A novel simple synthesis of bis(diorganoselenophosphoryl)selenides (R2PSe)2Se from secondary phosphines and elemental selenium

Article abstract of DOI:10.1016/j.tetlet.2010.02.068

Secondary phosphines R₂PH [R = Ph(CH₂)₂, 4-t-BuC₆H₄(CH₂)₂, 4-MeOC₆H₄(CH₂)₂, 2-Naphth(CH₂)₂] react with two equivalents of elemental selenium under mild conditions (85 °C, 3 h, toluene) to afford bis(diorganoselenophosphoryl)selenides (R₂PSe)₂Se in high yields (75-92%).

Full text of DOI:10.1016/j.tetlet.2010.02.068

Tetrahedron Letters 51 (2010) 2141–2143
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Tetrahedron Letters
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A novel simple synthesis of bis(diorganoselenophosphoryl)selenides
(R2PSe)2Se from secondary phosphines and elemental selenium
*
Alexander V. Artem’ev, Nina K. Gusarova, Svetlana F. Malysheva, Igor A. Ushakov, Boris A. Trofimov
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Secondary phosphines R2PH [R = Ph(CH2)2, 4-t-BuC6H4(CH2)2, 4-MeOC6H4(CH2)2, 2-Naphth(CH2)2] react
with two equivalents of elemental selenium under mild conditions (85 °C, 3 h, toluene) to afford bis(dior-
ganoselenophosphoryl)selenides (R2PSe)2Se in high yields (75–92%).
Received 18 January 2010
Revised 3 February 2010
Accepted 12 February 2010
Available online 16 February 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Secondary phosphines
Elemental selenium
Bis(diorganoselenophosphoryl)selenides
Bis(diorganoselenophosphoryl)selenides (R2PSe)2Se are used as
single-source precursors in metal organic chemical vapor deposi-
tion processes for the design of semiconducting thin films1 and
nanoparticles,2 possessing magneto-optical,3 electrical and other
properties.4 These compounds are promising extractants of heavy,
rare and transuranium elements,5 potent biologically active com-
pounds,6 RAFT-agents,7 and intermediates for the generation of
diselenophosphinate anions [R2PSe2]À as reactants used exten-
sively for the design of diverse nanomaterials.2,8
Reported methods for the preparation of bis(diorganoseleno-
phosphoryl)selenides are low yielding and time-consuming. Fur-
thermore, these methods utilize toxic phosphorus halides and
hence do not conform to modern environmental requirements.
Thus, bis(diphenylselenophosphoryl)selenide was synthesized by
the reaction of Ph2PCl with NaxSey, generated from sodium metal
and elemental selenium in liquid ammonia solution at À78 °C.9
The reaction afforded a mixture of products (along with unreacted
sodium). In addition, the results of this method were not reproduc-
ible.10 Recently, the synthesis of two representative selenides,
(R2PSe)2Se (R = i-Pr, Ph) were reported.11 These compounds were
prepared in moderate yield (41–43%) via multistep reactions of
toxic and difficult to obtain monochlorophosphines (R2PCl) with
highly flammable and harmful trichlorosilane, triethylamine and
selenium in toluene11 (Scheme 1).
vents. Along with the target compounds the reaction also gave
several byproducts.
Herein, we report a simple and convenient approach to the syn-
thesis of bis(diorganoselenophosphoryl)selenides via the reaction
of readily available secondary phosphines 1a–d with elemental
selenium. The initial phosphines were easily prepared from red
phosphorus and styrenes12 or 2-vinylnaphthalene13 in one step
(Scheme 2).
We found that secondary phosphines 1a–c reacted easily with
two equivalents of elemental selenium under mild conditions
toluene
R2PCl + HSiCl3 + NEt3
R2PSiCl3
+ [HNEt3]Cl
6 h, r.t.
toluene
2 R2PSiCl3
+ 3 Se
(R2PSe)2Se
+
Si2Cl6
20 h, reflux
Scheme 1.
R
1) KOH/H2O/toluene, 80 oC
In addition, this method is laborious requiring an argon atmo-
sphere, Schlenk equipment and especially pure anhydrous sol-
Pred
P H
2)
, KOH/DMSO/H2O,
60-75 oC
R
R
1a-d
R = Ph (a), 4-t-BuC6H4 (b), 4-MeOC6H4 (c), 2-Naphth (d)
* Corresponding author. Tel.: +7 395242 14 11; fax: +7 395241 93 46.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
Scheme 2.
0040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.02.068

