Formation of palladium phosphides in the reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus

Article abstract of DOI:10.1134/S1070363212020077

The reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium diphosphide PdP₂ that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to palladium phosphides Pd₅P₂, Pd₃P_0.8, Pd _4.8P, and free dibenzylideneacetone. Pleiades Publishing, Ltd., 2012.

Full text of DOI:10.1134/S1070363212020077

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 2, pp. 206–211. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © N.I. Skripov, L.B. Belykh, L.N. Belonogova, A.V. Rokhin, T.P. Stepanova, F.K. Shmidt, 2012, published in Zhurnal Obshchei
Khimii, 2012, Vol. 82, No. 2, pp. 210–215.
Formation of Palladium Phosphides in the Reaction
of Bis(dibenzylideneacetone)palladium(0)
with White Phosphorus
N. I. Skripov, L. B. Belykh, L. N. Belonogova, A. V. Rokhin, T. P. Stepanova, and F. K. Shmidt
Irkutsk State University, ul. K. Marksa 1, Irkutsk, 664003 Russia,
email: belykh@chem.isu.ru
Received December 9, 2010
Abstract—The reaction of bis(dibenzylideneacetone)palladium(0) with white phosphorus was studied using
the methods of NMR, UV spectroscopy, and X-ray powder diffraction. The products of the reaction are shown
to be palladium phosphides, their composition depending on the ratio of the reagents. The mechanism of the
formation of the palladium-enriched phosphides is suggested, which includes the formation of palladium
diphosphide PdP2 that subsequently reacts with the excess of bis(dibenzylideneacetone)palladium(0) leading to
palladium phosphides Pd5P2, Pd3P0.8, Pd4.8P, and free dibenzylideneacetone.
DOI: 10.1134/S1070363212020077
In recent 10–15 years a qualitative jump occurred
in the chemistry of elemental phosphorus. On the one
hand, the methods of activation of white phosphorus in
the coordination sphere of the transition metal
complexes were substantially developed, namely, the
coordination chemistry of white phosphorus [1–6]. The
structure of the formed phosphorus fragment is
strongly influenced by the nature of the ligands in the
coordination sphere of the transition metal. Transition
metal complexes having the molecule of Р4 as a η1-
ligand are stable only in the presence of bulky ligands
in the coordination sphere of the metal [6], otherwise
the splitting of the P–P bond occurs with subsequent
recombination of small fragments into binuclear com-
plexes or polyatomic aggregates [1–4], or hydrolytic
oxidation in the presence of water [3, 6]. The transition
metal plays a role of a stabilizer of all phosphorus
intermediates from the simplest phosphide anion to
complex phosphorus oligomers Рn with up to 14 phos-
phorus atoms.
increase the turnover number and turnover frequency
in hydrogenation of alkenes almost by the order of
magnitude [7, 8]. The main reason of the promoting
effect of white phosphorus on the catalytic properties
of the system Pd(acac)2–Р4–Н2 is the increase in the
dispersity and stability of the formed nanoparticles [8].
The modifying effect of elemental phosphorus on the
catalytic properties of palladium catalysts depends on a
number of factors: the nature of the acidoligand in the
precursor, reducer, concentration and the ratio of the
reagents [9]. We believe that one of the reasons of the
effect of the nature of the acidoligand on the properties
of nanosized palladium catalysts modified with ele-
mental phosphorus is the difference in the rates of
reduction of Pd(II) to Pd(0), subsequent reaction of
Pd(0) with elemental phosphorus, and clusterization of
Pd(0). For the active in hydrogenation palladium
catalysts modified with elemental phosphorus the
following model was suggested: the core of the nano-
particle consists of palladium phosphides, mainly
Pd6P, and its surface, of the active in the hydrogena-
tion Pd(0) clusters.
