Journal of Molecular Structure 1100 (2015) 174e179

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Synthesis, crystal structures, and characterization of double complex

salts [Au(en)2][Rh(NO2)6]$2H2O and [Au(en)2][Rh(NO2)6]
Pavel E. Plyusnin a, b, *, Evgenia V. Makotchenko a, b, Yury V. Shubin a, b, Iraida A. Baidina a,
Ilya V. Korolkov a, b, Liliya A. Sheludyakova a, b, Sergey V. Korenev a, b
a
b

Nikolaev Institute of Inorganic Chemistry, 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russia
Novosibirsk State University, 2, Pirogova Str., Novosibirsk 630090, Russia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 20 April 2015
Received in revised form
30 June 2015
Accepted 13 July 2015
Available online 15 July 2015

Double complex salts of rhodium(III) and gold(III) of the composition [Au(en)2][Rh(NO2)6]$2H2O (1) and
[Au(en)2][Rh(NO2)6] (2) have been prepared. Crystal structures of the compounds have been determined
by single crystal X-ray diffraction. The compounds have been characterized by PXRD, IR, far-IR, CHN and
DTA.
The complexes have a layered structures. The presence of water in 1 makes the structure of the hydrated DCS less dense as compared to the anhydrous one. The environment of the cation and the anion in
the two structures is the same, oxygen atoms of the nitro groups are involved in hydrogen bonds N
eH/O, N/O distances being approximately the same. The structures of 1 and 2 are notable in having
shortened contacts between the gold atoms and the oxygen atoms of the nitro groups of the neighboring
complex anions. The thermal behavior of the complexes in a hydrogen atmosphere was investigated. The
nal product of thermolysis prepared at the temperature 600
is a two-phase mixture of pure metallic
gold and the solid solution Rh0.93Au0.07.
2015 Elsevier B.V. All rights reserved.

Keywords:
Gold
Rhodium
Double complex salts
X-ray structural analysis
Thermal analysis

1. Introduction

2. Experimental

Double complex salts (DCS) are attractive as complex singlesource precursors for preparation of nanosized bimetallic systems
applied in heterogeneous catalysis [1,2], as well as for stabilization
and isolation of unstable ions [3]. Besides, such compounds can
exhibit expressed antimicrobial activity to some microorganisms
[4]. Currently, preparation of gold-rhodium catalysts is highly
topical. Such systems are known to be active in the reactions of
selective reduction of nitrogen oxides (NOx) [5], hydrogenization of
CO2 [6], partial methane oxidation [7]. One of the problems in
development of noble metal based catalysts is the inuence of
halide anions reducing their activity. Therefore, the main goal of
this study was the synthesis of halogen-free two-component goldrhodium precursor.

2.1. Materials and methods

Solid state IR spectra were measured on a Scimitar FTS 2000
spectrometer (4000e400 cm1, KBr pellets) and Vertex 80 IR-FT
spectrometer (400e100 cm1, PE pellets).
CHN analytical data were obtained with Euro EA 3000 automatic
analyzer.
Differential thermal analysis (c-DTA) of the synthesized compounds was carried out with TG 209 F1 Iris (NETZSCH) in
hydrogen (6.5% v/v H2 in He), ow rate 60 ml/min, heating rate of
10
C/min.
The
starting
complexes
Na3[Rh(NO2)6],
[Au(en)2]Cl3,
[Au(en)2](ClO4)3$H2O were synthesized by the literature methods
[8e10].
2.2. Synthesis of [Au(en)2][Rh(NO2)6]2H2O (1)

* Corresponding author. Nikolaev Institute of Inorganic Chemistry, 3, Acad. Lavrentiev Ave., Novosibirsk 630090, Russia.
E-mail address: plus@niic.nsc.ru (P.E. Plyusnin).
http://dx.doi.org/10.1016/j.molstruc.2015.07.023
0022-2860/ 2015 Elsevier B.V. All rights reserved.

