Complex salts trans-[Rh(β-Pic)4Cl2]X (X = Cl-, ReO4-, and ClO4-): Synthesis, crystal structures, and thermal properties

Article abstract of DOI:10.1134/S1070328410050052

Three novel complex salts containing the cation trans-[Rh(β-Pic) ₄Cl₂]⁺ with the anions Cl^- (I), ReO₄^- (II), and ClO₄^- (III) were obtained and characterized by elemental analysis, X-ray diffraction, NMR spectroscopy, and IR spectroscopy. The complex trans-[Rh(β-Pic) ₄Cl₂]ReO₄ crystallizes from DMF as a solvate in which solvent molecules fill the channels formed by the cations and anions. The thermal properties of complexes I, II, and II · DMF were examined by DTA. Final and some intermediate products of the thermolysis were isolated and characterized by physicochemical methods. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070328410050052

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2010, Vol. 36, No. 5, pp. 347–352. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © D.B. Vasil’chenko, E.Yu. Filatov, I.A. Baidina, P.E. Plyusnin, S.V. Korenev, 2010, published in Koordinatsionnaya Khimiya, 2010, Vol. 36, No. 5,
pp. 347–352.
–
–
Complex Salts transꢀ[Rh(βꢀPic) Cl ]X (X = Cl , ReO ,
4
2
4
–
and ClO ): Synthesis, Crystal Structures,
4
and Thermal Properties
D. B. Vasil’chenko *, E. Yu. Filatov , I. A. Baidina , P. E. Plyusnin , and S. V. Korenev
a,
a, b
a
a, b
a, b
a
Nikolaev Institute of Inorganic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
b
Novosibirsk State University, Novosibirsk, Russia
*
Eꢀmail: scrubberr@mail.ru
Received September 24, 2009
+
–
Abstract—Three novel complex salts containing the cation transꢀ[Rh(
β
ꢀPic) Cl ] with the anions Cl (
I),
4
2
–
II), and ClO4–
ReO4
(
(
III) were obtained and characterized by elemental analysis, Xꢀray diffraction, NMR
spectroscopy, and IR spectroscopy. The complex transꢀ[Rh(
vate in which solvent molecules fill the channels formed by the cations and anions. The thermal properties of
complexes
β
ꢀPic) Cl ]ReO crystallizes from DMF as a solꢀ
4
2
4
I, II, and II · DMF were examined by DTA. Final and some intermediate products of the therꢀ
molysis were isolated and characterized by physicochemical methods.
DOI: 10.1134/S1070328410050052
Rhodium complexes with heterocyclic ligands are
thoroughly studied [1] and their catalytic properties [RhA Cl ]X (A = Py and
are well known [2, 3]. In addition, the antibacterial
and anticancer activities of some rhodium(III) comꢀ
plexes with pyridine and its derivatives with aliphatic
substituents were widely discussed at different times
Earlier, we synthesized and studied the salts transꢀ
–
–
γ
ꢀPic ( ꢀpicoline); X = Cl ,
γ
4
–
2
–
ClO4 , and ReO4 ) [12, 13]. In both ligands A, the subꢀ
stituents and hydrogen atoms in the ring are arranged
symmetrically. From this viewpoint, it was interesting
to study the structures of similar complexes with ꢀ
β
[
4, 5]. Complex salts with the general formula
picoline (an asymmetric ligand) and compare the
thermal properties of these complexes.
transꢀ[RhA X ]Y (where A stands for a heterocyclic
4
2
ligand) were obtained and characterized by spectroꢀ
scopic methods over 100 years ago [6]; however, their
structural parameters and thermal properties have not Pic)
In this study, we obtained the salts trans
Cl ]Cl · 2H O ( trans [Rh( ꢀPic) Cl
trans [Rh( ꢀPic) Cl ]ReO DMF (II · DMF),
and trans [Rh( ꢀPic) Cl ]ClO (III and examined
ꢀ
[Rh(
]ReO
4
β
ꢀ
I
)
,
ꢀ
β
4
2
2
4
2
been studied in detail hitherto.
