Isolation of homoleptic platinum oxyanionic complexes with doubly protonated diazacrown cation

Article abstract of DOI:10.1016/j.molstruc.2016.10.088

Doubly protonated diazacrown ether cation (1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane DCH₂²⁺) was used for the efficient isolation of the homoleptic platinum complexes [Pt(NO₃)₆]^2- and [Pt(C

Full text of DOI:10.1016/j.molstruc.2016.10.088

Accepted Manuscript
Isolation of homoleptic platinum oxyanionic complexes with doubly protonated
diazacrown cation
Danila Vasilchenko, Sergey Tkachev, Iraida Baidina, Galina Romanenko, Sergey
Korenev
PII:
S0022-2860(16)31145-0
10.1016/j.molstruc.2016.10.088
MOLSTR 23089
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 19 September 2016
Revised Date: 27 October 2016
Accepted Date: 27 October 2016
Please cite this article as: D. Vasilchenko, S. Tkachev, I. Baidina, G. Romanenko, S. Korenev, Isolation
of homoleptic platinum oxyanionic complexes with doubly protonated diazacrown cation, Journal of
Molecular Structure (2016), doi: 10.1016/j.molstruc.2016.10.088.
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ACCEPTED MANUSCRIPT

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Isolation of Homoleptic Platinum Oxyanionic Complexes with Doubly
Protonated Diazacrown Cation.
Danila Vasilchenko,†,‡,* Sergey Tkachev,† Iraida Baidina,† Galina Romanenko,§
Sergey Korenev†,‡
†Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of
Science, 630090 Novosibirsk, Russian Federation
‡Novosibirsk State University, 630090 Novosibirsk, Russian Federation
§ International Tomography Centre, Russian Academy of Sciences, 630090 Novosibirsk,
Russian Federation
Abstract
2+
Doubly protonated diazacrown ether cation (1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane DCH2
)
was used for the efficient isolation of the homoleptic platinum complexes [Pt(NO3)6]2- and [Pt(C2O4)2]2- to
2+
crystalline solid phases from solutions containing mixtures of related platinum complexes. DCH2
molecules in nitric acid solution were shown to prevent the condensation of mononuclear [Pt(H2O)n(NO3)6-
]
n
n-2 species.
Keywords
Platinum, O-ligands, diazacrown, crystal structure, NMR
Introduction
The formation and reactivity of platinum complexes with small oxygen donor
ligands (O-ligands) are an area of coordination chemistry with a considerable practical
value. Complexes of platinum with oxygen donor ligands like nitrate and oxalate
represent good thermolabile starting compounds for the preparation of supported
catalytic systems based on highly dispersed metallic platinum or its oxide [1,2]. From
this point of view, the solution chemistry of such complexes is of significant interest,
especially for the elaboration of new techniques for the isolation of the individual
complex species.
Multinuclear NMR spectroscopy has been used to demonstrate the variety of
chelated and monodentate complexes formed between platinum(II) and oxalate ligands
during the reaction of K2PtCl4 and oxalic acid [3,4]. In addition, as was reported for the
first time by Krogmann and Dode [5], partial oxidation of platinum(II) oxalato complexes
occurs in air, resulting in the formation of an interesting series of one-dimensional
conductors [6–8]. Platinum nitric acid solutions represent even more complex mixtures
of mononuclear and polynuclear species existing in dynamic equilibrium [9,10].
The diversity of possible complex forms that a platinum cation can adopt in a
-
-
solution containing these ligand molecules (C2O4 , NO3 , H2O and OH-) has a hampering
effect on the detailed study of such systems and the isolation of individual metal