1.0 ml of Na3[Rh(NO2)6] aqueous solution (44.8 mg, 0.1 mmol)

was added with 1 ml of [Au(en)2](ClO4)3$H2O aqueous solution
(63.3 mg, 0.1 mmol) in several portions under stirring at room

P.E. Plyusnin et al. / Journal of Molecular Structure 1100 (2015) 174e179

temperature. The resultant precipitate was leaved under the

mother liquor for one day, then the precipitate was collected on a
frit, rinsed with cold water, ethanol, and dried in air for several
hours. The procedure gave 69 mg of white polycrystalline powder.
Yield 95%.
Elemental Anal. Calcd. for AuRhC4H20N10O14 (732.13): C, 6.56; H,
2.75; N, 19.13. Found: C, 6.6; H, 2.7; N, 19.2.
2.3. Synthesis of [Au(en)2][Rh(NO2)6] (2)
1.0 ml of Na3[Rh(NO2)6] aqueous solution (44.4 mg, 0.1 mmol)
was combined with 1.0 ml of [Au(en)2]Cl3 aqueous solution
(42.3 mg, 0.1 mmol) under stirring at room temperature. The
resultant precipitate was collected on a frit, rinsed with cold water
and ethanol. Then the precipitate was dried to constant weight in a
dessicator over P2O5 to give 68 mg of milk-colored polycrystalline
powder. Yield 98% (for anhydrous DCS).
Elemental Anal. Calcd. for AuRhC4H16N10O12 (696.10): C, 6.90; H,
2.32; N, 20.12. Found: C, 6.9; H, 2.3; N, 19.6.
2.4. Synthesis of [Au(en)2][Rh(NO2)6]nH2O
5.0 ml of [Au(en)2]Cl3 aqueous solution (169.2 mg, 0.4 mmol)
were added to 5.0 ml of Na3[Rh(NO2)6] aqueous solution (179.5 mg,
0.4 mmol) under continuous stirring at 5e60
. The resultant
white precipitate was collected on a frit, rinsed with cold water,
ethanol, and dried in air for several hours to give 282 mg of polycrystalline powder. Yield 98% on [Au(en)2][Rh(NO2)6]$2H2O. Water
content in this polycrystalline sample was determined with thermogravimetric and elemental analyses as 3.12%, corresponding to
n 1.3.
Elemental Anal. Calcd. for AuRhC4H18.6N10O13.3 (714.12): C, 6.73;
H, 2.62; N, 19.62. Found: C, 6.7; H, 2.6; N, 19.5.
2.5. Preparation of single crystals of [Au(en)2][Rh(NO2)6]2H2O (1)
and [Au(en)2][Rh(NO2)6] (2)
Single crystals of 1 and 2 were obtained at room temperature by
counter diffusion in U-shaped tubes. The tubes were charged with
solutions of [Au(en)2](ClO4)3$H2O and Na3[Rh(NO2)6] (concentration 0.002 M). In one-two days crystals appeared at the tube walls,
which were examined for diffraction quality. Few parallel experiments were carried out giving the crystals of both anhydrous
(needles) and hydrated (platelets) forms.
2.6. Crystal structure determination
Experimental data for solution of the crystal structures were
collected on a Bruker-Nonius X8 APEX CCD diffractometer using
graphite-monochromated Mo Ka radiation (l 0.7107 ). The
structures were solved by the direct method and rened by the
anisotropic-isotropic approximation (for hydrogen atoms);
hydrogen atoms were set in the geometrical positions. All calculations were performed using the SHELX-97 program package [11].
Crystal data and experimental details for 1 and 2 are given in
Table 1. Additional experimental information, including atomic
positional parameters, is supplied in CIF format as described in the
Supplementary material section.
2.7. Powder diffraction study
The PXRD analysis of the samples has been performed at room
temperature on a Shimadzu XRD-7000 diffractometer (CuKa radiation, Ni lter on the reected beam, scintillation detector with
amplitude discrimination). The patterns were recorded in the step