(
II
),
ꢀ
ꢀ
β
4
2
4
·
β
)
4
2
4
Thermolysis of platinum metal complexes containꢀ
ing heterocyclic ligands provides a tool for the syntheꢀ
sis of hybrid organic and inorganic materials with
interesting optical properties [7]. Moreover, decomꢀ
position of binary complexes of the general formula
their crystal structures and thermal properties.
EXPERIMENTAL
Synthesis of complex I. A small amount of hydraꢀ
1
1
n
2
2
m
–2
1
2
[
M L ][M L ], (M and M are dissimilar metals, zine hydrochloride (~6
×
10 mmol) was added to a
solution of RhCl (cRh = 0.08 mol/l; 5 ml) in 0.5 M
one of which is a noble metal) affords bimetallic powꢀ
ders with different phase compositions [8, 9], which
can be widely used in catalytic systems, materials for
microelectronics, and magnetic instruments [10]. The
preparation of such materials is impossible without
detailed and systematic investigations of processes
occurring in the thermolysis of the aforementioned
3
HCl. The mixture was heated on a boiling water bath.
ꢀPicoline (1 ml) was added to the vigorously stirred
hot solution; the solution turned lemon yellow. The
reaction mixture was cooled and mixed with an equal
volume of concentrated HCl. The resulting yellow
crystals were filtered off, washed with a minimum
amount of ice water, and dried in air. The yield was
β
compounds. The complex rhodium(III) salts trans
ꢀ
8
5%.
[
RhA X ]Y (where A is pyridine or picolines) are optiꢀ
4
2
mal models for such investigations [11] because they
contain no complex organic ligands, are relatively easy
to obtain in high yields, are stable in storage under
normal conditions, and resistant to strong oxidants Found (%):
and strong acids.
For C H Cl N O Rh
24
32
3
4
2
anal. calcd. (%): C, 46.65; H, 5.23; N, 9.09; Rh, 16.65.
C, 46.55; H, 5.40; N, 9.20; Rh, 17.20.
347

348
VASIL’CHENKO et al.
–
1
IR (
620 (
414 (
ν
, cm ): 3393 (
2
ν
(O–H)), 3032 (
ν
(C–H)), performed by calcining weighed samples of the comꢀ
1
1
1
3
δ
(H O)), 1607, 1580 (
ν
(C=N)), 1480, 1456, plexes in a quartz tubular vessel in a flow of hydrogen.
ν
(C=C) + (CH )), 1249, 1185, 1114, 1072, The vessel was heated to 600°C with a split furnace.
δ
3
040, 804, 701, 663 (
41 ( (Rh–Cl)), 236 (
H NMR ( , ppm): 8.188 (d, H(5),
.175 (s, H(1)), 7.922 (d, H(3), J = 8 Hz), 7.338 (dd, 209 F1 Iris Thermo Microbalance instrument
δ
CH)), 505, 429, 387 (
(Rh–N)).
δ(ring)), Because salt III decomposes explosively at ~250°С, an
ν
ν
analysis for its rhodium content was not made. Therꢀ
1
δ
J = 6.2 Hz), mal analysis of the complexes was carried out on a TG
8
H(4), J1 = 8 Hz, J2 = 6.2 Hz), 2.227 (s, Me).
(NETZSCH) under helium in an Al O3 crucible
2
1
For
, ppm): 8.809 (d, H(5),
.927 (d, H(3), = 7.8 Hz), 7.688 (dd, H(4), J1
.8 Hz, J2 = 5 Hz).
Synthesis of complex II. An excess of a saturated
solution of sodium perrhenate was added to a hot
0.05 M solution of complex . The resulting light yelꢀ
β
ꢀpicoline as a reference compound, H NMR (heating rate 10 K/min).
