis-verbanone, menthone, and 2β-hydroxybornan-3-one have been synthesized. The obtained oximes react with lithium tetrachloropalladate to give new chiral palladium complexes containing mono-or bid

Full text of DOI:10.1134/S1070363214010216

ISSN 1070-3632, Russian Journal of General Chemistry, 2014, Vol. 84, No. 1, pp. 137–142. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © Ya.A. Gur’eva, O.A. Zalevskaya, L.L. Frolova, I.N. Alekseev, P.A. Slepukhin, A.V. Kuchin, 2014, published in Zhurnal Obshchei
Khimii, 2014, Vol. 84, No. 1, pp. 144–149.
Chiral Palladium Сomplexes with Monoterpenoids Oximes
a
b
a
Ya. A. Gur’eva , O. A. Zalevskaya , L. L. Frolova ,
a
c
a
I. N. Alekseev , P. A. Slepukhin , and A. V. Kuchin
a
Institute of Chemistry, Komi Scientific Center, Ural Branch of the Russian Academy of Sciences,
ul. Pervomaiskaya 48, Syktyvkar, 167982 Russia
e-mail: gurjeva-ja@chemi.komisc.ru
b
Syktyvkar State University, Syktyvkar, Russia
c
Postovskii Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia
Received January 14, 2013
Abstract―Oximes of cis-caran-4-one, 3α- and 3β-hydroxycaran-4-ones, cis-verbanone, menthone, and 2β- hyd-
roxybornan-3-one have been synthesized. The obtained oximes react with lithium tetrachloropalladate to give
new chiral palladium complexes containing mono- or bidentate oxime ligands.
DOI: 10.1134/S1070363214010216
Oximes are known to readily form complexes with
many transition metal ions, including palladium.
Therefore, they are widely used in quantitative
palladium determination [1, 2] and extractive isolation
of palladium compounds from the mixtures [3, 4].
Oxime-based palladium complexes are applied as
catalysts in asymmetric synthesis [5, 6].
The oximes were synthesized via condensation of
the initial oxo derivatives with hydroxylamine
hydrochloride according to the standard procedure [7]
to yield 70–94% of the products.
Oximes I, IV, V were obtained in the form of Z-
and E-isomers mixtures, and the major isomers were
isolated by column chromatography; whereas the
individual isomers were obtained in the cases of IIa,
IIb, and III.
We prepared the oximes of (–)-cis-caran-4-one (I),
(+)-3α-hydroxycaran-4-one (IIa) and 3β-hydroxy-
caran-4-one (IIb), (+)-cis-verbanone (III), (–)-men-
thone (IV), and (+)-2β-hydroxybornan-3-one (V), and
applied them as ligands to form palladium complexes.
NOE
1
13
In the H and C NMR spectra of all the oximes
obtained, the signals were not duplicated thus proving
the presence of a single isomer. According to NOE
analysis, oximes I–IV were Z-isomers, and oxime V
was of E-configuration. In particular, the NOESY
spectra of oximes IIa and IIb revealed the interaction
of protons of two hydroxyl groups; that indicated the
formation of intramolecular hydrogen bond stabilizing
the Z-isomers. In the NOESY spectra of oximes I, III,
and IV, the interactions of the hydroxyl proton and the
protons of terpene moiety at position 10 (I), 5 (III) or
NOE
OH
NOE
OH
CH3 OH
N
OH
OH
N
N
3
4
2
1
5
6
7
8
9
Z-I
Z-IIа
Z-IIb
10
10
10
9
(IV) were revealed; that confirmed the Z-con-
figuration of the oximes. E-Configuration of oxime V
was elucidated from the NOE interaction between the
NOH group proton and H of terpene moiety.
1
OH
2
6
1
4
1
7
3
6
5
6
5
2
3
2
9
4
7
8
9
8
3
4
5
4
N
N
N
The prepared oximes I, IIa, III, and IV were found
to interact with lithium tetrachloropalladate in
methanol to give the stable complexes VI–IX, respec-
tively, with 53–83% yield.