175

mode in the angular range 2q 5e60
, step 0.05
. The samples

were prepared by applying an alcohol suspension on the polished
side of a standard quartz cuvette. Polycrystalline silicon
(a 5.4309 ) prepared similarly was used as the external
standard.
The single-phase nature of the prepared compounds was
determined by indexing the powder diffraction patterns of the
complexes using the single crystal XRD data. Indexing of the
diffraction patterns for the products of thermolysis was carried out
using the data for pure metals and compounds reported in the PDF
database [12], 2q range 5e120
was used. Unit cell parameters were
rened by the full-prole technique within the whole diffraction
range with the POWDERCELL 2.4 program [13].
3. Results and discussion
3.1. Synthesis of DCS 1 and 2
Double complex salts (DCS) containing complex cation of one
metal and complex anion of another metal are usually obtained in
solid state by exchange reaction through mixing aqueous solutions
of the corresponding complexes. The preparation of pure DCS is
possible provided complete or almost complete absence of side
reactions resulting in by-products that contaminate the target
compound. The DCS's, as a rule, are formed with high yields due to
low solubility of them in water. So, estimated solubility of 1 and 2 in
water is 2$103 . The compounds obtained are insoluble in
ethanol, acetone, chloroform, acetonitrile, dimethylformamide.
It is known that solid DCS can be isolated as anhydrous, hydrates, or mixtures depending on the synthesis conditions [14,15].
In our case the room temperature syntheses (~20
C) followed by
fast separation of the precipitate always gave the two-phase
product containing both anhydrous and hydrates DSCs. We tried
to vary synthetic conditions (temperature, time) in order to obtain
the single-phase product. The preparations of the single-phase
polycrystalline products were attempted at decreased (5
) and
elevated (60
) temperatures, but in vain. In all cases the syntheses
at temperatures within 5e60
followed by fast separation of the
precipitate afforded the two-phase product.
According to PXRD, this product is a mixture of anhydrous
complex [Au(en)2][Rh(NO2)6] 2 and hydrate [Au(en)2][Rh(NO2)6]$
nH2O with the structure of 1 (Fig. 1c).
Depending of experimental conditions (temperature, initial
concentration of reagents) the contents of phase 1 varies in range of
30e80%. As a result, the content of crystallization water in the
isolated products is variable (n ranges from 0.4 to 1.3) and depends
on the exposure of the precipitate to the mother liquor. This is
conrmed by thermogravimetric studies, PXRD and elemental
analysis. Therefore, we failed to isolate the single-phase product by
tuning the temperature of the synthesis. Simultaneous formation of
single crystals of 1 and 2 at room temperature in the same reaction
vessel (U-shaped tube) suggests their possible parallel formation
on preparation of polycrystalline samples of the DCS. The experiments involving prolonged synthesis revealed the possibility of
preparation of a pure single-phase product. So, the storage of the
precipitate formed on combination of the solutions of the starting
complexes under the mother liquor for one day affords the singlephase product [Au(en)2][Rh(NO2)6]$2H2O. Powder diffraction
pattern of this product (Fig. 1e) was completely indexed using
single crystal data for [Au(en)2][Rh(NO2)6]$2H2O (2) (Fig. 1d).
Apparently, in aqueous solution the DCS dihydrate is thermodynamically preferable over the anhydrous salt.
The quickest possible combining of the starting solutions
(temperature 5e60
) followed by separation of the precipitate
does not afford the pure anhydrous DCS. The anhydrous salt

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P.E. Plyusnin et al. / Journal of Molecular Structure 1100 (2015) 174e179

Table 1
Crystal data and experimental details for 1 and 2.

Stoichiometric formula
Formula weight
Temperature (K)
Wavelength ()
Crystal size (mm3)
Crystal system
Space group
Unit cell dimensions (,
)

Volume (3), Z
Dx (g cm3)
Absorption coefcient (mm1)
F(000)
q range for data collection (
)
Limiting indices

Reections collected
Independent reections
Completeness (%)
Max. and min. transmission
Renement method
Data/parameters
Goodness-of-t on F2
Final R indices [I > 2s(I)]
R indices (all data)

