Phosphorus Compounds with the VI B Group Elements *
Y . MONTEIL a n d H .
VINCENT
University Claude Bernard, Lyon I, Laboratoire de Physico-Chimie minerale, Associe au C.N.R.S. N° 116,
Service du Pr. Cueilleron, 43, Bd. du 11 novembre 1918, 69621 Villeurbanne, France
(Z. Naturforsch. 31 b, 668-672 [1976]; received October 7, 1975)
Binary Phosphorus Chalcogenides, Phase Diagrams, Ternary Phosphorus Chalcogenides
The preparation and the properties of phosphorus sulfides and selenides are reviewed.
The exact number of phosphorus sulfides and selenides has been determined from the
phase diagram. Phosphorus does not react with tellurium. The ternary diagram P-S-Se
shows no P-S-Se compounds. The domains of P-S and P-Se glasses has been also determined. IR and mass spectrometry show that phosphorus sulfides and selenides have a
tetrahedral arrangement of P atoms close to that of white phosphorus.
Introduction
Phosphorus reacts with the V I B group elements
o f the periodic table a large number o f c o m p o u n d s .
These
compounds
are
characterized
by
their
structural analogies: they derive f r o m the P4 tetraedron o f the white phosphorus molecule.
T h e structures o f several binary c o m p o u n d s are
known:
Besides
Pt,s3 (1)
P4S5 (3)
phosphorus, sulfur, selenium, tellurium and o x y g e n
t h e y are represented in Fig. 1.
P 4 Se 3 (2)
P4Se5U)
can exhibit cage like structures. Only phosphorus
oxides have been studied nearly completely 9 .
A . Binary Compounds Pre-XOT ( X = S, Se or Te)
A.I.
Research of the binary
A . I . 1. P h o s p h o r u s
compounds
sulfides
T h e exact number o f P - S c o m p o u n d s has been
determined f r o m the phase diagram 1 0 . This diagram
is presented in Fig. 2. I t
exhibits 3
congruent
P4S10, P4S7 and P4S3 and 4 n o n compounds P4S9, P4S5, P4S4 and
melting c o m p o u n d s
congruent melting
P4S2. This last sulfide is metastable. The c o m p o u n d s
with congruent melting exist with 2 allotropic forms.
A . I . 2. P h o s p h o r u s
selenides
T h e phosphorus selenides had been less studied
than the phosphorus sulfides. The reason is that
* Paper, presented at the 1. International Symposium
on Inorganic Heterocycles, Besan^on (France), June
16-19,1975.
Requests for reprints should be sent to Prof. Dr
Y.
MONTEIL,
Lab.
de
Physico-Chimie
minerale
I,
associe au C.N.R.S., Service du Pr. Cueilleron, 43,
Bd. du 11 novembre 1918, F-69621
Villeurbanne,
France.
Fig. 1. Structures of differents compounds.
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Y . M O N T E I L - H . V I N C E N T • P H O S P H O R U S COMPOUNDS W I T H T H E V I B G R O U P E L E M E N T S
669
Fig. 4. Phase diagram P-Se.
A . I . 3. R e s e a r c h o f p h o s p h o r u s t e l l u r i d e s
Fig. 2. Phase diagram P-S.
selenium gives glasses with phosphorus over a large
range o f concentration 1 1 . These glasses are p r o d u c e d
even when the P - S e mixtures are c o o l e d d o w n
slowly after thermal treatment. The glassy range
spreads over 3 - 5 2 at. % P.
The curve o f the evolution o f the T g glassy
transition temperature o f these glasses plotted
against the phosphorus content o f the sample
(Fig. 3) shows that in the 0 - 5 2 at. % P range, there
are t w o phosphorus selenides with congruent
melting at the Se/P = 2,5 and Se/P = 1 ratios.
T h e result is confirmed b y the P - S e phase
diagram. I t shows only 3 phosphorus selenides
melting congruently: P4Seio, P4Se4 and P4Se3
(Fig. 4). The c o m p o u n d P4Ses although described
in the literature 7 has not been f o u n d , m a y be due
to metastability. The P4Se7 pattern has been
observed in the combination f o r m e d b y reacting
P4Seio with pyridine 1 4 .
T o our knowledge, only a siogle phosphorus
telluride has been described, P2Te3 1 5 . The preparation consists in heating white phosphorus with
p o w d e r e d tellurium at 320 °C during 1 hour in a
sealed tube.
T h e same procedure has been followed. The
p r o d u c t which was obtained corresponds t o the
author's description. I t presents the same appearance and the same density. However, o n l y tellurium
was f o u n d b y radiocristallographic analysis. The
a b o v e m e t h o d gives a mixture o f tellurium and red
phosphorus, the latter being amorphous t o X - r a y .
I t is n o t necessary to use white phosphorus which is
transformed into red phosphorus at 320 °C.
W e therefore studied several mixtures o f tellurium
and red phosphorus systematically b y
DTA.
