Reaction of secondary phosphine selenides with elemental selenium: Synthesis of bis(diorganoselenophosphoryl)selenides

Full text of DOI:10.1134/S1070363210100312

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 10, pp. 2063–2064. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Artem’ev, N.K. Gusarova, S.F. Malysheva, I.A. Ushakov, B.A. Trofimov, 2010, published in Zhurnal Obshchei Khimii, 2010,
Vol. 80, No. 10, pp. 1743–1744.
LETTERS
TO THE EDITOR
Reaction of Secondary Phosphine Selenides
with Elemental Selenium:
Synthesis of Bis(diorganoselenophosphoryl)selenides
A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva, I. A. Ushakov, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: boris_trofimov@irioch.irk.ru
Received April 1, 2010
DOI: 10.1134/S1070363210100312
It is known that secondary phosphine oxides are
oxidized with oxygen to form phosphinic acids
R2P(O)OH [1]. Similarly proceeds the reaction of the
secondary phosphine sulfides with elemental sulfur
leading to dithiophosphinic acids R2P(S)SH [2]. In the
present work we first report on the reaction of the
secondary phosphine selenides with elemental
selenium. It turned out that the heating (80–85°С, 3 h)
of bis(2-arylethyl)phosphine selenides (Iа, Ib) with
one equivalent of elemental selenium in toluene does
not result in the expected diselenophosphinic acids
R2P(Se)SeH. Under these conditions, bis(diorgano-
selenophosphoryl)selenides (IIа, IIb) were obtained in
78 and 80% yield, respectively.
whose subsequent intermolecular condensation affords
the target bis(diorganoselenophosphoryl)selenides II.
R
Se
Se
II
I
P
_[H2Se]
R
SeH
The synthesized compounds II are precursors of
nanodimensional metal phosphides or selenides [3],
promising ligands for preparation of metal complexes
of the new type [4], potential extragents for heavy
metals and reactive starting reagents for organo-
elemental synthesis. Conventional methods of their
synthesis based on the use of difficultly available
diorganochlorophosphines [5, 6], sodium polyselenides
[6], or toxic and flammable trichlorosilane [5] are
laborious, low effective (the yields do not exceed 43%)
and do not match modern ecological requirements.
Recently the synthesis of bis(diorganoselenophos-
phoryl)selenides from secondary phosphines and
elemental selenium was published [7].
Ar
Se
P
+ Se
H
Ar
Iа, Ib
Se
Se
Therefore, the reaction of the secondary phosphine
selenides with elemental selenium is performed for the
first time and based on this reaction a new convenient
and preparative method is elaborated for the
preparation of bis(diorganoselenophosphoryl)selenides,
promising ligands for the design of coordination
compounds and precursors of the semiconducting and
magnetooptical nanomaterials.
P
Ar
P
Ar
toluene
80_85oC, 3 h
Se
Ar
Ar
IIа, IIb
Ar = Ph (a), 4-t-BuC6H4 (b).
Bis[di(2-phenylethyl)selenophosphoryl]selenide
(IIа). To the solution of bis(2-phenylethyl)phosphine
selenide Ia (0.32 g, 1.0 mmol) in 8 ml of toluene
The reaction can be represented by the following
scheme: secondary phosphine selenides I react with
elemental selenium to form diselenophosphinic acids
2063