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complexes in the solid phase. Molecular recognition technology, based on
supramolecular interactions, is of use in the industrial practices of the separation and
selective isolation of platinum-group metals by the ion-exchange technique. For
example, the SuperLig@ family of ion-exchange resins, based on macrocyclic ligands
anchored to a silica gel support, is used for the selective removal of platinum, palladium
and rhodium from solutions [11]. On the other hand, the selective isolation of metal
complexes is also possible by the electrostatic interaction of metal complexes with a
cation of appropriate size.
In this work we used doubly protonated diazacrown ether dication (1,4,10,13-
tetraoxa-7,16-diazoniacyclooctadecane – DCH22+) for the efficient isolation of the
homoleptic platinum complexes [Pt(NO3)6]2- and [Pt(C2O4)2]2- from solutions containing
mixtures of related platinum complexes. The combination of positive charge, structural
+
2+
flexibility and the presence of H-bond donor groups (NH2 ) provides DCH2 molecules
the ability to form complementary pairs with the mentioned platinum oxyanionic
complexes.
Experimental materials
1. Starting reagents and physical measurements
All the reactants were purchased from commercial suppliers and used as
received. [Pt(H2O)2(OH)4] was prepared from hexachloroplatinic acid ("The Gulidov
Krasnoyarsk Non-Ferrous Metals Plant" Open Joint Stock Company, 39.1% of platinum)
as described previously [12]. Nitrate salt DCH2(NO3)2 was precipitated from ethanol
solution of DC (Alfa Aesar, 96%) by an excess of concentrated nitric acid, filtered off
and dried in air stream.
195Pt NMR spectra were recorded at 107.5 MHz using an Avance III 500 Bruker
spectrometer with a 5 mm broad-band probe. A 90° ex citation pulse of 15 µs was
applied. All spectra were recorded at 24°C. δ195Pt (ppm) values are reported relative to
the external reference – a 2 M solution of H2[PtCl6] in 1 M hydrochloric acid. The usual
spectral window of 67 kHz (620 ppm) was used with an acquisition time of 0.1 s and
pulse delay of 0.7 s to allow the 195Pt nuclei to relax completely. A line-broadening factor
of 1 Hz was applied in the processing of all experimental FID data.
X-ray powder diffraction analysis of the polycrystalline samples was carried out
on a DRON-RM4 diffractometer (Cu Kα radiation, graphite monochromator in the
reflected beam, scintillation detector with amplitude discrimination). The samples were
prepared by deposition of a suspension in hexane on the polished side of a cell made of
fused quartz. A sample of polycrystalline silicon (a = 5.4309 Å), prepared similarly, was
used as an external standard.
Raman scattering spectra were measured on a Triplemate SPEX spectrometer
with CCD camera and microscope for the detection of the backscattering spectra with
excitation by a 488 nm laser line.
The simultaneous TG–DSC/EGA–MS measurement was performed in an
apparatus consisting of an STA 449 F1 Jupiter thermal analyser and a QMS 403D
Aëolos quadrupole mass spectrometer (NETZSCH, Germany). The spectrometer was
connected online to a thermal analyser (STA) instrument by a quartz capillary heated to