H
OH
9
OH
H
OH
7
8
CH
3
NOE
Z-III
NOE
NOE
Z-IV
E-V
1
37

1
38
GUR’EVA et al.
OH
N
OH
N
OH
Cl
Cl
Pd
Pd
Cl
Cl
N
N
HO
OH
OH
VI
VII
OH
OH
N
N
Cl
Cl
Pd
Pd
Cl
Cl
N
N
OH
OH
VIII
IX
1
13
In the IR spectra of the VI–IX complexes,
H NMR and C NMR spectra of the complexes X
and XI confirmed their suggested structure. In
absorption bands of C=N stretching were shifted to
lower frequencies as compared with those in the
spectra of initial oximes, indicating that imino group
participated in coordination. The NMR data confirmed
the monodentate nature of the oxime ligands.
1
particular, the H NMR spectra contained all the
signals assigned to the starting oximes, the signals of
the hydroxyl protons in positions 3 and 2 were shifted
downfield by 1.8 ppm (X) and 0.8 ppm (XI), con-
firming their participation in coordination to palladium.
1
13
H and C NMR spectra of all the complexes VI–
The structure of X was elucidated from X-ray
diffraction data as well; the spacial structure of the
molecule is shown in the Figure. The crystals of X
IX did not contain the duplicated signals, thus
indicating formation of the only isomer; in particular,
formation of the thermodynamically more stable trans-
isomer could be assumed. In NOESY correlation
spectra of VI–IX, the same protons NOE interactions
were observed that were previously used to identify the
initial oximes. Therefore, the oximes configuration
was retained in the course of the complexes formation.
were assigned to the P2 2 2 chiral space group of
1
1 1
orthorhombic crystal system. In the molecule of X, the
chlorine atoms were cis-positioned in the distorted
square-planar surrounding of the palladium atom. The
organic part acted as neutral bidentate chelating ligand,
forming the five-membered ring. Cyclohexyl moiety
existed in the half-chair conformation (envelope) with
five ring atoms situated in the same plane (the
Oximes IIa, IIb, and V were N,O-bidentate ligands
capable of formation the chelate complexes. Indeed,
reactions of oximes IIb and V with lithium
tetrachloropalladate resulted in chelate complexes X
2
deviation being of <0.04 Å), and the C atom was out-
of-plane by 0.664 Å.
(
80%) and XI (90%), respectively.
Noteworthily, chelation of IIb changed the
configuration of the C=N bond of the oxime. That was
likely caused by additional stabilization of the formed
complex operative only in the case of the E-isomer.
Such configuration change was only possible in the
case of the β-isomer (IIb); under the same conditions,
the corresponding α-isomer (IIa) formed the VII
complex containing monodentate ligand.
V
IIb
Li PdCl
Li PdCl4
2
2
4
Cl
Cl
H
O
Pd
H
O
N
Cl
Cl
OH
Pd
To conclude, palladium coordination compounds
with monodentate oximes VI–IX as well as chelates X
and XI were obtained. The complexes structure was
confirmed by IR and NMR spectroscopy and elemental
N
OH
XI
X
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014

CHIRAL PALLADIUM СOMPLEXES WITH MONOTERPENOIDS OXIMES
139
analysis as well as by X-ray diffraction analysis (in the
case of X).
EXPERIMENTAL
IR spectra of thin films or KBr pellets were
registered with IR Prestige 21 Shimadzu spectrometer.
1
13
H and C NMR spectra of solutions in CDCl were
3
recorded with Bruker AVANCE-II-300 spectrometer
1
13
at 300 MHz ( H) or 75 MHz ( C). The signals
1
assignment was confirmed using two-dimensional Н–
Н and Н– С correlation spectra (COSY, NOESY,
General view of X molecule.
1
1
13
HSQC, and HMBC). Optical rotation was measured
with automatic P3002RS Kruss polarimeter (Germany).