(
δ
J = 5 Hz), 8.707 (s, H(1)),
Single crystals of complexes II and III were grown
from their saturated solutions in DMF. Air evaporaꢀ
tion for seven days gave large yellow crystals suitable
7
7
J
=
for Xꢀray diffraction analysis. Complex I crystallized
from both water and DMF as thin plates unsuitable for
Xꢀray diffraction analysis.
~
I
low precipitate was filtered off, washed with a miniꢀ
mum amount of water, and dried in air. The yield was
Xꢀray diffraction of complexes II · DMF and III. An
array of reflection intensities was collected on a
BrukerꢀNonius X8Apex automated fourꢀcircle difꢀ
9
5–98%.
For C H Cl N O ReRh
fractometer (a CCD area detector, MoK radiation,
24
32
2
4
4
α
graphite monochromator) at room temperature. Crysꢀ
tallographic parameters and the data collection statisꢀ
tics for complexes II · DMF and III are given in
Table 1. The structures were solved by direct methods
and refined in the anisotropic and isotropic (for H)
approximations. Part of the H atoms was located from
anal. calcd. (%): C, 36.19; H, 3.54; N, 7.03; Rh + Re, 36.31.
Found (%): C, 36.00; H, 3.20; N, 6.40; Rh + Re, 36.30.
–
1
IR (
581 (
ν
, cm ): 3104, 3044, 2923 (
ν
(C–H)), 1607,
(C=C) +
1
ν
(C=N)), 1481, 1456, 1419 (
ν
δ
(CH )), 1245, 1191, 1115, 1070, 1039, 799, 698, 662
3
(
(
δ
(CH)), 905 (
(Rh–Cl)), 323 (
Synthesis of complex III. An excess of concenꢀ
ν
(Rh–O)), 503, 430, 390 (
(ring)), 341 difference electronꢀdensity maps and part of them was
δ
–
ν
δ
(ReO )), 236 (
ν
(Rh–N)).
located geometrically. All calculations were performed
with the SHELXꢀ97 program package [14]. Theoretiꢀ
4
trated HClO was added to a hot ~0.05 M solution of cal diffraction patterns for these complexes were calꢀ
4
complex
filtered off, washed with a minimum amount of water, Selected bond lengths in complexes III and II · DMF
I
. The resulting light yellow precipitate was culated from singleꢀcrystal Xꢀray diffraction data.
and dried in air. The yield was 95–98%.
are listed in Table 2. Additional crystallographic
parameters have been deposited with the Cambridge
Crystallographic Data Collection (nos. 680021 (III
and 680022 (II · DMF); http://www.ccdc.cam.
ac.uk/).
)
For C H Cl N O Rh
24
32
3
4 2
anal. calcd. (%): C, 32.48;
Found (%): C, 32.50;
H, 3.33;
H, 3.20;
N, 6.31.
N, 6.30.
Xꢀray powder diffraction analysis of polycrystalline
–1
IR (
583 (
ν
, cm ): 3108, 3031, 2923 (
(C=N)), 1481, 1453, 1420 (
(CH)), 1093 monochromator, scintillation detector with amplitude
(ring)), discrimination). To prepare samples, the complexes
ν
(C–H)), 1610, samples was carried out on a DRONꢀRM4 diffractoꢀ
1
ν
ν
(C=C) + meter (Cu
K
radiation, reflectedꢀbeam graphite
α
δ
(CH )), 1246, 1193, 797, 697, 662 (
δ
3
–
4
(
ν
(Cl–O)), 621 (
δ
(ClO )), 502, 430, 386 (
δ
3
40 ( (Rh–Cl)), 233 (
ν
ν
(Rh–N)). The band
δ(CH) is
were suspended in hexane and applied to the polished
side of a fused quartz cell. A similarly prepared sample
partly masked by the broad absorption band
Salt
III are poorly soluble even in boiling water (0.27 and
.19 g/l, respectively). All the salts are well soluble in
ν
(Cl–O).