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280°C. The QMS was operated with an electron-impact ionizer with an energy of 70 eV.
The ion currents of the selected mass/charge (m/z) numbers were monitored in
multiple-ion detection (MID) mode with a collection time of 1 s for each channel. The
measurements were made in a helium flow in the temperature range of 30–700°C using
a heating rate of 10°C min -1, a gas flow rate of 30 mL min-1 and open Al2O3 crucibles.
The sample mass was 20 mg. Analysis of the thermal data was performed with Proteus
analysis software [13].
2. Preparation of solutions
2.1. Solution NT (nitric acid solution)
A sample of [Pt(H2O)2(OH)4] (150 mg, 0.5 mmol) was dissolved in 1 mL of nitric acid
(15.7 M) and allowed to equilibrate for 5 days at room temperature in a dark place.
2.2. Solution NT1 (diluted solution of nitric acid)
A sample of [Pt(H2O)2(OH)4] (30 mg, 0.1 mmol) was dissolved in 1 mL of nitric acid
(15.7 M) and the resulting solution was transferred to an NMR tube. The 195Pt NMR
spectrum of the solution was recorded immediately after the preparation and then after
7 days, 30 days and 90 days. Between measurements the solution was stored in the
NMR tube at room temperature (20 ± 2°C) in a dark p lace.
2.3. Solution NT2 (diluted solution of nitric acid with addition of DС)
A sample of [Pt(H2O)2(OH)4] (30 mg, 0.1 mmol) and 0.2 mmol of DCH2(NO3)2 were
dissolved in 1 mL of nitric acid (15.7 M). The resulting solution was transferred to an
NMR tube and the 195Pt NMR spectrum of the solution was recorded immediately after
the preparation and then after 7 days, 30 days and 90 days. Between measurements
the solution was stored in the NMR tube at room temperature (20 ± 2°C) in a dark place.
2.4. Solution OX (oxalic acid solution)
A sample of [Pt(H2O)2(OH)4] (150 mg, 0.5 mmol) was boiled in 10 mL of oxalic acid
water solution until fully dissolved, and the volume was reduced to 5 mL. The resulting
solution was allowed to equilibrate in a closed container for 5 days at room temperature
in a dark place.
3. Isolation of solid phases
3.1. (DCH2)[Pt(NO3)6] (1)
Solid diazacrown was added to Solution NT. This mixture was allowed to stand in a
desiccator under solid KOH at room temperature. After 5 days yellow prisms were
filtered out, washed with a minimal volume of 15.8 M HNO3 and acetone, and dried in
an air stream. Yield: 65%. Analysis calculated (found) for C12H28N8O22Pt: C, 17.33
(17.3); H, 3.39 (3.4); N, 13.48 (13.6). Single crystals for X-ray analysis were collected
from the mother liquor.
3.2. (DCH2)[Pt(C2O4)2] (2)

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Solid diazacrown was introduced into Solution OX, resulting in the deposition of a fine
pale orange precipitate, which was filtered out, washed with water, ethanol and ether
and then dried in a stream of air. Yield: 70%. Analysis calculated (found) for
C16H28N2O12Pt: C, 30.24 (30.1); H, 4.44 (4.4); N, 4.41 (4.2). Single crystals for X-ray
analysis were obtained by recrystallization of the product from hot water.
The powder diffraction patterns of polycrystalline powders of compounds 1 and 2 were
completely indexed using single-crystal data; no additional reflections were revealed.
4. X-ray crystallographic data collection and refinement
Crystal data and experimental details for 1 and 2 are given in Table 1S. Experimental
data for the determination of the crystal structure of 1 were collected on a Bruker APEX-
II CCD diffractometer at 240 K using graphite-monochromated Cu Kα radiation (λ =
1.54178 Å). Experimental data for the determination of the crystal structure of 2 were
collected on a Bruker-Nonius X8 APEX CCD diffractometer at 296 K using graphite-
monochromated Mo Kα radiation (λ = 0.7107 Å). All calculations were carried out with
the SHELX-97 crystallographic software package [18]. The structure was solved by the
standard heavy-atom method and refined by the anisotropic approximation. The H
atoms were refined in their geometrically calculated positions; a riding model was used
for this purpose. Absorption corrections were applied empirically using the SADABS
software [14].
CCDC 1491951 (1) and 1491954 (2) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Results and Discussion
Solutions containing mixtures of nitrato or oxalato complexes of platinum were
obtained from [Pt(H2O)2(OH)4] (often referred to as H2Pt(OH)6) by interaction with nitric
or oxalic acid, respectively. The resulting solutions (Solution NT and Solution OX, see
Experimental Section for details) were characterized by 195Pt NMR spectroscopy to
describe the platinum speciation. As is clearly seen from the spectra (Figures 1 and 2),
platinum was distributed in these solutions over several complex forms. The nitric acid
solution (Solution NT) contained a mixture of mononuclear species [Pt(H2O)n(NO3)6-n]n-
2, including the [Pt(NO3)6]2- anion, whose signals were located in the range 3500–3950
ppm, and polynuclear hydroxo-bridged nitrato complexes of platinum(IV) with resonance
lines in a weaker field range [9,10].