Elemental analysis was performed with EA 1110
(
rider model). The unit cell parameters at 295(2) K for
the red rhombic crystal (0.23 × 0.16 × 0.11 mm) were
as follows: space group P2 2 2 , a = 7.1140(5), b =
1
Z = 4, C H Cl NО Pd; d = 1.803 g cm , μ =
1
reflections were collected, including 4726 independent
ones (Rint 0.0258), and 2767 ones with I > 2σ(I).
Completeness at θ 30.00° was of 99.7%. Final
(
CHNSO) elemental analyzer.
1
1 1
3
2.1058(9), c = 15.4189(11) Å, V = 1327.89(17) Å ,
The reaction progress was monitored by TLC using
–
3
1
0
17
2
2
calc
Sorbfil plates, eluting with С Н –Et O or benzene–
6
14
2
−
1
.785 mm . In the range of 3.13 < θ < 33.51, 10964
acetone (5 : 1) mixtures and detecting with iodine
vapor or with 10% solution of phosphomolybdic acid
in ethanol followed by heating to 100–120°C. Silica
gel (Alfa Aesar, 70–230 μ) was used for column chro-
matography purification. Palladium chloride was used
as received.
refinement parameters: R = 0.0272, wR = 0.0410
1
2
[reflections with I > 2σ(I)], R = 0.0538, wR = 0.0420
1 2
(
all reflections) at S factor of 1.002. The absolute
The following initial monoterpenoids were used:
structure parameter was of 0.02 (2), the highest and the
lowest residual electron density being of 0.583 and –
1
2
0
3
α-hydroxycaran-4-one {[α] +35° (с 0.6, EtOH), the
D
spectral data were consistent with [8]}, 3β-hydroxyl-
−3
.534 ēÅ , respectively.
2
0
caran-4-one {[α] +25° (с 0.4, EtOH), the spectral
D
2
0
cis-Caran-4-one oxime (I). Yield 70%, mp 42°C,
data were consistent with [9]}, cis-verbanone {[α]
D
white crystals, soluble in chloroform, acetone, benzene,
and DMSO; R 0.5 [hexane–diethyl ether (3 : 1),
detection with a solution of phosphomolybdic acid],
–
29.5° (с 1.0, EtOH), the spectral data were consistent
2
0
with [10]}, menthone {[α] –25° (с 0.5, EtOH),
f
D
prepared by oxidation of commercial (–)-menthol with
potassium dichromate in acidic medium [11]}, 2-hyd-
2
0
−1
[α] –15.6° (с 0.2, EtOH). IR spectrum, ν, cm : 3285
D
2
0
1
roxybornan-3-one {[α] +114° (с 0.2, EtOH)}, cis-
(ОН), 1649 (C=N). Н NMR spectrum (300 MHz,
CDCl
s (3Н, СН
(
Н , J 5.0, J
Н ), 2.40 d. d (1Н, Н , J
(
spectrum (75 MHz, CDCl ), δ , ppm: 14.76 (С ),
1
(
Found, %: C 72.6; H 10.4; N 8.5. C H NО.
Calculated, %: C 71.9; H 10.2; N 8.4.
D
2
0
1
caran-4-one {[α] –134° (с 1.5, EtOH), obtained as
3
), δ, ppm (J, Hz): 0.82 m (1Н, Н , J1,6 5.4), 0.85
D
9
6
described in [12, 13]}.
3
), 0.91 d. d (1Н, Н , J6,1 5.4, J6,5 8.6), 1.04 s
8
3
10
3
3Н, СН ), 1.08 d (3Н, СН , J 6.5), 1.12 d. d (1Н,
10,3
Single crystal X-ray diffraction analysis of the
compound X was performed with automatic four-circle
Xcalibur 3 diffractometer equipped with CCD-detector
2
2
β
13.2), 2.15 m (1Н, Н ), 2.25 m (1Н,
α
2α,2β
3
5
α
8.6, J5α,5β 18.6), 2.93 d
5α,6
18.6), 9.35 br. s (1Н, NOH). С NMR
5
13
1Н, Н , J
β
5β,5α
[
λ(MoK ) 0.71073 Å]. Data were collected and
9
α
3
C
1
processed following the standard procedures [14].