Different compositions have been chosen, the
a t o m i c ratios being P / T e = 2 ; 1.33; 1; 0 . 8 ; 0.4. The
D T A curve o n heating discloses o n l y t w o endothermic phenomena due t o the elements melting.
T h e elements mixture were heated u p t o 800 °C
in thick silica tubes (3 m m ) . Heating was continued
during various times u p t o a week. Then, the samples
are slowly cooled (l°/min). X - r a y diagrams show
n o t a single line which cannot be assignated t o
either tellurium or phosphorus.
A.I I. Structure of the binary
compounds
T h e different binary c o m p o u n d s o f P with S, Se
and T e are summarized in the following Table.
The
asterix
crystal.
has n o t
structure o f c o m p o u n d s noted with an
has been deduced f r o m X - r a y o n a single
The exact structure o f the other c o m p o u n d s
y e t been determined.
670
Y . M O N T E I L - H . V I N C E N T • P H O S P H O R U S COMPOUNDS W I T H T H E V I B G R O U P ELEMENTS 670
P-S
P-Se
P-Te
P4S10*
P4S9
P4S7*
P4S5*
P4S4
P4S3*
P4S2
P4Seio
—
1
p4Sio
P4Se5*
P4Se4
P4Se3*
1
/
4 S e 10
P4S4
like structure f o r these t w o compounds. I n mass
spectroscopy, the molecular peaks
P4S4
and P4Se4
are observed. A fragmentation scheme o f P4Se4 is
presented in Fig. 5. The presence of the P4Se3+ ion
enables one t o propose a cage like structure. There
is a similar fragmentation for P4S4.
On an other hand, the I R absorption spectra o f
and P4Se4 exhibit a specific b a n d for the
e x o c y c l i c P - S b o n d at 690 c m - 1 and the e x o c y c l i c
P - S e at 500 c m " 1 . I t must be noticed that the I R
spectrum of
P4S4 is
identical t o
P4S5 which
again it cage like structure. A t
confirms
last the
good
agreement between the experimental enthalpy o f
f o r m a t i o n of
P4S4
j
1
1J
750
and P4Se4 are insoluble in
all solvents. Some arguments are in f a v o u r o f a cage
P4S4
1
•
1/1
1?
is unstable at r o o m tem-
perature and therefore difficult t o study.
The compounds
n
.'""A
/'
P4S2
25
j
P
The compound
20
•
and the enthalpy o f formation
600
/
40 n
\\
\
400
r
250cm-1
Fig. 6. IR absorption spectra of P4S10 and P4Seiocalculated f r o m the different bonds energies P - S
and P - P is another argument in favour of the
proposed structural 1 6 .
P4Seio is amorphous t o X - r a y s . Many authors
g a v e it the P4Seio formula in preference t o P2Ses.
This former f o r m u l a P4Seio is confirmed b y our
mass and I R spectrometric studies and we propose
a structure which is analogous t o P 4 S 1 0 1 2 .
I n our mass spectral studies we did n o t observe
the molecular peak corresponding t o P4Seio. The
largest mass observed corresponds to P2Ses + ; but
the presence o f ions with tetrahedral structure as
PSe3 + , P2Se2+ and P 3 S e + and the likeness o f dissociation fragments o f P4Seio and P4S10 show that
P4Seio has also a tetrahedral structure. The lack o f
molecular peak can be explained b y a dissociation
o f P4Seio in P2Ses radicals in the gas phase. The
same p h e n o m e n o n was observed with P4S10
11
•
I R absorption spectra o f P4Seio and P4S10 are
presented in Fig. 6. These t w o spectra have the
same general appearance with respect t o the absorption bands distribution.
A t t e m p t s t o obtain P4S4, P4Se4 and P4Seio as
single cristals b y a v a p o r transport method are n o w
in
progress.
The
radiocristallographic
study
on
these w o u l d confirm the proposed structures without
ambiguity.
A.III.
Preparative
methods
A . I I I . 1. S t a r t i n g f r o m r e d p h o s p h o r u s a n d
sulfur
A l l phosphorus sulfides can be prepared b y this
method.
P-Se
/ V
P+
The
reaction
temperature
necessary
is
a b o v e 300 °C. A slow cooling process is necessary to
Se +
Fig. 5. Splitting scheme of P4Se4 by mass spectroscopy.
o b t a i n the l o w temperature f o r m s and compounds
with incongruent melting.
Y. MONTEIL-H. VINCENT • PHOSPHORUS COMPOUNDS W I T H THE VI B GROUP ELEMENTS
P4Se3 19 and P4Se4 20 are also obtained from the
elements. The a form of P4Se3 is obtained after
treatment with carbon disulfide 21 . Cristaline P4Se4
is prepared at 350 °C. A glass is obtained above this
temperature. It has not been possible to obtain
P4Seio by this method.
A. I I I . 2. S t a r t i n g f r o m w h i t e
sulfur and selenium
phosphorus,
White phosphorus is more reactive than red
phosphorus. At 120 °C, the reaction between the
two elements is vigorous and exothermic. In this
way we obtained quantitatively the phosphorus
selenides P 4 Sei 0 , P 4 Se 4 and P 4 Se 3 12>20.