On the other hand, a field is developed connected
with the use of white phosphorus as a modifier for
preparation of nanoparticles highly effective in hydro-
genation. In particular, we have first shown that
introduction of white phosphorus into the reaction
system prior to the stage of reduction of palladium bis-
(acetylacetonate) [Pd(acac)2] with hydrogen allows to
It is known that palladium phosphides can be
obtained by various methods: the high temperature
synthesis from the elements [10], thermal decomposi-
tion of organometallic precursors, in particular, phos-
phine complexes formed in situ from the metal salt and
206

FORMATION OF PALLADIUM PHOSPHIDES
207
Transformation of complex Pd(dba)2 in DMF in inert atom-
sphere: c0[Pd(dba)2] 1 mM, Т 30°С
trioctylphosphine [11], decomposition of tertiary, secon-
dary and primary phosphines in the coordination
sphere of Pd(0) in hydrogen atmosphere [12, 13], reac-
tion of metal nanoparticles with trioctylphosphine at
280–300°С [14]. For chemical simulation of separate
stages of formation of palladium catalysts modified
with elemental phosphorus for hydrogenation carried
out under mild conditions and for elaboration of new
approaches to the synthesis of nanoparticles effective
in hydrogenation, we have studied the reaction of bis
(dibenzylideneacetone)palladium(0) [Pd(dba)2] with
white phosphorus at room temperature. The Pd(dba)2
complex was chosen due to the fact that dibenzyl-
ideneacetone is a relatively labile ligand and is not
subjected to destructive transformations in the palla-
dium coordination sphere.
Concentration of Pd(dba)2
Concentration of
Time, min
dba, mM
c, mM
%
20
60
0.711
71.1
0.59
0.570
0.313
0.164
0.095
0
57.0
31.2
16.4
9.5
0.90
90
1.36
120
150
180
1.74
1.93
0
2.06
tion, ε525 = 33540 l mol–1 cm–1) was ca. 2 mM (see the
table).
Dibenzylideneacetone (dba) forms with the
platinum group metals several types of complexes in
which it acts as a monodentate alkene with electron-
withdrawing substituent, M(dba)3 (M = Pd, Pt) or as a
bridging ligand in binuclear complexes of platinum
The decrease in the concentration of complex
Pd(dba)2 in DMF is due to the substitution of the
coordinated dibenzylideneacetone by the DMF solvent
molecules, which are unable to stabilize Pd(0) com-
plexes. Taking into account the composition of the
Pd(dba)2 complex in the solution, the process can be
represented by the following stoichiometric equations.
.
and palladium, M2(dba)3 Solv (Solv = СHCl3, CH2Cl2,
C6H6) [15]. Bis(dibenzylideneacetone)palladium(0)
Pd(dba)2 used by us as a precursor belongs to binuclear
.
complexes M2(dba)3 (dba) (М = Pd, Pt) with three
Pd2(dba)3(Solv) + xSolv ⇄ 2Pd(0){Solv}x+1 + 3dba,
Pd(0){Solv}x+1 → 1/nPdn + (x + 1)Solv.
bridging dibenzylideneacetone ligands in the s-cis, s-
trans–conformation, where the molecule of dibenzyl-
ideneacetone is captured during crystallization instead
of the molecule of the solvent. The binuclear structure
of the Pd(dba)2 complex is retained in the solution
[15].
Here, Solv is DMF, х ≤ 3.
The formed palladium nanoclusters of the average
size, according to the transmission electron micro-
scopy, of ~3 nm are aggregatively unstable and
interact with the formation of branched chains (Fig. 1).
Pd2(dba)3(dba) + Solv ⇄ Pd2(dba)3(Solv) + dba
Since DMF is in excess, the decomposition of the
Pd(dba)2 complex in DMF at 30°С obeys the kinetic
equation of the pseudo-first order.
Hereinafter we will use the traditional designation
for bis(dibenzylideneacetone)palladium [Pd(dba)2].