Absorption was accounted for analytically (polyhedral
crystal model [15]). The structure was solved and
refined using the SHELX software package [16].
Refinement was performed with a full-matrix least
10
7
5
6.20 (С ), 18.48 (С ), 19.30 (С ), 20.19 (С ), 20.53
6
8
2
3
4
С ), 28.13 (С ), 29.39 (С ), 34.53 (С ), 163.78 (С ).
1
0
17
2
square of F using anisotropic approximation for all
3α-Hydroxycaran-4-one oxime (IIa). Yield 70%,
mp 101–102°С, white crystals, soluble in chloroform,
acetone, benzene, and DMSO; R
ether (2 : 1), detection with solution of phosphor-
molybdic acid], [α]
the non-hydrogen atoms. The hydrogen atoms were
placed into geometrically calculated positions and
included into the refinement with isotropic
approximation and dependent thermal parameters
0.4 [hexane–diethyl
f
2
0
+155.5° (с 0.2, EtOH). IR
D
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014

1
40
GUR’EVA et al.
−
1
20
−1
spectrum, ν, cm : 3377 (ОН), 3183 (ОН), 1653
acid], [α] –48.8° (с 0.3, EtOH). IR spectrum, ν, cm :
D
1
1
(
(
5
C=N). Н NMR spectrum (300 MHz, CDCl ), δ, ppm
J, Hz): 0.83 s (3Н, СН ), 0.85 d. d. d (1Н, Н , J
.0, J1,2β 9.4, J1,6 10.5), 1.00 d. d. d (1Н, Н , J 1.8,
J6,5α 8.7, J6,1 10.5), 1.07 s (3Н, СН ), 1.38 s (3Н,
СН ), 1.44 d. d (1Н, Н , J 5.0, J2α,2β 15.3), 2.25 d. d
1Н, Н , J 9.4, J2β,2α 15.3), 2.41 br. s (1Н, ОН), 2.62
3285 (ОН), 1664 (C=N). Н NMR spectrum
3
9
3
1
9
3
(300 MHz, CDCl ), δ, ppm (J, Hz): 0.94 d (3Н, СН ,
1,2α
3
6
8
10
J9,7 6.8), 0.97 d (3Н, СН , J 6.8), 1.01 d (3Н, СН ,
6,5β
3 8,7 3
8
3
6
5
J10,1 6.2), 1.18 m (1Н, Н ), 1.40 m (1Н, Н ), 1.69 m
α α
(1Н, Н ), 1.75 m (1Н, Н ), 1.86 m (1Н, Н ), 1.91 m
(1Н, Н ), 1.92 m (1Н, Н ), 2.16 septet (1Н, Н , J
β 7,8,9
1
3
0
2
α
2
1
6
2α,1
α
β
2
β
5
4
7
(
2β,1
5
5
β
2
β
13
d. d (1Н, Н , J
8.7, J5α,5β 18.7), 2.89 d. d (1Н, Н ,
6.8), 3.08 m (1Н, Н ), 9.15 br. s (1Н, NOH). С NMR
α
5α,6
1
3
9
J5β,6 1.8, J5β,5α 18.7), 9.03 br. s (1Н, NOH). С NMR
spectrum (75 MHz, CDCl ), δ , ppm: 14.43 (С ),
6.74 (С ), 17.71 (С ), 18.65 (С ), 19.06 (С ), 24.87
С ), 28.01 (С ), 34.78 (С ), 69.84 (С ), 162.46 (С ).
spectrum (75 MHz, CDCl ), δ , ppm: 19.05 (С ),
3
C
7
9
8
10
5
21.46 (С ), 21.75 (С ), 26.34 (С ), 26.81 (С ), 31.90
3
C
7
1
5
6
2
1
6
4
3
1
(
(С ), 32.39 (С ), 32.81 (С ), 48.76 (С ), 161.44 (С ).
Found, %: C 71.2; H 11.6; N 8.3. C H NО.
1
0
8
2
3
4
1
0
19
Found, %: C 66.2; H 9.42; N 7.6. C H NО .