At room temperature, in carbon disulfide solution,
white phosphorus reacts slowly with sulfur to give
P4S5 22 . WTien iodine is present, in the same solvent,
it is the P4S7 sulfide which precipitates rapidly 2 3 .
The action of iodine can be explained by a first step
reaction between phosphorus and iodine which
leads to P2I4 which then reacts with sulfur to give
P4S7 according to the reaction:
2 P2I4 + 7 S -> P4S7 + 4 I2
F A L I U S 24
obtained P4S7 rapidly by reacting sulfur
with P2I4.
Analogous reactions between selenium and P2I4
have now been carried out. In the dark, two ternary
compounds are formed depending on the ratio
Se/P2l4 2 5 , 2 6 - These compounds are unstable: when
heated at 100 °C, iodine is split off and a solid
residue remains which is black and amorphous under
X-ray. P4Seio is present in this residue as shown by
tnass spectroscopy.
A. I I I . 3. S t a r t i n g f r o m P 4 X 3 ( X = S o r S e )
* Reaction with sulfur (or selenium)
It is possible to obtain the complete set of
sulfides by reacting P4S3 with sulfur 27 . Contrary,
P4Se3 yields only the two compounds P4Se4 20 and
P4Seio 12 . The temperature must not exceed the
*iven values in order to avoid the formation of
glassy products:
P 4 Se 3 + Se
P 4 Se 3 + 7 Se
300 °C
215 °C
>- P 4 Se 4
• P 4 Seio
* Reaction with halogens
671
The action of halogens on the P4X3 ( X = S or Se)
heterocycles leads to different compounds depending
on the halogen.
a) With iodine two compounds are obtained,
P4S3I2 and P4Se3l2. These two iodides possess also
a cage like structure 2 8 - 3 0 .
b) With bromine, there is attack of the cage. At
room temperature, in CS2 solution, P4S10, P4S7 and
PBr3 are obtained 3 1 . At 0 °C, the reaction is more
simple: besides PBr 3 only P4S5 is obtained. As P4S5
is insoluble in the solvent, it is obtained in a pure
state 7 .
An analogous reaction, with P4Se3, has been
carried out at 0 °C using the same conditions. After
one week, one obtains a dark product which is
amorphous to X-ray. Mass spectrometry shows ions
resulting from the fragmentation of P4Seio besides
small amounts of P4Se4+ and P4Se3+ ions. These
latter ions do not result from the fragmentation of
the P4Seio cage. They can only be explained b y the
existence of the compound P4Ses.
The action of bromine on P4Se4 selenide is
vigourous and the cage is broken. Whatever the
temperature, PBr3 and SeBr4 are obtained.
A. I I I . 4. R e a c t i o n o f PC1 3 w i t h H 2 X
( X = S or Se)
The reaction between H2S and PCI3 leads to a
mixture having a P4S5.8 composition 3 2 .
The action of H 2 Se on PCI3 at room temperature
has been studied. Phosphorus trichloride has been
used pure or diluted in carbon tetrachloride.
Hydrogen selenide reacts at once to give a solid.
The end of the reaction is marked by end of the
evolution of hydrogen chloride.
The residue is amorphous to X-rays: it seems
to be a mixture of different phosphorus selenides.
From this mixture, it has been possible to extract
P4Se3 either by dissolving in carbon disulfide or by
sublimation at 10"1 torr and 215-300 °C. After
purification, I R and mass spectra of the residues
show the existence of P4Seio and P4Ses.
B. Ternary Compounds
W e tried to find ternary compounds based on
phosphorus and containing 2 of the 3 elements S,
Se and O in order to obtain heterocycles. The P4O6S4
ternary compound is known and can be obtained
according to the scheme:
672
Y . M O N T E I L - H . V I N C E N T • P H O S P H O R U S COMPOUNDS W I T H T H E V I B G R O U P ELEMENTS 672
160 °C
P406 + 4 S
2 P 4 Sio + 3 P 4 Oio
450 °C
P406S4
33
>• 5 P 4 0 6 S 4
34
N o reaction has been noticed between P 4 Oio and
P 4 Seio- On an other hand, P 4 Seio reacts with P 4 SioT h e reaction is a complex o n e : P 4 S? is mainly
p r o d u c e d and is easily recognized f r o m its X - r a y
diagram.
The existence o f ternary c o m p o u n d s o f P, S and
Se has been studied systematically b y D T A and
radiocristallography. W e tried t o substitute sulfur
b y selenium a t o m s in the molecules o f phosphorus
sulfide and vice versa. The similar properties o f the
sulfur and selenium compounds let foresee a possible
substitution without basic change in the structural
properties of the compounds. T o this end, we plotted
the ternary diagram P - S - S e
35 • 36 .
T h e isometric projection in Fig. 7 gives a general
view o f the spatial diagram. N o mixed phosphorus
Fig. 7. Ternary diagram P-S-Se.
chalcogenides can be discerned in this diagram.
1
2
3
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