Since the dibenzylideneacetone ligand is one of the
most labile from the known π-ligands, the relative
kinetic stability of the Pd(dba)2 complex in solution
may depend on the nature of the solvent. As showed
the UV spectroscopy, the intensity of the 525 nm
absorption band of complex Pd(dba)2 (d → d* transit-
ion, ε525 = 6400 l mol–1 cm–1) in an inert atmosphere in
benzene remained unchanged during 20 days for the
concentration of 3 mM. At the same time, when
Pd(dba)2 was dissolved in DMF, the intensity of the
absorption band at 525 nm in the UV spectrum at 30°С
decreased. After 3 h, complex Pd(dba)2 in DMF was
completely destroyed and the solution contained free
dibenzylideneacetone whose concentration calculated
from the absorption band at 325 nm (n → π* transi-
r = kIc[Pd(dba)2].
Here, r is the reaction rate, k1 is the rate constant (min–1),
c is the current concentration.
The numerical value of the rate constant k1
calculated from the equation kI = 1/tln c0/c is equal to
1.28×10–2 min–1, (с0 is the initial concentration, t is the
time of the reaction).
Considering the results on the kinetic stability of
bis(dibenzylideneacetone)palladium(0) in the solution,
the experiments on the reaction of Pd(dba)2 with
elemental phosphorus were carried out in benzene. The
reaction in an inert atmosphere proceeds smoothly at
room temperature. Addition of the solution of white
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208
SKRIPOV et al.
cPd, mM
50 nm
t, min
Fig. 2. Kinetic curves of transformation of Pd(dba)2 for the
reaction of white phosphorus in benzene at various molar
ratios of the reagents: [P4]:[Pd(dba)2] = (1) 0.05, (2) 0.1,
(3) 0.25, and (4) 0.5. сPd(dba)2 3.3 mM, Т 20°С.
Fig. 1. TEM image of palladium nanoclusters formed from
complex Pd(dba)2 in DMF: cPd 1 mM, Т 30°С.
Pd2(dba)3Solv + P4 ⇄ 2PdP2 + 3dba + Solv,
phosphorus to the solution of complex Pd(dba)2 in
benzene with the ratio [P4]:[Pd] = 0.5 or [P]:[Pd] = 2.0
(to one phosphorus atom) results in a change in the
color from wine red to yellow in 10–20 s from the
beginning of the reaction and in the formation of a
black precipitate. In the UV spectrum of the reaction
system Pd(dba)2–0.5 Р4 {c0[Pd(dba)2] 3.280 mM} the
absorption band at 525 nm is absent suggesting the
complete transformation of the Pd(dba)2 complex. The
concentration of dibenzylideneacetone is 5.864 mM,
consequently, all dibenzylideneacetone from its com-
plex Pd(dba)2 remains in the solution. In the 31Р NMR
spectrum of the system Pd(dba)2–0.5Р4 taken after
10 min from the beginning of the reaction the signal of
white phosphorus (δР –522 ppm) is lacking, and no
other signals are registered in the region of 500 to
–550 ppm.
where Solv is benzene.
We have found that the reaction between Pd(dba)2
and elemental phosphorus at room temperature does
not stop at the stage of the phosphide PdP2 formation.
For the ratio [P4]:[Pd] < 0.5 ([P4]:[Pd] = 0.1; 0.25) in
the system Pd(dba)2–nР4 the transformation of the
complex Pd(dba)2 is also close to quantitative although
the time of the reaction, according to the UV spectral
data, increases from 10–20 s for [P4]:[Pd] = 0.5 to 3 h
for [P4]:[Pd] = 0.25; 24 h ([P4]:[Pd] = 0.1, conversion
90%). For the ratio [P4]:[Pd] = 0.05 the conversion of
Pd(dba)2 after 6 days is ~70%.