C4H20AuN10O14Rh
732.13
150(2)
0.71073
0.05  0.05  0.01
Triclinic
-1
a 7.7979(7)
b 8.0418(7)
c 8.4740(7)
465.43(7), 1
2.612
8.852
350
2.68e27.66
6  h  10
7  k  10
10  l  11
3477
2138 [R(int) 0.0292]
99.9
0.9167 and 0.6659
Full-matrix least-squares on F2
2138/147
0.985
R1 0.0324, wR2 0.0547
R1 0.0408, wR2 0.0573

C4H16AuN10O12Rh
696.10
296(2)
0.71073
0.40  0.15  0.01
Monoclinic
P21/c
a 7.5030(2)
b 8.4141(2)
c 13.4080(3)
846.44(4), 2
2.731
9.719
660
2.71e28.38
9  h  10
11  k  11
11  l  17
11372
2099 [R(int) 0.0288]
99.3
0.9091 and 0.1112
Full-matrix least-squares on F2
2099/131
1.037
R1 0.0154, wR2 0.0410
R1 0.0180, wR2 0.0429

[Au(en)2][Rh(NO2)6] can be obtained by removal of the water of

crystallization on drying the precipitate of [Au(en)2][Rh(NO2)6]$
nH2O in a dessicator over P2O5 or sulfuric acid. The anhydrous
compound can be also prepared by heating of the dehydrate
[Au(en)2][Rh(NO2)6]$2H2O to 120
in inert, reductive, or oxidative
atmosphere. The diffraction pattern of the anhydrous product
(Fig. 1a) was completely indexed using the single crystal data for
[Au(en)2][Rh(NO2)6] (2) (Fig. 1b). The absence of water is conrmed
by IR spectroscopy. It is noteworthy that on dehydration the sample
changes its color from white to milky.
On the prolonged growth of single crystals the side processes of
substitution of the inner-sphere ligands (en) and (NO
2 ) with
chloride ions of [Au(en)2]Cl3 become possible, so [Au(en)2](ClO4)3
was chosen as the starting compound. If prolonged treatment of the
reaction mixture is avoided, any of the above complexes can be
used.

Fig. 1. Experimental and simulated diffraction patterns for 1 and 2.

a 70.977(2)
b 67.927(2)
g 81.811(2)

a 90
b 90.3620(10)
g 90

3.2. Crystal structures of 1 and 2

The structure of 1 is built from complex cations [Au(en)2]3,
[Rh(NO2)6]3 anions, and crystallization water molecules. The
structure of compound 2 involves complex cations [Au(en)2]3 and
[Rh(NO2)6]3 anions. In both cases the atoms of gold and rhodium
occupy special positions on inversion centers; the structure of the
complex moieties of 1 with atomic labeling is shown in Fig. 2.
In the centrosymmetric hexanitro-anion the Rh atom coordinates six nitrogen atoms of the NO2 groups, the coordination
polyhedron of Rh is a slightly distorted octahedron [RhN6]. Bond
angles NeRheN are close to the ideal value of 90
: deviations are
within 1.5
for 1 and 0.8
for 2. The average distance RheN is
2.048 in 1 and 2.046 in 2 being close to the values reported for
hexanitrocomplexes of rhodium, e.g., [Co(NH3)6][Rh(NO2)6] [16],
[Pd(NH3)4]3[Rh(NO2)6]2 [17]. In the nitro groups of the complex
anions the lengths of the bonds NeO show little variation
(1.227e1.252, av. 1.226 in 1 and 1.218e1.246, av. 1.232 in 2);
average bond angles dNdO are 119.1
in 1 and 119.0 in 2. The
planes of the nitro groups are approximately orthogonal: dihedral
angles are 90 6
in 1 and 90 9.9
in 2.
In both structures the centrosymmetric gold cation has a slightly
distorted square coordination environment consisting of four N
atoms of two bi-dentate en ligands, the average distance AueN is

Fig. 2. ORTEP diagram of 1.