I
is well soluble in water (27.9 g/l). Salts II and of polycrystalline silicon (
external standard. Diffraction patterns were recorded
in the step mode: = 5 –60 for the complex salts
and = 5 –135 for their thermolysis products. The
a = 5.4309 Å) was used as an
0
2θ
°
°
DMF, pyridine, ethanol, and acetone; they are insolꢀ
uble in hexane.
2θ
°
°
complexes contain the only phase, which is evident
from singleꢀcrystal Xꢀray diffraction data.
IR spectra were recorded on a Scimitar FTS 2000
instrument in the 4000–400 cm range (KBr pellets)
and a Vertex 80 spectrometer in the 400–100 cm
range (polyethylene pellets). H NMR spectra were
–1
–
1
Xꢀray powder diffraction analysis of thermolysis
products was carried out with consideration to the data
recorded on a Bruker DPXꢀ250 spectrometer in D O contained in the PDF card file for pure compounds
at room temperature with DMSO as a standard. Analꢀ [15]. The parameters of the metallic phases were
yses for C, H, and N were carried out on a Euro EA refined for the whole array of data with the PowderCell
1
2
3000 instrument. An analysis for the metal content was 2.3 application [16].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 5
2010

COMPLEX SALTS
349
Table 1. Crystallographic parameters and the data collection and refinement statistics for salt III and solvate II · DMF
Value
Parameter
II · DMF
III
FW
869.61
645.76
Space group
P4/n
P
1
a,
b,
c,
Å
Å
Å
10.7300(4)
11.7134(4)
14.4452(4)
69.9970(10)
69.0310(10)
73.9450(10)
1568.26(9)
1.842
11.35310(10)
11.35310(10)
10.3220(2)
90
α
, deg
, deg
, deg
V, Å3
, g/cm3
β
90
γ
90
1330.43(3)
1.612
ρ
calcd
Z
2
2
θ scan range, deg
2.10–32.60
14786/12573
1.97–30.52
2040/1883
Number of measured/independent reflections
Ranges of h, k, and l indices
–16 <
17 <
12 <
h
k
l
< 15
< 17
< 21
–10 <
–16 <
–14 <
h
k
l
< 16
< 12
< 14
–
–
GOOF on F2
1.031
1.062
0.470, –0.313
112
Δρmax, Δρmin,
Number of parameters refined
R1 and wR2 > 2
R1 and wR2 for all reflections
e
Å–3
1.434, –0.982
529
,
I
σ(
I
)
R1 = 0.0292, wR2 = 0.0608
0.0383, 0.0635
R1 = 0.0181, wR2 = 0.0485
0.0211, 0.0498
RESULTS AND DISCUSSION
As in the case of pyridine and ꢀpicoline, a substiꢀ
propeller with four blades”. Such a propeller can be
dextroꢀ and levorotatory. In addition, because of the
asymmetric structure of Pic ligands, the methyl group
can be oriented upward or downward relative to the
plane for a particular direction of the propeller’s rotaꢀ
tion. However, the salts obtained contain both the
γ
tution reaction of a solution of RhCl in HCl with ꢀ
β
3
picoline catalyzed by reducing agents affords the catꢀ
+
ion trans
ꢀ
[Rh(
β
ꢀPic) Cl ] . The hydrate trans
ꢀ
[Rh(βꢀ
4
2
Pic) Cl ]Cl · 2H O crystallizes in concentrated HCl.
4
2
2
“
right” and “left” cation forms and the methyl groups
Because of its fairly high solubility, ~15–20% of rhodꢀ
ium remains in solution. Salts II and III are poorly
soluble in water and can be isolated from an aqueous
of Pic ligands are aligned in all the cations. The bond
lengths and bond angles in the tetrahedral anions do
not deviate much from the standard values and agree
with our previous data [12, 13].
solution of complex
Recrystallization of salt II from DMF results in the
formation of solvate II DMF, which is not the case of
salt III (Xꢀray diffraction data). The crystal structures
I in nearly quantitative yields.