Calculated, %: C 71.0; H 11.2; N 8.3.
10
17
2
Calculated, %: C 65.6; H 9.28; N 7.6.
2
β-Hydroxybornan-3-one oxime (V). Yield 75%,
3
β-Hydroxycaran-4-one oxime (IIb). Yield 91%,
mp 128–129°С, white crystals, soluble in chloroform,
yellow oil, soluble in chloroform, acetone, benzene,
acetone, benzene, and DMSO; R 0.3 [hexane–diethyl
f
and DMSO; R 0.5 [hexane–diethyl ether (1 : 2), detec-
ether (1 : 2), detection with solution of phosphor-
f
2
0
20
tion with solution of phosphomolybdic acid], [α]
molybdic acid], [α] –91.7° (с 0.1, EtOH). IR spec-
D
D
−
1
−1
1
+
54.4° (с 0.2, EtOH). IR spectrum, ν, cm : 3331
trum, ν, cm : 3537 (ОН), 3395 (ОН), 1688 (C=N). Н
1
(ОН), 1653 (C=N). Н NMR spectrum (300 MHz,
NMR spectrum (300 MHz, CDCl ), δ, ppm (J, Hz):
3
9
3
9
10
8
CDCl ), δ, ppm (J, Hz): 0.83 s (3Н, СН ), 0.84 m (2Н,
Н , Н ), 1.05 s (3Н, СН ), 1.44 s (3Н, СН ), 1.45 m
0.91 s (3Н, СН ), 0.99 s (3Н, СН ), 1.05 s (3Н, СН ),
3
6
3 3 3
1
8
3
10
5
6
5
1.24 m (1Н, Н ), 1.32 m (1Н, Н ), 1.67 m (1Н, Н ),
α α β
3
2
2
β
5
α
6
4
(
1Н, Н ), 2.21 m (1Н, Н ), 2.43 m (1Н, Н ), 2.98 m
1.86 m (1Н, Н ), 3.08 d (1Н, Н , J 4.3), 3.98 s (1Н,
α
β 4,6β
5
β
2
13
(
1Н, Н ), 3.90 br. s (1Н, ОН), 8.25 br. s (1Н, NOH).
Н ), 4.45 br. s (1Н, ОН), 9.45 br. s (1Н, NOH).
С
1
3
С NMR spectrum (75 MHz, CDCl ), δ , ppm: 14.58
NMR spectrum (75 MHz, CDCl ), δ , ppm: 10.79
3
C
3
C
9
7
1
6
5
10
9
8
6
5
(С ), 15.13 (С ), 18.73 (С ), 18.93 (С ), 19.12 (С ),
(С ), 19.03 (С ), 21.33 (С ), 22.89 (С ), 33.72 (С ),
47.08 (С ), 47.67 (С ), 49.54 (С ), 77.73 (С ), 170.45
(С ). Found, %: C 66.2; H 9.8; N 7.4. C10H17NО .
1
0
8
2
3
1
4
7
2
2
6.92 (С ), 27.95 (С ), 35.03 (С ), 71.14 (С ), 163.74
4
3
(С ).
2
Calculated, %: C 65.6; H 9.3; N 7.6.
cis-Verbanone oxime (III). Yield 71%, mp 64–65°С,
white crystals, soluble in chloroform, acetone, benzene,
General procedure of the palladium complexes
preparation. Suspension of palladium(II) chloride
(0.2 mmol) and lithium chloride (0.5 mmol) in
methanol (5 mL) was refluxed during 1 h (water bath).
