Atom-economic synthesis of ammonium diselenophosphinates from secondary phosphine selenides, elemental selenium, and ammonia

Full text of DOI:10.1134/S1070363210070315

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 7, pp. 1383–1384. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Artem’ev, N.K. Gusarova, S.F. Malysheva, A.A. Tatarinova, B.A. Trofimov, 2010, published in Zhurnal Obshchei Khimii,
2010, Vol. 80, No. 7, pp. 1217–1218.
LETTERS
TO THE EDITOR
Atom-Economic Synthesis of Ammonium Diselenophosphinates
from Secondary Phosphine Selenides,
Elemental Selenium, and Ammonia
A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva, A. A. Tatarinova, and B. A. Trofimov
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gusarova@irioch.irk.ru
Received March 11, 2010
DOI: 10.1134/S1070363210070315
R1
There are no data in the literature on ammonium
Se
H
Ph
Ph
diselenophosphinates. At the same time, alkylammo-
nium diselenophosphinates are now actively studied as
convenient “single-source” precursors of nanodimen-
sional metal phosphides [1] or selenides [2-3]
possessing unique semiconducting [4], magneto-op-
tical [5–6] and electric properties [2]. Alkylammonium
diselenophosphinates are also ligands of interest for
the design of metal complexes [7], promising extra-
gents for rare, noble, and transuranium elements [8],
potential biologically active compounds [9] and pre-
cursors for synthesis, for example, of esters R12P(Se)·
SeR2 [10–12]. Conventional methods of the synthesis
of alkylammonium diselenophosphinates are multistep,
labor-consuming, and require the use of aggressive
phosphine halides and organometal compounds [4].
Recently, we have suggested a new convenient ap-
proach to the synthesis of mono-, di-, and trialkylam-
monium diselenophosphinates based on the reaction of
secondary phosphine selenides with elemental
selenium and amines [13].
+ Se + NH3
P
R1
Iа, Ib
R1
Se
−
Ph
Ph
EtOH/H2O
+
P
NH4
Se
R1
IIа, IIb
R1 = H (а), Me (b).
by deprotonation of the secondary phosphine selenide
by ammonia, reacts with elemental selenium to give
diselenophosphinate anion B.
Se
Se
NH3
R2P
R2P
Se−
R2P
−
+
−
H
NH4
A
Se
Se
−
Se
R2P
In the present work we report on the atom-econo-
mic synthesis of the first representatives of ammonium
diselenophosphinates by the reaction of the available
[14, 15] bis(2-phenylalkyl)-phosphine-selenides (Ia,
Ib) with elemental selenium and ammonia.
B
Therefore, the three-component reaction between
the secondary phosphine selenides, elemental sele-
nium, and ammonia is the effective atom-economic
method of synthesis of the earlier unknown ammonium
diselenophosphinates, promising intermediates for the
design of semiconducting and magneto-optical nano-
materials and highly reactive precursors for the
synthesis of organoelemental compounds and coor-
dination structures.
The experiments showed that the three-component
reaction readily proceeds in water–ethanol medium
(22–24оС, 0.5 h) to afford ammonium diselenophos-
phinates (IIа, IIb) in 92 and 85% yield, respectively.
The reaction can be represented by the following
scheme: the ambident selenophosphinite anion А formed
1383