On the kinetic curves of the dependence of con-
centration of Pd(dba)2 on time of the reaction with white
phosphorus two parts can be distinguished (Fig. 2). In
the first (initial) part the rate of the reaction varies
depending on concentration of white phosphorus from
1.10×10–4 ([P4]:[Pd] = 0.05) to 2.04×10–4 ([P4]:[Pd] =
0.1) and 4.54.10-4 ([P4]:[Pd] = 0.25) mol l–1 min–1, that
corresponds to the first order with respect to phos-
phorus. In the second part of the kinetic curve the rate
diminishes 15–40 times. Such a sharp decrease in the
reaction rate in the solution can be caused by inhibition
by the reaction products or by changing the type of the
reaction from homogeneous to heterogeneous. It is
noteworthy that in the 31Р NMR spectrum of the
system Pd(dba)2–nР4 (n = 0.05; 0.25) taken after
10 min from the beginning of the reaction the signal of
white phosphorus disappears and no other signals are
The black precipitate isolated from the reaction
system Pd(dba)2–0.5Р4 (sample 1) is X-ray amorphous
and so highly disperse that even an amorphous halo
cannot be registered on the X-ray diffractogram. After
calcination of sample 1 for 4 h at 400°С, on the dif-
fraction curve broadened reflections of crystalline
phases were registered belonging to palladium
phosphides PdP2 and Pd5P2, the former predominant.
Hence, the reaction of Pd(dba)2 with white phosphorus
in benzene at the ratio [P4]:[Pd] = 0.5 leads pre-
dominantly to the formation of the phosphide PdP2
most enriched with phosphorus, whose formation,
taking into account the composition of the Pd(dba)2
complex in the solution, can be represented by the
following stoichiometric equation.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 2 2012

FORMATION OF PALLADIUM PHOSPHIDES
209
registered in the region of 500 to –550 ppm both in the
starting period and after one day.
temperature with the initial rate of 7×10–7 mol l–1 min–1
{с0[Pd(dba)2] 3.550 mM, Pd(dba)2:PdP2 = 11}.
Quantitative phase analysis of sample 2 was
impossible. Taking into account that the ratio [P4]:[Pd] =
0.05 (or [P]:[Pd] = 0.20 to one phosphorus atom), no
more than 10% of PdP2 calculated on Pd(dba)2 can be
formed in the first stage. This is consistent with the
experimental data. Since the conversion of Pd(dba)2 is
70% and the ratio P/Pd in the precipitate ~0.3, it can be
shown that 80% of PdP2 and 52% of Pd(dba)2 will be
consumed for Pd3P0.8 formation; 3.5% of Pd(dba)2 will
react with 4.4% Pd3P0.8 to give Pd4.8P (3.5%). Thus,
sample 2 contains mainly phosphide Pd3P0.8 (89.8%)
and small amounts of PdP2 (3.7%) and Pd4.8P (6.5%).
In total, the spectral and kinetic data allow an
assumption that at various ratios of the reagents in the
first stage Pd(dba)2 reacts with white phosphorus with
the formation of palladium phosphide PdP2. Further
transformations of Pd(dba)2 are caused by its reaction
with PdP2. Since PdP2 is poorly soluble, the reaction of
Pd(dba)2 should proceed on the surface of palladium
nanophosphide. Transition from homogeneous to
heterogeneous reaction in this case would give rise to a
sharp decrease in the reaction rate.
To establish the nature of the intermediates and the
final products of transformation the black precipitate
formed in the reaction system Pd(dba)2–0.05Р4 was
isolated (sample 2). Taking into account that the con-
version of Pd(dba)2 was about 70%, and the solution,
as showed the NMR spectroscopy data, did not contain
phosphorus or the products of its transformations, the
ratio P/Pd in the precipitate should be equal to ~1:3.
Therefore, it was proved experimentally that the
reaction of Pd(dba)2 with white phosphorus at room
temperature affords palladium phosphides, their
composition depending on the initial ratio of the
reagents. The formation of the palladium-enriched
phosphides proceeds via a series of subsequent steps
including the formation of palladium diphosphide,
which further reacts with the excess of Pd(dba)2 giving
rise to palladium phosphides Pd5P2, Pd3P0.8, Pd4.8P.