The so obtained dark-red solution of lithium tetra-
chloropalladate was added to solution of an oxime
(0.2 mmol) in methanol (3 mL). The reaction mixture
was stirred at room temperature during 1–8 h. After
that, the solvent was evaporated in vacuum, and the
residue was extracted with chloroform and precipitated
with hexane. The resulting products were in the form
of powder or crystalline.
and DMSO; R 0.3 [hexane–diethyl ether (3 : 1), detec-
f
2
0
tion with solution of phosphomolybdic acid], [α]
12.4° (с 0.2, EtOH IR spectrum, ν, cm : 3215 (ОН),
674 (C=N). Н NMR spectrum (300 MHz, CDCl ), δ,
ppm (J, Hz): 0.95 s (3Н, СН ), 1.15 d (3Н, СН , J
.3), 1.21 d (1Н, Н , J
m (1Н, Н ), 2.27 m (1Н, Н ), 2.39 d (1Н, Н , J
0.0), 2.55 d. d (1Н, Н , J 5.9, J7β,7α 9.9), 2.62 d. d
D
−
1
+
1
1
3
8
10
3
3
10,2
7
α
9
7
9.9), 1.33 s (3Н, СН ), 1.98
7α,7β 3
1
2
3
α
3α,3β
7
2
(
1
β 7β,5
5
3
1Н, Н , J5 5.9, J5,3β 10.4), 3.02 d. d (1Н, Н , J
,7β β 3β,5
1
3
0.4, J3β,3α 20.0), 8.98 br. s (1Н, NOH). С NMR
spectrum (75 MHz, CDCl ), δ , ppm: 21.66 (С ),
1
0
3
C
3
8
9
7
2
(
4.44 (С ), 26.84 (С ), 27.39 (С ), 30.78 (С ), 31.82
Complex VI. Yield 188 mg (61%), mp 121–122°С
2
6
1
5
4
С ), 40.35 (С ), 47.67 (С ), 48.33 (С ), 164.85 (С ).
(
decomp.), yellow powder, soluble in chloroform,
Found, %: C 72.8; H 10.9; N 8.2. C H NО.
1
0
17
acetone, benzene, and DMSO; R 0.7 [benzene–acetone
f
Calculated, %: C 71.9; H 10.2; N 8.4.
20
(
5 : 1), detection with iodine vapor], [α] –262.5°
D
–
1
Menthone oxime (IV). Yield 70%, mp 51–52°С,
white crystals, soluble in chloroform, acetone,
(с 0.2, CHCl
3
). IR spectrum, ν, cm : 3304 (ОН), 1643
), δ, ppm
1
(C=N). Н NMR spectrum (300 MHz, CDCl
3
1
6
benzene, and DMSO; R 0.8 [hexane–diethyl ether
(J, Hz): 0.76 m (1Н, Н ), 0.85 m (1Н, Н ), 0.98 m (1Н,
f
2
α
8
3
9
3
(
3 : 1), detection with solution of phosphomolybdic
Н
), 1.05 s (3Н, СН
), 1.07 s (3Н, СН
), 1.55 d. d (1Н,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014

CHIRAL PALLADIUM СOMPLEXES WITH MONOTERPENOIDS OXIMES
141
5
10
10
6
Н , J 8.0, J
15.2), 1.80 d (3Н, СН , J 7.3), 2.15
(3Н, СН , J
6.4), 1.53 m (1Н, Н ), 1.78 m (1Н,
α
5α,5β
3
10,3
3
10,1
α
2
5
5
5
1
m (1Н, Н ), 3.40 d. d (1Н, Н , J 7.3, J
m (1Н, Н ), 8.72 br. s (1Н, NOH). С NMR spectrum
75 MHz, CDCl ), δ , ppm: 14.59 (С ), 19.92 (С ),
15.2), 3.37
Н ), 2.05 m (1Н, Н ), 2.07 m (1Н, Н ), 2.08 m (1Н,
β
β
5β,5α
α
β
3
13
2
7
6
Н ), 2.18 m (1Н, Н ), 2.91 m (1Н, Н ), 2.92 m (1Н,
α
β
9
7
2
β
4
13
(
2
Н ), 3.81 m (1Н, Н ), 11.08 br. s (1Н, NOH).