It should be noted that crystals of both complexes
were grown from DMF, but only perrhenate salt II
forms a solvate with DMF. This can be explained by
the nonequivalence of the geometrical parameters of
·
+
contain the octahedral cation trans
ꢀ
[Rh(βꢀPic) Cl ]
4 2
–
–
(
Fig. 1), the tetrahedral anions ReO4 and ClO4 , and the anions. In the crystal structure of perchlorate III
,
the packing of four cations makes a cavity for the
DMF molecules (in solvate II · DMF,). In the octaheꢀ
dral cation, the NRhN angles vary from 89.00(32)° to
1.60(36)° and the ClRhN angles vary from
8.80(24)° to 91.70(31)°. The dihedral angles between However, the larger Re
–
anion. The ClO4 anion fits exactly into the cavity.
9
8
–
4
O
anion (Re–O, 1.7 Å; Cl
⎯
O,
the planes of four Py rings and the equatorial plane 1.44 Å) cannot accommodate itself to this cavity,
RhN (40.5(3)°–49.3(4)°) shape the cation into “a forming a more strained structure. When salt II crysꢀ
4
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 5
2010

350
VASIL’CHENKO et al.
Table 2. Selected bond lengths in structures II · DMF and III* lel to the axis
z
and the cations are stacked. The shortꢀ
est Cl⋅⋅⋅Cl distance between the cations in the stack is
.627 Å. Each of the aforesaid channels is made up of
Bond
d, Å
Bond
d, Å
5
four such stacked structures. The anions are inside the
channels. A similar structure was found in the clathꢀ
II · DMF
Re(1)–O(1)
Re(1)–O(2)
Re(1)–O(4)
Re(1)–O(3)
Rh(1)–N(4)
Rh(1)–N(3)
Rh(1)–N(2)
Rh(1)–N(1)
Rh(1)–Cl(2)
Rh(1)–Cl(1)
N(1)–C1(5)
N(2)–C(25)
C(11)–C(12)
1.720(8)
1.722(7)
1.725(8)
1.728(8)
2.047(8)
2.054(8)
2.056(8)
2.057(9)
2.340(3)
2.347(3)
C(12)–C(13) 1.363(14)
C(13)–C(14) 1.399(14)
C(14)–C(15) 1.412(11)
C(14)–C(16) 1.500(13)
C(21)–C(22) 1.352(14)
C(22)–C(23) 1.410(14)
C(23)–C(24) 1.386(13)
C(24)–C(25) 1.419(13)
C(24)–C(26) 1.470(12)
rate transꢀ[MnPy (CNS) ] ·Py [17], in which neutral
4 2
transꢀ[MnPy (CNS)2] molecules form channels for
4
pyridine molecules.
The thermal stability of the salts obtained depends
on the anion nature. For instance, salt
begins to decompose at ~100°C, releasing two water
I (Fig. 4a)
molecules into the gaseous phase. In the next step, one
β
ꢀpicoline molecule is replaced by a chloride ion to
give a mixture of isomers Rh( ꢀPic) Cl3. In a separate
experiment, the released substance was condensed
β
3
1
and identified as
TG curve, this step is virtually immediately followed
by the third one. In this step, as with the salt [Rh(
Pic) Cl ]Cl · 2.5H O, first another ꢀpicoline molecule
β
ꢀpicoline ( H NMR data). In the
γ
ꢀ
O(1
A
)–C(1
A
)
1.218(13)
1.337(14)
1.422(13)
1.475(14)
β
4
2
2
1.342(13) C(1
A)–N(1
A
)
is removed to form a polymeric product and then the
organic ligand undergoes thermal degradation. The
final thermolysis products are metallic rhodium and
amorphous carbon. The weight of the thermolysis
products agrees with the following scheme:
1.352(12) N(1
1.410(12) N(1
III
A
)–C(3
A)
A
)–C(2A)
Rh(1)–N(1)
Rh(1)–N(1)i
Rh(1)–N(1)ii
Rh(1)–N(1)iii 2.066(1)
2.066(1)
2.066(1)
2.066(1)
Cl(3)–O(1)vi
N(1)–C(5)
N(1)–C(1)
C(1)–C(2)
1.4418(10)
1.3495(15)
1.3512(15)
1.3890(16)
1.3858(18)
1.4987(19)
1.3789(19)
1.3849(18)
[Rh(βꢀPic) Cl ]Cl
4
2
⋅
2H O
2
Rh + 12C +
β
ꢀPic
↑
+ 2H O
2
↑
+ (other gaseous products)↑.