From the diffraction pattern analysis, sample 2 is a
combination of crystalline and amorphous phases. On
the diffraction curve of sample 2 on the profile of the
amorphous halo for the reflection angles 2θ = 30°–75°
the reflections of crystalline phases were registered,
which belong to palladium phosphides PdP2; Pd3P0.8,
and Pd4.8P; an admixture of highly disperse palladium
metal is also possible. Palladium phosphide Pd3P0.8 is
known to crystallize in the cementite type (Fe3C), and
its difference from the ideal composition in the
phosphide Pd3P (Pd/P = 3:1) is due to random
vacancies of phosphorus [16]. We failed to identify
some reflections of the crystalline phases in the range
of small reflection angles 2θ = 6°–30°.
EXPERIMENTAL
UV spectra were registered on a SF-2000 spec-
trophotometer in quartz cell 0.01 cm thick. NMR
spectra were registered on a VXR-500S Varian pulse
spectrometer. 31Р chemical shifts are given relative to
85% phosphoric acid. Positive values correspond to
1
downfield shifts. H and 13С chemical shifts are given
relative to tetramethylsilane.
Diffraction pattern analysis of the catalysts samples
was performed on a DRON-3M diffractometer, CuKα
radiation. Analysis of the samples by transmission
electron microscopy was performed on a Philips EM-
410 microscope. A drop of the in situ formed catalyst
solution was put on a grid covered with carbon film
and dried in argon atmosphere. The conditions of the
experiment excluded melting and decomposition of the
studied samples under the action of the electron beam.
The results of analysis of sample 2 of palladium
phosphide PdP2 are consistent with the aforementioned
hypothesis that, irrespective of the ratio of the
reagents, the reaction of Pd(dba)2 with white
phosphorus proceeds via the formation of palladium
phosphide, whose further slow reaction with Pd(0)
results in the palladium-enriched phosphides.
Pd2(dba)3Solv + P4 = 2PdP2 + 3dba + Solv,
PdP2 + 2Pd2(dba)3 = Pd5P2 + 6dba,
2Pd5P2 + Pd2(dba)3 = 4Pd3P + 3dba,
0.93Pd3P + Pd2(dba)3 = Pd4.8P + 3dba.
Solvents (benzene, DMF) were purified by standard
procedures used in the work with organometallic
compounds [17]. DMF was additionally stored over
dry copper sulfate to remove water and amines till the
formation of green solution and was twice distilled in a
vacuum (8 Torr) at the temperature no higher than 42°С.
Benzene was finally dried by distillation over LiAlH4
Additional experiments have shown that palladium
phosphide PdP2 does react with Pd(dba)2 at room
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 2 2012

210
SKRIPOV et al.
and stored in an argon atmosphere in sealed ampules
over molecular sieves 4А. The concentration of water
in benzene determined by the Fisher method [18] was
1.1×10–3 M, in DMF, 0.8 M.
ideneacetone ligands in the palladium complex and of
free dibenzylideneacetone is proved by the presence of
four singlets in the region of 180–190 ppm with δС
189.4, 184.9, 182.2, 181.1 ppm.
The reaction of bis(dibenzylideneacetone)palla-
dium(0) and white phosphorus with different ratio of
the reagents was performed in dry oxygen-free argon
atmosphere in a finger type vessel in benzene solution.
White phosphorus was purified mechanically from
the surface products of oxidation and washed with dry
benzene. The solution of white phosphorus in benzene
was prepared and stored in an inert atmosphere in a
finger type vessel, whose design allowed us to
evacuate it and fill with argon. 31P NMR spectrum: δР
–522 ppm.
а. To the wine-red solution of 0.5 g (9.4×10–4 mol)
of Pd(dba)2 in 210 ml of benzene 9.4 ml (4.7×
10–4 mol) of the solution of white phosphorus in
benzene was added. At mixing, the solution rapidly
changes the color from wine red to black; after 10–20 s
from the beginning of the reaction a black precipitate
was formed and the solution turned yellow. The filtrate
was analyzed by the methods of 31Р NMR and UV
spectroscopy. When the reaction was completed the
solution was decanted from the precipitate, the
precipitate was washed thrice with benzene (10 ml)
and dried in a vacuum (30°С, 1 Torr). Yield 0.16 g.