P.E. Plyusnin et al. / Journal of Molecular Structure 1100 (2015) 174e179

2.036 , the chelate angle NeAueN is 83.5 in 1 and 83.1 in 2. These

values are close to those found in compounds [Au(en)2]Cl3,
[Au(en)2]2[Cu(C2O4)2]3$8H2O, [Au(en)2](ReO4)3 [18]. The ethylenediamine metallocycles have the gauche conformation with nonequal displacement of the carbon atoms from the plane AuN2. The
deviations of the atoms C(11) and (12) from the plane AuN2 are
0.18 and 0.52 for 1 and 0.26 and 0.43 for 2. Intraligand bond
lengths NdCav and CeC are 1.502, 1.500 for 1 and 1.491, 1.500
for 2, respectively.
The structures of 1 and 2 are notable in having shortened contacts between the gold atoms and the oxygen atoms of the nitro
groups of the neighboring complex anions. The distances (2.801
in 1 and 3.056 in 2) are shorter than the sum of van der Waals
radii of Au and O atoms (3.60 ) [19]. These intermolecular contacts
complement the coordination environment of the gold atom to bipyramidal (Fig. 3).
Found distances Au/(axial) match well to the literature values
[18,20]. Non-covalent interactions between structural units, which
are longer than the sum of the covalent radii but shorter than the
sum of the van der Waals radii of the relevant atoms, were termed
secondary bonds by N.W. Alcock [21]. The presence of such bonds
have been elucidated in diverse gold(III) complexes [22]. Although
they are considered as weak, they play an important role in organization of solids.
General packing of the structural units in the crystals is shown
in Figs. 4 and 5. In 1 complex cations and anions are packed in layers
(110), each gold cation is surrounded with four rhodium anions,
and vice versa; the distances Au/Rh are 5.187e5.986 . Within the
layers, in addition to the gold contacts, complex cations and anions
are also joined by NeH/O hydrogen bonds with N/ distances
2.92e3.01 . Crystallization water molecules located between the
layers link them via hydrogen bonds OwdH/ and NeH/Ow with
the distances 2.91, 3.02 (/) and 2.85 (/N) . The shortest
distance between the water molecules in the structure of 1 is 3.30
suggesting the absence of hydrogen bonding between them. The
presence of water in 1 makes the structure of the hydrated DCS less
dense as compared to the anhydrous one. This is indicated by V/Z
values: 465.4 for 1 and 423.2 for 2. (The volume per structural unit
is higher in the hydrated DCS than in the anhydrous DCS). On water

177

Fig. 4. Overall packing of the structural units in the structure of 1 as viewed along the
a axis.

removal (heating, drying agent) the structure is compacted.

In 2 the complex cations and anions are arranged in layers, each
gold cation is surrounded with four rhodium anions and vice versa;
the distances Au/Rh are 5.637 . In the structure the complex
cations and anions are also connected by hydrogen bonds NeH/O
and d/ with /N distances 2.86e3.05 and / distances
3.19e3.37 .
Therefore, the structures are similar in layered arrangement of
the cations and anions. The environment of the cation and the
anion in the two structures is the same, oxygen atoms of the nitro
groups are involved in hydrogen bonds NeH/O, N/O distances
being approximately the same. Weak intermolecular interactions
gold-oxygen (of nitro group) are observed both in the structures of
DCS 1 and 2.

3.3. Spectroscopic characterization of 1 and 2

Fig. 3. Octahedral environment of gold(III) in the structure of 1 as complemented by

Au/O contacts.

Table 2 presents the frequencies of the major vibrations in IR

spectra of the hydrated and anhydrous DCS, as well as the sample
with n 0.5 (mix). Water content in this polycrystalline sample
was determined with thermogravimetric and elemental analyses.
Band assignment was made by comparison of the experimental
spectra and the literature data [23]. In general, in the regions of
vibrations of en and NO2 groups the spectra are similar. IR spectra of
1 and mix exhibit a broad band around 3540e3480 cme1 originating from the stretching vibration n(H) of the crystallization
water molecules, thus indicating the presence of hydrogen bonds.
Relative intensity of the n(H) band in the spectrum of mix
(n 0.5) is much smaller than in the spectrum of 1 (n 2.0), what
is related to different water content in these samples. The formation of hydrogen bonds OwdH/ and NeH/Ow is conrmed by
X-ray crystallography data. The spectra of the hydrated and anhydrous DCS are signicantly different in the region of n(NH2) vibrations. For mix and anhydrous 2 there is an intensive band at
3240 cme1, which is red-shifted in 1 by 10 cme1 (3230 cme1). Also,
the spectra of 1 and 2 exhibit essential dissimilarity in the region of
deformational vibrations of the coordinated nitrite ion (d(ONO)).
An intensive band at 828 cme1 is observed in the spectrum of 1,
which is split into two bands at 832 and 821 cme1 in compound 2.