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Figure 1. NMR spectrum of [Pt(H2O)2(OH)4] solution in nitric acid (Solution NT). Signals of polynuclear
(tetranuclear) species are marked with an orange colour. The [Pt(NO3)6]2- signal is pointed out with an
arrow.
The oxalic acid solution of [Pt(H2O)2(OH)4] (Solution OX) comprised both Pt(IV)
and Pt(II) complexes due to the reduction of tetravalent platinum by oxalate ions. The
signal in the high-field range of the 195Pt NMR spectrum of this solution (-540 ppm)
corresponds to the [Pt(C2O4)2]2- anion (with a fraction of about 50%), while the two
signals around 2600–2900 ppm are resonances of the [Pt(H2O)2(C2O4)2] and
[Pt(H2O)4(C2O4)]2+ species [3,4]. Prolonged standing of Solution OX resulted in a
deepening of its blue colour, which originates from the formation of polynuclear
Pt(II)/Pt(IV) clusters with an intense charge transfer [15].
Figure 2. NMR spectrum of [Pt(H2O)2(OH)4] solution in oxalic acid (Solution B).
Since the homoleptic Pt complexes ([Pt(NO3)6]2- in Solution NT and [Pt(C2O4)2]2-
in Solution OX) were not the only form of platinum in the given solutions (their mole
fractions were about 5% and 50%, respectively), attempts to crystallize these species in
the form of solid salts by evaporation with alkali metal salts were unsuccessful. It has

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been reported that protonated diazacrown (DCH22+) appeared to be a suitable cation to
isolate anionic aquafluorocomplexes of germanium [16]. We adopt this approach to
crystallize the platinum complexes from Solution NT and OX and have founded that
2+
DCH2
selectively isolates homoleptic complexes ([Pt(NO3)6]2- and [Pt(C2O4)2]2-
correspondingly) from such multispecies solutions.
Slow concentration of Solution NT (evaporation at room temperature) with the
addition of diazacrown (DC) yielded yellow crystals of 1. This compound was sparingly
soluble in concentrated nitric acid, with the formation of the mononuclear aquanitrato
Pt(IV) species, while in water it slowly decomposed to form hydrated platinum oxide
(PtO2·3H2O). The thermal decomposition of the complex 1 in inert atmosphere
proceeded at about 150°C as a one-stage process and resulted in the formation of
metallic platinum with an admixture of amorphous carbon. The gaseous products
escaping in this process were determined by mass spectrometry as CO, CO2, N2 and
H2O (Figure 1S).
The compound 1 crystallizes in monoclinic P21/n space group. The asymmetric
unit cell of 1 consists of one half of the protonated diazacrown molecule and half of the
hexanitratoplatinate(IV) anion. The oxygen atoms of the nitrato ligands form a trigonal
antiprismatic (D3d) polyhedron around the platinum(IV) cations located on the axes or
edges of the unit cell. The geometric characteristics of the PtO6 polyhedron (see Table
1 for details) and the mutual orientation of the nitrato groups are almost the same as
reported earlier for a different salt of the [Pt(NO3)6]2- anion [1,9]. This fact indicates that
the unusual trigonal antiprismatic shape of the PtO6 polyhedron is not a result of
packing effects but the stable form of the [Pt(NO3)6]2- anion. An analogous geometry
was recently reported for the homoleptic nitrato complexes of tin(IV) [17], rhodium(III)
[18] and chromium(III) [19] and interpreted (in the former work) as consequence of
ligands crowding in coordination spheres. The Raman spectrum taken from solid 1
demonstrates two clearly resolved signals around 350 cm-1 corresponding to Pt-O
stretching vibrations of the PtO6 polyhedron also founded in the spectrum of Solution
NT (Figure 2S). The coordination of the nitrate ion to the platinum centre causes
substantial elongation of the N-O bonds by ca. 0.14 Å.
2+
Figure 3. Mutual arrangement of species ([Pt(NO3)6]2- anion and two DCH2 dications) in the crystal
structure of I. The planes of DCH22+ molecules are marked with grey, H-bonds are shown as broken lines.
Hydrogen atoms are omitted for clarity.