The decomposition of salt II (Fig. 4b) begins at
300°C and is accompanied by the weight loss correꢀ
~
sponding to the removal of a
hydrogen atom required to form HCl can be released
as a result of C–Rh or C–C (between two ꢀpicoline
β
ꢀPicHCl molecule. The
Rh(1)–Cl(2)
Rh(1)–Cl(1)
2.3414(6) C(2)–C(3)
2.3542(6) C(2)–C(6)
1.4418(10) C(3)–C(4)
1.4418(10) C(4)–C(5)
1.4418(10)
β
molecules) bond formation. This step produces a
black resinous substance that solidifies into a glassy
mass upon cooling. The substance is insoluble in water
or organic solvents; its IR spectrum retains characterꢀ
istic absorption bands of the perrhenate anion. With an
increase in the temperature, the organic ligand
degrades and the final thermolysis product is a mixture
of amorphous carbon and the solid solution Rh Re0.5.
Cl(3)–O(1)
Cl(3)–O(1)iv
Cl(3)–O(1)v
*
The symmetry operation codes for equivalent atoms of III are
i ii iii iv
1
.5 – x, 1.5 – y, z; 1.5 – x, y, z; x, 1.5 – y, z; 1.5 – x,
v vi
0
.5 – y, z; –0.5 + x, 1 – y, 1 – z; 1 – x, 0.5 + y, 1 – z.
0.5
The experimental weight of the final thermolysis prodꢀ
uct corresponds to the overall scheme:
tallizes from DMF, the formation of solvate II · DMF
[
Rh(βꢀPic) Cl ]ReO
4
2Rh Re + 18C
0.5 0.5
2
4
becomes more favorable. Similar structural features
+
β
ꢀPic
Solvate II
110 (Fig. 4c). According to Xꢀray powder diffracꢀ
↑
+ (other gaseous products).
were observed for the salt [RhPy Cl ]ReO4, which crysꢀ
4
2
tallizes as both this salt and its dehydrate.
· DMF releases a DMF molecule at
~
°С
The general view of structure II DMF is shown in
·
tion data, the firstꢀstep product is structurally identical
with the starting pure salt II. At higher temperatures,
the TG curve is shaped like that of salt II described
above and has the same quantitative characteristics.
Fig. 2. Dimethylformamide molecules are in the
channels formed by the cations and anions. The dipole
moments of adjacent DMF molecules are collinear
but oppositely directed. Thus, the dipolar interactions
additionally stabilize the solvate structure. The
The perchlorate salt decomposes explosively at
>
270°С; so its thermal transformations were not studꢀ
ied.
Thus, for the salts containing the cation transꢀ
Cl
⎯Rh–Cl axes of the cations are all perpendicular to
the plane (0011). The shortest distances are Rh⋅⋅⋅Rh
(
6.841 Å) and Rh⋅⋅⋅Re (6.782 Å).