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P.E. Plyusnin et al. / Journal of Molecular Structure 1100 (2015) 174e179

Fig. 5. Overall packing of the structural units in the structure of 2 as viewed along the a axis.

Table 2
The vibrational frequencies (cm1) of the main bands in the IR spectra of 1, 2 and mix.
[Au(en)2][Rh(NO2)6]$2H2O (1)
3533
3474
3230
3181
3102
1630
1604
1566
1407
1335
783
828
626
577
380
270
252
a

[Au(en)2][Rh(NO2)6]$0.5H2O
(mix)

Assignmenta

n(H)

3241
3123
3070

3539
3477
3240
3182
3074

1598
1556
1406
1330
789
832
821
625
578
386
284
270
255

1600
1556
1407
1331
787
831
822
625
578
384
284
271
256

[Au(en)2][Rh(NO2)6] (2)

n(NH2)
d(OH)
d(NH2)
na(NO2)
ns(NO2)
r(NH2)
d(ONO)
rw(NO2)
n(AuN)
n(RhN)
rr(NO2)

Symbols: n, stretching; d, bending; r, rocking.

3.4. Thermal behavior of the complexes

Thermal analysis curves for 1 are shown in Fig. 6 (hydrogen,
heating rate 10
C/min). The rst decomposition stage occurs
within 50e100
and corresponds to removal of the crystallization
water molecules. According to PXRD, the product obtained at this
stage is the DCS [Au(en)2][Rh(NO2)6], which is stable on further
heating to 150
. The second decomposition stage takes place
within 150e240
and is accompanied by a pronounced exo-effect.
As indicated by PXRD, the intermediate product obtained at the
temperature of 240
is a mixture of metallic gold and an X-ray
amorphous phase. The third decomposition stage in the temperature range 240e350
results in almost complete decomposition of
the compound. Minor weight loss above 350
is associated with
removal of residual decomposition products of the organic ligand.

PXRD indicates (Fig. 7.) that the nal product of thermolysis prepared at the temperature 600
is a two-phase mixture of pure
metallic gold (a 4.078(1) ) and the solid solution Rh0.93Au0.07
(a 3.823(1) ).
Thermal decomposition of the samples with intermediate content of water occurs in the same way (Fig. 8.). The water removal
stage is absent for compound 2, while further decomposition
within temperature range 150e600
takes place as described
above.
4. Conclusions
Novel double complex salts [Au(en)2][Rh(NO2)6]$2H2O and
[Au(en)2][Rh(NO2)6] have been prepared and characterized. The
structures of the complexes have been determined by single crystal

P.E. Plyusnin et al. / Journal of Molecular Structure 1100 (2015) 174e179

179

X-ray diffraction. Such compounds are promising as possible precursors for novel bimetallic systems.

Acknowledgement
This work was supported by the Ministry of Education and
Science of Russian Federation and by RFBR, research project No. 1403-00411-a.

Appendix A. Supplementary material

CCDC 429470 and 429469 for 1 and 2 contain the supplementary crystallographic data. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via http://www.
ccdc.cam.ac.uk/data_request/cif.

References
Fig. 6. TG, DTG and DTA curves of 1 in hydrogen atmosphere (6.5% v/v H2 in He, 10
C/
min).

Fig. 7. Powder diffraction patterns of decomposition products of 1 in hydrogen

atmosphere.

Fig. 8. TG curves in hydrogen atmosphere (6.5% v/v H2 in He, 10
C/min). 1 e [Au(en)2]

[Rh(NO2)6]$2H2O; 2 e [Au(en)2][Rh(NO2)6]; 3 e [Au(en)2][Rh(NO2)6]$nH2O.

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