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The overall packing of ions in the crystal structure of 1 presents columns running
along the a axis (Figure 3S). These columns are constructed from alternate [Pt(NO3)6]2-
2+
anions and DCH2 dications connected through a network of H-bonds. Two of the six
-
NO3 ligands of the [Pt(NO3)6]2- anion are directed to the DCH22+ dications in a column,
and the oxygen atoms of these groups form H-bonds with the nitrogen centres of the
-
macrocyclic cation. The remaining four NO3 ligands are oriented to the neighbouring
columns and only weakly interact with the cationic species. The DCH22+ dications adopt
a planar conformation, with distances between planes in the columnar structures
DCH22+–[Pt(NO3)6]2-–DCH22+ of about 10 Å (Figure 3).
Table 1. Selected metal–ligand and intra-ligand bond lengths, metal-centred bond angles and related H-
bonds parameters for compound 1.
Bonds, Å
Angles, °
Pt-O31 2.002(3) O311-Pt-O31
Pt-O11 2.007(5) O311-Pt-O11
Pt-O21 2.013(3) O31-Pt-O11
N1-O12 1.211(5) O11-Pt-O111
N1-O13 1.220(5) O311-Pt-O21
N1-O11 1.347(5) O31-Pt-O21
N2-O23 1.210(7) O11-Pt-O21
N2-O22 1.219(6) O111-Pt-O21
N2-O21 1.326(6) O21-Pt-O211
180.0(2)
79.3(1)
100.7(1)
180.0(1)
80.2(1)
99.8(1)
77.7(2)
102.3(2)
180.0(1)
121.4(3)
120.7(3)
122.3(3)
N3-O32 1.205(6)
N3-O33 1.219(5)
N3-O31 1.347(5)
N1-O11-Pt
N2-O21-Pt
N3-O31-Pt
Hydrogen bonds
O13…H7B…N7
2.14 0.91
2.25 0.91
2.36 0.91
150.7
158.1
135.1
O21…H7A…N7
O11…H7A…N7
1-X,2-Y,1-Z; 21-X,2-Y,1-Z
According to the previously reported data [9,10], in a fresh nitric acid solution of
[Pt(H2O)2(OH)4] only the mononuclear species [Pt(H2O)n(NO3)6-n]n-2 is present. After
standing of the solution at room temperature, the condensation of these complexes
progressed to form polynuclear species, whose 195Pt NMR signals appear in the low-
2+
field range 3900–4500 ppm. Because DCH2
molecules show a unique
complementarity with [Pt(NO3)6]2- anions in the solid state, we assumed that an
analogous strong interaction of the macrocyclic cation with the anionic species
[Pt(H2O)n(NO3)6-n]n-2 in the nitric acid solution could prevent the condensation process.
To verify this hypothesis, two nitric acid solutions of H2Pt(OH)6 were prepared: with
(Solution NT2) and without (Solution NT1) the addition of DCH2(NO3)2 (the nitrate salt
was chosen instead of DC itself to avoid acidity changes). The solutions’ compositions
were monitored over the course of 3 months by 195Pt NMR spectroscopy.
Inspecting Figure 4, one can see that the formation of polynuclear complexes was
suppressed in Solution NT2, where diazacrown was added, in comparison with the