2064
ARTEM’EV et al.
amorphous selenium (0.08 g, 1.0 mmol) was added at
room temperature. The mixture was stirred at heating
(80–85°С, 3 h), cooled, filtered, toluene was removed
in a vacuum. The residue was ground in hexane
(10 ml), hexane was decanted, the residue was dried in
a vacuum (40–45°С, 2 h, 1 mm Hg) to obtain selenide
IIа, 0.28 g (78%) as a yellow powder, mp 112–114ºС
(hexane). UV spectrum (acetonitrile), λmax, nm: 289. IR
spectrum (KBr), cm–1: 3059, 3023, 2917, 2890, 2855,
1949, 1878, 1805, 1640, 1599, 1492, 1447, 1389,
1329, 1269, 1211, 1133, 1019, 1006, 938, 901, 825,
C48H68P2Se3. Calculated, %: С 61.08; Н 7.26; Р 6.56; Se
25.10.
IR spectra were recorded on a Bruker IFS-25 spec-
trometer, UV spectra, on a UV/VIS Perkin Elmer
1
Lamda 35 spectrometer. Н, 13С, 31Р and 77Se NMR
spectra were obtained on a Bruker DPX-400
spectrometer (400.13, 101.61, 161.98 and 76.31 MHz,
respectively) in CDCl3, external standards 85% Н3РО4
(for 31Р) and Me2Se (for 77Se). All experiments were
run in an inert atmosphere (argon). Secondary
phosphine selenides Iа, Ib were prepared from red
phosphorus, elemental selenium, and styrene [8] or 4-
tert-butylstyrene [9] respectively.
1
743, 699, 571, 501, 454. Н NMR, δ, ppm (J, Hz):
2.61–2.69 m (4Н, CH2P), 3.05–3.14 m (12H, CH2P,
CH2Ph), 7.19–7.30 m (20Н, Ph). 13С NMR, δС, ppm:
29.53 (CH2Ph), 37.88 d (CH2P, 1JCP = 32.0 Hz), 126.32
ACKNOWLEDGMENTS
3
(Cр), 128.04 (Co), 128.40 (Cm), 139.09 d (Ci, JCP
=
=
18.0 Hz). 31Р NMR, δР, ppm: 56.04 (satellites: JP–Se
1
This work was performed with the financial support
from the Russian Foundation for Basic Research (grant
no. 08-03-00251).
378.5 Hz, JP=Se = 749.2 Hz, JPP = 19.1 Hz). 77Se
NMR, δSe, ppm: –140 d (P=Se, 1JP=Se = 749.1 Hz), 284
t (P–Se–P, 1JP–Se = 378.4 Hz). Found, %: С 53.39; Н
5.09; Р 8.55; Se 32.85. C32H36P2Se3. Calculated, %: С
53.42; Н 5.04; Р 8.61; Se 32.92.
1
2
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Bis[di{2-(4-tert-butylphenyl)ethyl}selenophos-
phoryl]selenide (IIb) was prepared similarly from bis-
[2-(4-tert-butylphenyl)ethyl]phosphine selenide Ib.
Yield 0.38 g (80%), yellow powder, mp 195–197ºС
(hexane). UV spectrum (acetonitrile), λmax, nm: 287.
IR spectrum (KBr), cm–1: 3093, 3055, 3022, 2959,
2902, 2864, 1902, 1791, 1685, 1634, 1607, 1517,
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728, 669, 563, 519, 485, 429. 1Н NMR, δ, ppm (J, Hz):
1.27 s (36Н, Me), 2.55–2.64 m (4H, CH2P), 2.96–3.09
m (12H, CH2P, CH2Ar), 7.11–7.29 m (16Н, C6H4). 13С
NMR, δС, ppm: 29.02 (CH2C6H4), 30.96 (Me3С), 34.04
(CMe3), 37.89 d (CH2P, 1JCP = 31.9 Hz), 125.27 (C-2 in
C6H4), 127.75 (C-3 in C6H4), 136.02 d (C-1 in C6H4,
3JCP = 16.5 Hz), 149.24 (C-4 in C6H4). 31Р NMR, δР,
ppm: 56.13 (satellites: 1JP–Se = 377.1 Hz, 1JP=Se = 744.8
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2
Hz, JPP =17.6 Hz). 77Se NMR, δSe, ppm: –139 d
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(P=Se, 1JP=Se = 744.5 Hz), 284 t (PSeP, 1JPSe = 377.6 Hz).
Found, %: С 61.12; Н 7.22; Р 6.50; Se 25.20.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 10 2010