The sample is X-ray amorphous. To make it crystal-
line, it was kept in a sealed tube at 400°С in inert
atmosphere for 4 h and cooled slowly. The diffraction
pattern analysis of sample 1 after heating showed the
following reflections on the diffraction curve, d/n, A
(I/I0): 4.004(46) (not identified), 3.340(15) (Pd5P2),
2.998(31) (not identified), 2.930(65) (PdP2), 2.878(94)
(PdP2), 2.722(100) (Pd5P2, PdP2), 2.515(29) (Pd5P2,
PdP2), 2.448(15) (Pd5P2), 2.284(32) (Pd5P2), 2.122(31)
(Pd5P2), 2.111(37) (Pd5P2), 2.080(38) (Pd5P2), 2.052
(38) (PdP2), 2.002(35) (PdP2), 1.982(15) (Pd5P2), 1.900
(23) (PdP2), 1.838(33) (Pd5P2), 1.795(31), 1.735(23)
(Pd5P2), 1.689(20) (PdP2), 1.489(15) (not identified),
1.470(25) (Pd5P2, PdP2) 1.367(15) (Pd5P2), 1.349(11)
(Pd5P2), 1.308(11) (Pd5P2). The reflections were
assigned according to the known X-ray characteristics
of PdP2 [10] and Pd5P2 (PDF 19-887) [25].
Dibenzylideneacetone was synthesized by the reac-
tion of benzaldehyde with acetone [19] and crystal-
1
lized from ethanol. H and 13C NMR spectra in СDCl3
coincide with the literature data [20].
Bis(dibenzylideneacetone)palladium(0) was prepared
by reduction of PdCl2 with methanol in the presence of
sodium acetate and dibenzylideneacetone using the
procedure described in [21, 22], as dark-violet pre-
cipitate with mp 152°С (150°С [23]). Taking into
account that Pd(dba)2 exists in solution in the dimeric
form Pd2(dba)3Solv [15], the following designations
1
were used for description of the H NMR spectra of
Pd(dba)2. Three bridging bidentate dibenzyl-
ideneacetone ligands in the s-cis-s-trans-conformation
were designated as dba(1), dba(2), dba(3), the alkene
fragment of dibenzylideneacetone in the cis-position to
the carbonyl group, as cis-alkene, in the trans-position,
as trans-alkene. The signals were assigned according
to [24].
HB
C1
O
C3
HA
Ph
C2
C4
C5
HA
Ph
HB
1H NMR (СDCl3, δ, ppm) dba (1): cis-alkene 6.65 d
b. To the wine-red solution of 0.69 g (1.2×
10–3 mol) of Pd(dba)2 in 260 ml of benzene 4 ml
(6.0×10–5 mol) of the solution of white phosphorus in
benzene was added. A black precipitate is immediately
formed although the solution remains wine-red. The
mixture was treated as above. The filtrate was
analyzed by the methods of 31Р NMR and UV
spectroscopy. After 6 days the solution was decanted
from the precipitate, the precipitate (sample 2) was
washed thrice with benzene (10 ml) and dried in
vacuum (30°С, 1 Torr). Yield 0.15 g. Sample 2 is a
combination of crystalline and amorphous phases. The
diffraction pattern analysis of sample 2 showed the
(1H, CНА, 3JHH 13.4 Hz), 6.77 d (1H, CНВ, 3JHH 13.4 Hz);
3
trans-alkene: 4.99 d (1H, СНА, JHH 13.4 Hz), 5.94 d
3
(1H, СНВ, JHH 13.4 Hz);. dba (2): cis-alkene 6.37 d
3
3
(1Н, СНА, JHH 13.4 Hz), 6.47 d (1Н, СНВ, JHH 13.4
3