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intensive polycondensation process in Solution NT1. It should be noted that no solid 1
was formed during the standing of Solution NT2 and evaporation was required up to
[Pt] ≈ 1 M before 1 began to crystallize.
Figure 4 Evolution of 195Pt NMR spectra obtained for nitric acid solution of [Pt(H2O)2(OH)4] with (Figure 4
right, Solution NT1) and without (Figure 4 left, Solution NT2) addition of solid diazacrown, [Pt] = 0.1 M
for both solutions, [DCH22+] = 0.2 M. a) – the spectra immediately after preparation of the solutions, b) –
after 1 week, c) – after 1 month d) – after 3 months. Signals of polynuclear (tetranuclear) species are
marked with an orange colour.
Contrary to an evaporation-induced growth of the crystals of 1 from Solution NT,
the addition of solid DC or its water solution to Solution OX immediately deposited the
pale yellow solid DCH2[Pt(C2O4)] (2). Deposition of 2 prevented the formation of the
mentioned polynuclear Pt(II)/Pt(IV) charge-transfer complexes by the Krogmann
mechanism [4,15]; thus, the navy colour of the solution disappeared completely upon
the addition of DC. Recrystallization of 2 was only possible from hot (boiling) water
solution because of its low solubility.
Analogously to 1, column-like cation–anion agglomerates can also be found in the
crystal structure of 2 (Figure 5, Figure 4S). The platinum centre in the planar oxalato
complex [Pt(C2O4)2]2- is surrounded by four oxygen atoms at about 2 Å (Table 2) and
has geometric characteristics similar to those reported previously for this anion [2].
Stretching Pt-O vibrations of this PtO4 polyhedron are registered in Raman spectrum of
solid 2 (Figure 5S) as a band at about 300 cm-1.
The terminal oxygen atoms of the [Pt(C2O4)2]2- anion form a network of H-bonds
2+
with the DCH2 dications, which in this case adopt a chair conformation and envelop
the oxalate ligands (Figure 5). The distances between the planes of DCH22+ dications in
2+
the column are 11.2 Å – slightly longer than such distances in 1. The DCH2 dications
and [Pt(C2O4)2]2- connect with each other through the system of H-bonds (2.80–3.00 Å)
+
between the oxygen atoms of the oxalate ligands and the NH2 groups of the
macrocycle (Table 2).

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Figure 5. Mutual arrangement of [Pt(C2O4)2]2- anion and two DCH22+ dications in the crystal structure of II.
2+
The planes of DCH2 molecules are marked with grey, H-bonds are shown as broken lines. Hydrogen
atoms of methylene groups are omitted for clarity.
Table 2. Selected metal–ligand and intra-ligand bond lengths, metal-centred bond angles and related H-
bonds parameters for compound 1.
Bonds, Å
Angles, °
Pt1-O2 2.008(3) O2-Pt1-O22
Pt1-O22 2.008(3) O2-Pt1-O12
180.0
97.62(14)
82.4(1)
Pt1-O12 2.020(4)
O2-Pt1-O1
Pt1-O1 2.020(4) O22-Pt1-O1
O1-C1 1.264(6) O12-Pt1-O1
97.6(1)
180.0(1)
113.1(3)
113.2(3)
O2-C2 1.284(6)
O3-C1 1.222(6)
O4-C2 1.205(6)
C1-C2 1.558(7)
C1-O1-Pt1
C2-O2-Pt1
Hydrogen bonds
O3…H1N…N1K
2.24 0.90
2.09 0.90
1.98 0.90
142.5
136.5
160.7
O4…H1N…N1K
O3…H2N…N1K
1-X,2-Y,-Z; 21-X,1-Y,1-Z
The powder of 2 was stable on heating in an inert atmosphere up to 250°C, upon
which it decomposed in one stage to give the gaseous products CO, CO2, H2O and N2
(Figure 6S) and metallic platinum (with an admixture of amorphous carbon). It should be
noted that thermal decomposition of both 1 and 2 in a hydrogen stream yielded pure
metallic platinum without a carbon admixture.

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Conclusions
Homoleptic anionic complexes of platinum [Pt(C2O4)2]2- and [Pt(NO3)6]2- were
selectively isolated from solutions containing complicated mixtures of related complexes
by using the macrocyclic cation DCH22+. The structures of the salts and their properties
were studied. For the aquanitrato complexes of platinum, DCH22+ was demonstrated to
act as an effective suppressor of their polycondensation.
Acknowledgment
This work was supported by the Russian foundation for basic research grant 16-03-
00549 A and 14-03-00411 A. D.V. thanks the Ministry for Education and Science of the
Russian Federation for the award of a fellowship of the President of the Russian
Federation for young scientists.
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ACCEPTED MANUSCRIPT
Protonated diazacrown selectively isolates platinum(IV) homoleptic complexes.
Intensive H-bonding connects the macrocycle and platinum(IV) complexes.
Condensation of platinum nitrato complexes can be suppressed by diazacrown.