NMR spectrum (75 MHz, DMSO-d ), δ , ppm: 18.16
С
3
C
1
1
0
6
5
0.09 (С ), 20.75 (С ), 20.80 (С ), 22.23 (С ), 27.75
6 C
8
2
3
4
9
10
8
5
1
(
4
С ), 27.91 (С ), 35.09 (С ), 177.02 (С ). Found, %: C
(С ), 21.17 (С ), 22.10 (С ), 24.29 (С ), 27.39 (С ),
2
6
7
4
7.8; H 6.87; N 3.8. C H N О PdCl . Calculated, %:
C 46.9; H 6.65; N 5.2.
30.56 (С ), 31.82 (С ), 32.09 (С ), 50.87 (С ), 172.11
20
34
2
2
2
3
(С ). Found, %: C 46.7; H 7.44; N 5.3. C20
О PdCl . Calculated, %: C 46.6; H 7.40; N 5.4.
H N ·
38 2
2
2
Complex VII. Yield 170 mg (53%), mp 127–128°С
(
decomp.), yellow powder, soluble in acetone,
Complex X. Yield 168 mg (80%), mp 139–140°С
benzene, and DMSO; R 0.2 [benzene–acetone (5 : 1),
(decomp.), red crystals, soluble in chloroform, acetone,
f
2
0
detection with iodine vapor], [α] +59.4° (с 0.2,
and benzene; R 0.4 [benzene–acetone (5 : 1), detection
D
f
–
1
20
D
acetone). IR spectrum, ν, cm : 3375 (ОН), 3184 (ОН),
with iodine vapor], [α] –117.8° (с 0.2, CHCl ). IR
spectrum, ν, cm : 3227 (ОН), 1618 (C=N). Н NMR
3
1
–1
1
1
643 (C=N). Н NMR spectrum (300 MHz, DMSO-
1
d ), δ, ppm (J, Hz): 0.70 d. d. d (1Н, Н , J 4.5, J
.4, J1,2β 9.5), 0.71 s (3Н, СН ), 0.85 d. d (1Н, Н , J
.4, J6,5α 8.5), 0.99 s (3Н, СН ), 1.20 s (3Н, СН ),
.25 d. d (1Н, Н , J 4.5, J2α,2β 14.9), 2.09 d. d (1Н,
9.5, J2β,2α 14.9), 2.31 d. d (1Н, Н , J 8.5,
J5α,5β 17.6), 2.82 d (1Н, Н , J
ОН), 10.45 br. s (1Н, NOH). С NMR spectrum (75
MHz, DMSO-d ), δ , ppm: 14.69 (С ), 17.53 (С ),
spectrum (300 MHz, CDCl ), δ, ppm (J, Hz): 0.85 m
6
1,2α
1,6
3
9
6
6
9
3
1
8
8
1
(1Н, Н ), 0.98 s (3Н, СН ), 1.02 m (1Н, Н ), 1.04 s
3
6,1
10
8
8
10
2
(3Н, СН ), 1.82 s (3Н, СН ), 1.95 m (1Н, Н ), 2.31 m
3 3 α
3
3
2
α
2
5
5
(1Н, Н ), 2.74–2.95 m (2Н, Н , Н ), 5.70 br. s (1Н,
2α,1
β α β
2
β
5
α
13
Н , J
ОН), 9.20 br. s (1Н, NOH). С NMR spectrum (75
2β,1
5α,6
5
β
9
6
17.6), 3.37 br. s (1Н,
MHz, CDCl ), δ , ppm: 15.08 (С ), 18.17 (С ), 21.68
5β,5α
3 C
1
3
7
1
5
10
8
(С ), 21.92 (С ), 24.08 (С ), 25.89 (С ), 27.73 (С ),
9
1
2
3
4
33.50 (С ), 88.42 (С ), 171.97 (С ). Found, %: C 34.3;
H 5.2; N 3.81. C H NО PdCl . Calculated, %: C
6
C
5
7
6
10
1
(
7.80 (С ), 17.83 (С ), 20.40 (С ), 26.50 (С ), 28.54
1
0
17
2
2
8
2
3
4
С ), 35.71 (С ), 68.43 (С ), 161.09 (С ). Found, %: C
33.2; H 4.7; N 3.88.