Hz); trans-alkene: 4.96 d (1Н, СНА, JHH 13.4 Hz),
3
5.89 d (1Н, СНВ, JHH 13.4 Hz); dba (3): cis-alkene
5.13 d (1Н, СНА, 3JHH 13.4 Hz), 5.34 d (1Н, СНВ, 3JHH
3
13.4 Hz); trans-alkene: 6.16 d (1Н, СНА, JHH
12.2 Hz), 6.81 d (1Н, СНВ, JHH 12.2 Hz); dba (free):
3
3
7.76 d (2Н, 2СНА, JHH 16 Hz), 7.11 d (2Н, 2СНВ,
3JHH 16 Hz). The signals with δ 4.96 and 4.99 ppm are
overlapped [24]. The presence of three dibenzyl-
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FORMATION OF PALLADIUM PHOSPHIDES
211
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following reflections on the crystalline phase in the
range of reflection angles 2θ = 30°–75° and on the
profile of amorphous halo at 2θ 35°–45°, d/n, A (I/I0):
2.910(8) (PdP2), 2.871(24) (PdP2), 2.796(6) (Pd4.8P),
2.739(17) (PdP2), 2.667(5) (Pd12P3.2), 2.623(15)
(Pd4.8P), 2.548(7) (Pd12P3.2, Pd4.8P), 2.505(28) (PdP2,
Pd12P3.2, Pd4.8P), 2.473(15), 2.420(18) (Pd4.8P), 2.362
(28) (Pd12P3.2, Pd4.8P), 2.320(34) (Pd12P3.2, Pd4.8P),
2.288(40) (Pd12P3.2), 2.247(53) (Pd12P3.2, Pd4.8P), 2.222
(47) (Pd12P3.2, Pd4.8P), 2.188(35), 2.168(27) (Pd4.8P),
2.118(24) (Pd12P3.2, Pd4.8P), 2.100(22) (Pd12P3.2), 2.075
(20) (Pd12P3.2, Pd4.8P), 2.068(20) (Pd4.8P), 2.044(16)
(PdP2), 2.022(12) (Pd4.8P), 1.987(11) (PdP2, Pd12P3.2,
Pd4.8P), 1.958(11) (Pd4.8P), 1.933(11) (Pd4.8P), 1.920
(11), 1.902(10) (PdP2, Pd4.8P), 1.882(6) (Pd12P3.2,
Pd4.8P), 1.880(4) (Pd12P3.2, Pd4.8P), 1.837(7) (Pd12P3.2),
1.802(4) (Pd4.8P), 1.779(4) (Pd12P3.2), 1.767(4)
(Pd12P3.2), 1.749(4) (Pd12P3.2), 1.714(2) (PdP2), 1.680
(2) (Pd12P3.2), 1.595(2) (Pd12P3.2), 1.519(2) (Pd12P3.2),
1.454(1) (PdP2, Pd12P3.2), 1.374(4) (Pd12P3.2), 1.366(4)
(PdP2), 1.318(7) (PdP2). The reflections were assigned
according to to the known X-ray diffraction data for
PdP2 [10], Pd12P3.2 (PDF 42-0922) and Pd4.8P (PDF 19-
0890) [23]. Palladium phosphide Pd12P3.2 is also
denoted as Pd3P0.8. The presence of admixture of
palladium metal is possible: d/n (I/I0): 2.247, 1.958,
1.374. Some lines at small reflection angles was not
identified; 1.318(7) (PdP2).
16. Andersson, Y., Rundqvist, S., Tellgren, R., and Tho-
mas, J.O., J. Solid State Chem., 1980, vol. 32, p. 321.
17. Gordon, A.J. and Ford, R.A., A Handbook of Practical
Data, Techniques, and References, New York: Wiley,
1972.
ACKNOWLEDGMENTS
18. Mitchell, J. and Smith, D., Aquametry, Moscow:
Khimiya, 1980.
This work was carried out in the framework of the
Federal Targeted Program “Scientific and Pedagogical
Staff of Innovative Russia” (State contract no. P 1344).
19. Vulfson, N.S., Preparativnaya organicheskaya khimiya
(Preparative Organic Chemistry), Мoscow: Khimiches-
kaya Literatura, 1959.
20. Spectral Database for Organic Compounds (SDBS),
National Institute of Advanced Industrial Science and
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 2 2012