1384
ARTEM’EV et al.
Ammonium bis(2-phenylethyl)diselenophosphinate
100, 162, 76.3 МHz, respectively) in DMSO-d6,
external standards 85% Н3РО4 (for 31Р) and Me2Se (for
77Se). All experiments were run in an inert atmosphere
(argon) in commercial ethanol.
(IIа). To the solution of bis(2-phenylethyl)phosphine-
selenide (Iа) (0.32 g, 1.0 mmol) in 8 ml of ethanol
amorphous selenium (0.08 g, 1.0 mmol) and 25%
aqueous ammonia (0.12 ml, ~1.6 mmol) were added at
room temperature, the mixture was stirred for 0.5 h,
filtered, the solvent was removed in a vacuum, the
residue was ground in hexane (2×10 ml), hexane was
decanted, the residue was dried (35–40оС, 1 h, 0.5 mm
Hg). 0.38 g (92%) of salt IIа was obtained as white
fine-crystalline powder, mp 217–219ºС (ether). IR
spectrum (KBr), cm–1: 3060, 3023, 2944, 2789, 1949,
1876, 1810, 1752, 1633, 1601,1495, 1453, 1397, 1265,
1208, 1193, 1156, 1137, 1126, 1068, 1028, 1008, 958,
938, 909, 832, 810, 751, 736, 697, 620, 566, 517, 506,
ACKNOWLEDGMENTS
This work was performed with the financial support
from the Russian Foundation for Basic Research (grant
no. 08-03-00251).
REFERENCES
1. Maneeprakorn, W., Nguyen, C.Q., Malik, M.A.,
O’Brien, P., and Raftery, J., Dalton Trans., 2009, p. 2103.
2. Fan, D., Afzaal, M., Mallik, M.A., Nguyen, C.Q.,
O’Brien, P., and Thomas, P.J., Coord. Chem. Rev.,
2007, vol. 251, p. 1878.
3. Panneerselvam, A., Nguyen, C.Q., Malik, M.A.,
O’Brien, P., and Raftery, J., J. Mater. Chem., 2009,
vol. 19, p. 419.
4. Nguyen, C.Q., Afzaal, M., Malik, M.A., Helliwell, M.,
Raftery, J., and O’Brien, P., J. Organomet. Chem.,
2007, vol. 692, p. 2669.
5. Hasegawa, Y., Adachi, T., Tanaka, A., Afzaal, M.,
O’Brien, P., Doi, T., Hinatsu, Y., Fujita, K., Tanaka, K.,
and Kawai, T., J. Am. Chem. Soc., 2008, vol. 130, p. 5710.
1
481, 413. Н NMR spectrum, δ, ppm (J, Hz): 2.26–
2.31 m (4H, CH2Р), 2.95–3.02 m (4H, CH2Ph), 7.15–
7.28 m (14H, Ph, NH4). 13С NMR spectrum, δС, ppm:
30.58 d (CH2Ph, 2JPC 1.8 Hz), 44.84 d (CH2P, 1JPC 36.9
Hz), 125.50 (Cр), 128.09 (Со), 128.25 (Сm), 142.50 d
3
(Ci, JCP 16.4 Hz). 31Р NMR spectrum, δР, ppm: 24.29
1
(plus doublet of satellites with JPSe 610 Hz). 77Se
NMR spectrum, δSe, ppm: –36 d (1JPSe 616 Hz). Found,
%: С 46.10; Н 5.29; N 3.31; Р 7.31; Se 37.75.
C16H22NPSe2. Calculated, %: С 46.06; Н 5.31; N 3.36;
Р 7.42; Se 37.85.
6. Tanaka, A., Adachi, T., Hasegawa, Y., and Kawai, T.,
J. Alloy. Compd., 2009, vol. 488, p. 538.
Ammonium
bis(2-phenylpropyl)diselenophos-
7. Lobana, T.S., Wang, J.-C., and Liu, C.W., Coord.
Chem. Rev., 2007, vol. 251, p. 91.
8. Egorova, N.S., Candidate Sci. (Chem.) Dissertation,
Мoscow, 2007.
phinate (IIb) was prepared similarly from bis(2-
phenylpropyl)phosphineselenide (Ib).Yield 0.38 g
(85%), white powder, mp 154–156ºС (ether). IR
spectrum (KBr), cm–1: 3250, 3080, 3060, 2957, 2867,
2765, 1947, 1880, 1806, 1638, 1601, 1582, 1493,
1451, 1392, 1306, 1283, 1234, 1196, 1182, 1148,
1086, 1075, 1047, 1027, 1005, 995, 911, 847, 829,
763, 747, 732, 699, 584, 562, 544, 532, 488, 462, 404.
1Н NMR spectrum, δ, ppm (J, Hz): 1.27–1.35 m (6H,
Me), 2.04-2.24 m (4H, CH2P), 3.36–3.52 m (2H, CH),
7.08–7.22 m (14H, Ph, NH4). 13С NMR spectrum, δС,
9. Wolf, C. and Lerebours, R., Org. Biomol. Chem., 2004,
vol. 2, p. 2161.
10. Kimura, T. and Murai, T., J. Org. Chem., 2005, vol. 70,
p. 952.
11. Murai, T. and Kimura, T., Curr. Org. Chem., 2006,
vol. 10, p. 1963.
12. Moon, J., Nam, H., Kim, S., Ryu, J., Han, C., Lee, C.,
and Lee, S., Tetrahedron Lett., 2008, vol. 49, p. 5137.
13. Trofimov, B.A., Artem’ev, A.V., Gusarova, N.K.,
Malysheva, S.F., Fedorov, S.V., Kazheva, O.N.,
Alexandrov, G.G., and Dyachenko, O.A., Synthesis,
2009, vol. 19, p. 3332.
14. Sukhov, B.G., Gusarova, N.K., Ivanova, N.I.,
Bogdanova, M.V., Kazheva, O.N., Aleksandrov, G.G.,
D’yachenko, O.A., Sinegovskaya, L.M., Malysheva, S.F.,
and Trofimov, B.А., Russ. J. Struct. Chem. Engl.
Transl., 2005, vol. 46, no. 6, p. 1066.
2
ppm: 23.98 and 24.37 d (Ме JPC 5.2 Hz), 37.02 and
37.40 (СНРh), 52.22 and 52.63 d (CH2P, 1JPC 34.0 and
35.0 Hz), 125.01 (Cр), 127.52 and 127.54 (Со), 128.30
(Cm), 149.49 and 149.60 d (Ci, 3JPC 12.9 Hz). 31Р NMR
spectrum, δР, ppm: 22.94 and 24.14 (plus doublet of
1
satellites with JPSe 607 and 612 Hz), the ratio of
intensities 52 : 48. 77Se NMR spectrum, δSe, ppm:
–23.2 and 23 d (1JPSe 607 Hz). Found, %: С 48.50; Н
5.77; N 3.11; Р 6.69; Se 35.43. C18H26NPSe2. Cal-
culated, %: С 48.55; Н 5.89; N 3.15; Р 6.96; Se 35.46.
15. Malysheva, S.F., Artem’ev, A.V., Gusarova, N.K.,
Timokhin, B.V., Tatarinova, A.A., and Trofimov, B.A.,
Russ. J. Gen. Chem. Engl. Transl., 2009, vol. 79, no. 8,
p. 1617.
IR spectra were recorded on a Bruker IFS-25
1
spectrometer. Н, 13С, 31Р, 77Se NMR spectra were
registered on a Bruker DPX-400 spectrometer (400,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 7 2010