4
8.8; H 6.70; N 5.3. C H N О PdCl . Calculated, %:
20 34 2 4 2
Complex XI. Yield 195 mg (90%), mp 163–164°С
decomp.), yellow powder, soluble in acetone and
C 47.9; H 6.30; N 5.2.
(
benzene; R 0.7 [benzene–acetone (5 : 1), detection
Complex VIII. Yield 170 mg (55%), mp 155–156°С
decomp.), yellow powder, soluble in chloroform,
f
2
0
with iodine vapor], [α] –21.4° (с 0.2, acetone). IR
(
D
–
1
1
spectrum, ν, cm : 3415 (ОН), 1632 (C=N). Н NMR
spectrum (300 MHz, CDCl ), δ, ppm (J, Hz): 0.71 s
acetone, benzene, and DMSO; R 0.8 [benzene–acetone
f
2
0
(
5 : 1), detection with iodine vapor], [α] –5.5° (с 0.2,
3
D
9
10
8
–
1
(
3Н, СН ), 0.88 s (3Н, СН ), 0.95 s (3Н, СН ), 1.07
CHCl ). IR spectrum, ν, cm : 3292 (ОН), 1661
3 3 3
3
5
6
6
1
m (1Н, Н ), 1.13 m (1Н, Н ), 1.56 m (1Н, Н ), 1.67 m
1Н, Н ), 2.81 d (1Н, Н , J
J2,ОН 4.8), 5.22 d (1Н, ОН, J
NOH). С NMR spectrum (75 MHz, CDCl ), δ , ppm:
1.55 (С ), 19.48 (С ), 21.70 (С ), 23.46 (С ), 33.52
С ), 46.49 (С ), 47.10 (С ), 49.59 (С ), 77.57 (С ),
67.39 (С ). Found, %: C 34.3; H 5.2; N 3.7.
(
(
1
(
2
2
(
C=N). Н NMR spectrum (300 MHz, CDCl ), δ, ppm
J, Hz): 1.04 s (3Н, СН ), 1.12 d (3Н, СН , J 7.3),
10.4), 1.43 s (3Н, СН ), 2.04 m
1Н, Н ), 2.27 m (1Н, Н ), 2.49 d (1Н, Н , J
.71 m (1Н, Н ), 3.13 d. d (1Н, Н , J
0.9), 3.87 d. d (1Н, Н , J 5.3, J5,3β 10.4), 8.08 br. s
1Н, NOH). С NMR spectrum (75 MHz, CDCl ), δ ,
ppm: 21.30 (С ), 24.69 (С ), 26.55 (С ), 30.58 (С ),
α
α
β
3
5
4
2
8
10
3
(
4.1), 3.69 d (1Н, Н ,
4.8), 10.21 br. s (1Н,
β
4,6β
3
10,2
7
9
3
.30 d (1Н, Н , J
ОН,2
α
7α,7β
1
3
1
2
3
α
20.9),
3
C
3α,3β
1
0
9
8
5
7
3
β
1
(
1
10.4, J3β,3α
β
3β,5
6
1
4
7
2
5
5
,7β
3
1
3
3 C
1
0
8
9
7
C H NО PdCl . Calculated, %: C 33.2; H 4.7; N 3.9.
10 17
2
2
3
2
6
1
3
(
0.80 (С ), 31.63 (С ), 40.73 (С ), 47.07 (С ), 51.02
С ), 176.79 (С ). Found, %: C 47.1; H 6.86; N 5.1.
ACKNOWLEDGMENTS
5
4
This work was financially supported by the Russian
Foundation for Basic Research (project No. 13-03-
C H N О PdCl . Calculated, %: C 47.0; H 6.65; N 5.4.
20
34
2
2
2
Complex IX. Yield 257 mg (83%), mp 141–142°С
decomp.), yellow powder, soluble in acetone, benzene,
and DMSO; R 0.7 [benzene–acetone (5 : 1), detection
9
8805).
(
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f
2
0
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–
1
1
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9
8
d (3Н, СН , J 6.8), 0.91 d (3Н, СН , J 6.8), 1.11 d
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9,7
3
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014

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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014