–
+
–
The crystal structure III (Fig. 3) can be represented
as a system of cationꢀformed channels aligned with the
axis z. In this structure, the Cl–Rh–Cl axes are paralꢀ
[
Rh( ꢀPic) Cl ] with the anions Cl , ClO4 , and
β
4 2
–
ReO4 , the dependence of the thermal properties on
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 5
2010

COMPLEX SALTS
351
00
C(6)
C(2)
(а)
6
100
3
6 amu (–2H O)
2
C(3)
C(2)
T
C(4)
C(3)
C(4)
90
500
400
300
200
C(6)
O(1)
93 amu (–Pic)
C(1)
N(1) Cl(1)
C(5)
80
C(1)
70
N(1)
N(1)
129 amu (–PicHCl)
O(1)
O(1)
C(5)
60
Rh(1)
Cl(3)
C(5) O(1)
C(1)
50
Rh +12C
100
Cl(2)
C(6)
C(2)
C(3)
N(1)
C(5)
TG
40
C(1)
C(4)
C(3)
0
0
00:28 00:43 00:57 01:12 01:26
C(2)
Time (h:min)
C(6)
(b)
C(4)
1
00
Fig. 1. Structure III (hydrogen atoms are omitted).
95
90
85
80
75
70
65
130 amu (–PicHCl)
RhRe +18C
100
200
300
400
500
600
T, °C
(c)
100
73 amu (–DMF)
Fig. 2. General view of the structure of solvate II · DMF
along the axis . DMF molecules are shown as balls with
the respective van der Waals radii.
90
80
70
60
y
130 а.е.м. (–PicHCl)
RhRe +18C
1
00 200 300 400 500 600 700
T, °C
Fig. 4. TG curves of (a) salt I, (b) salt II, and (c) solvate II ·
DMF.
Rh
Cl
O
N
C
the composition is of the same fundamental character
as for related complexes with pyridine and ꢀpicoline.
However, the steps in the thermolysis of salt are not
z
x
y
γ
I
well resolved, which is probably due to the closer temꢀ
peratures at which the corresponding processes start.
Fig. 3. General view of the crystal structure of salt III
.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 36
No. 5
2010

352
VASIL’CHENKO et al.
+
Note that the cations trans
ꢀ
[Rh(
β
ꢀPic) Cl ] and
6. Jorgensen, S.M., J. Prakt. Chemie, 1885, vol. 27, p. 478.
4
2
+
[
RhPy Cl ] have close sizes and form similar strucꢀ
tures (e.g., solvation of perrhenate salts). The salt
Rh( ꢀPic) Cl ]ReO forms no solvates because the
cavities made by the cation packing are noticeably
larger and can accommodate both perchlorate and
perrhenate ions.
4 2
7. Aleksandrova, E.L. and Khimich, N.N., Fiz. Tekh.
Poluprovodn. (St.ꢀPeterburg), 2004, vol. 38, no. 11,
p. 1280 [Semiconductors (Engl. Transl.), vol. 38, no. 11,
p. 1280].
[
γ
4
2
4
8. Korenev, S.V., Venediktov, A.B., Shubin, Yu.V., et al.,
Zh. Strukt. Khim., 2003, vol. 44, no. 1, p. 74.
9
. Zadesenets, A.V., Filatov, E.Yu., Yusenko, K.V., et al.,
Inorg. Chim. Acta, 2008, vol. 361, p. 199.
ACKNOWLEDGMENTS
1
1
1
0. Toshima, N. and Yonezawa, T., New J. Chem., 1998,
We are grateful to N.V. Kurat’eva for performing Xꢀ
ray diffraction experiments, N.I. Alferova for her
assistance in recording the IR spectra, and I.V. El’tsov
for recording the NMR spectra and for his assistance
in their interpretation.
p. 1179.
1. Kovrova, N.B., Bondarenko, V.S., Korniets, E.D.,
et al., Zh. Obshch. Khim., 1994, vol. 64, p. 885.
2. Vasil’chenko, D.B., Baidina, I.A., Filatov, E.Yu., and
Korenev, S.V., Zh. Strukt. Khim., 2009, vol. 50, no. 2,
p. 349.
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2010