2142
A. V. Artem’ev et al. / Tetrahedron Letters 51 (2010) 2141–2143
Se
P
Se
R
R
P
Se
Se (2 equiv.)
R
R
PH
85 oC, 3 h, toluene
R
R
2a-c
1a-c
R = H (a); t-Bu (b); OMe (c)
Scheme 3.
Se
Se
P
P
Se
Se (2 equiv.)
85 oC, 3 h, toluene
PH
2d
1d
Scheme 4.
(85 °C, toluene, 3 h) to give bis[di(2-arylethyl)selenophospho-
ryl]selenides 2a–c in 83–92% isolated yields14 (Scheme 3). The
use of more than two equivalents of selenium did not affect the
reaction.
molecular condensation of two molecules of diselenophosphinoic
acid B (stage 3) leads to bis(diorganoselenophosphoryl)selenide 2
and hydrogen selenide (identified by qualitative reaction with cad-
mium acetate).
Secondary bis[2-(2-naphthylethyl)]phosphine 1d with bulky
naphthyl groups was also utilized, thus demonstrating the general-
ity of the process. Using the same conditions (85 °C, 3 h, PhMe) the
reaction of phosphine 1d with two equivalents of elemental sele-
nium afforded selenide 2d in 75% yield14 (Scheme 4).
It is noteworthy that diselenophosphinoic acids R2P(Se)SeH and
bis(diorganoselenophosphoryl)diselenides (R2PSe)2Se2, as the ex-
pected products of the oxidation of secondary phosphines by two
or threefold amounts of elemental selenium, were not formed un-
der the present conditions. For example, the physico-chemical and
spectral characteristics of selenide 2a were different from those of
the diselenide, [(PhCH2CH2)2PSe]2Se2, which was synthesized inde-
pendently from potassium bis(2-phenylethyl)diselenophosphinate
and iodine.15
The structures of compounds 2 were confirmed by multinuclear
1H, 13C, 31P and 77Se NMR techniques. For example, the 77Se NMR
spectra of bis[di(2-arylethyl)selenophosphoryl]selenides 2 showed
a doublet of double the integration of that of the bridging selenium
with
a
chemical shift at 138–140 ppm (1JP@Se = 745–749 Hz),
assignable to the P@Se bond.12b,16 The resonance signals of the
bridging selenium atom with a chemical shift at 284–285 ppm
(1JP–Se = 377–379 Hz) appear as triplets due to the splitting of
two magneto-equivalent phosphorus atoms. In the 31P NMR spec-
tra of compounds 2, the signals of the magneto-equivalent phos-
phorus atoms were observed as a singlet (ca. 56 ppm) showing a
set of satellite signals from the 77Se nuclei, as is typical for such
systems.17 Analysis of the satellite signals allowed determination
of the values of the 2JP,P constants (17–10 Hz), transmitted through
the bridging selenium atom.17
The mechanism for the formation of selenides 2 can be rational-
ized as follows (Scheme 5). In the first stage (1), the secondary
phosphine 1 reacts with elemental selenium to furnish secondary
phosphine selenide A. The latter, with a second equivalent of ele-
mental selenium, gives diselenophosphinoic acid B (stage 2). Inter-
In summary, a novel and simple method for the synthesis of
bis(diorganoselenophosphoryl)selenides via the unexpected reac-
tion of secondary phosphines with elemental selenium is reported.
The selenides obtained can be applied as ligands for the design of
metal complexes, as potential single-source precursors for conduc-
tive, magneto-optical and other nanomaterials, as promising
extractants of rare elements, as potent biologically active com-
pounds, and as reactive building blocks for organic and elemento-
organic synthesis.
R
R
R
R
Se
H
Se
P
P
SeH
(1)
(2)
R2PH
Acknowledgements
A
1
This work was supported by the President of the Russian Feder-
ation (programme for the support of leading scientific schools,
grant no. NSh-263.2008.3) and the Russian Foundation for Basic
Research (project no. 08-03-00251).
R
R
Se
Se
P
A
SeH
B
Se
P
R
Se
P
References and notes
2 B
(3)
- H2Se
R
R
Se
1. Nguyen, C. Q.; Adeogun, A.; Afzaal, M.; Malik, M. A.; O’Brien, P. Chem. Commun.
2006, 2184.
2. (a) Fan, D.; Afzaal, M.; Mallik, M. A.; Nguyen, C. Q.; O’Brien, P.; Thomas, J. P.
Coord. Chem. Rev. 2007, 251, 1878; (b) Nguyen, C. Q.; Afzaal, M.; Malik, M. A.;
Helliwell, M.; Raftery, J.; O’Brien, P. J. Organomet. Chem. 2007, 692, 2669.
R
2
Scheme 5.

A. V. Artem’ev et al. / Tetrahedron Letters 51 (2010) 2141–2143
2143
3. (a) Hasegawa, Y.; Adachi, T.; Tanaka, A.; Afzaal, M.; O’Brien, P.; Doi, T.; Hinatsu,
Y.; Fujita, K.; Tanaka, K.; Kawai, T. J. Am. Chem. Soc. 2008, 130, 5710; (b) Tanaka,
A.; Adachi, T.; Hasegawa, Y.; Kawai, T. J. Alloys Compd. 2009, 488, 538.
4. Maneeprakorn, W.; Nguyen, C. Q.; Malik, M. A.; O’Brien, P.; Raftery, J. Dalton
Trans. 2009, 2103.
d: À139 (d, 1JP=Se = 744.5 Hz, P@Se), 284 (t, 1JP–Se = 377.6 Hz, P–Se–P). Calcd for
C48H68P2Se3: C, 61.08; H, 7.26; P, 6.56; Se, 25.10. Found: C, 61.17; H, 7.34; P,
6.58; Se, 24.97.
Bis[di(4-methoxyphenethyl)selenophosphoryl]selenide 2c: yellow powder, yield
0.374 g (89%), mp 150–152 °C (hexane). IR (KBr, m
/cmÀ1): 3126, 3099, 3061,
5. Mastrukova, T. A.; Artychin, O. A.; Odinets, I. L.; Tananaev, I. G. Russ. Chem. J.
2005, 86.
6. Matolcsy, G.; Nadasy, M.; Andriska, V. Pesticide Chemistry; Elsevier: Budapest,
1988.
7. Moon, J.; Nam, H.; Kim, S.; Ryu, J.; Han, C.; Lee, C.; Lee, S. Tetrahedron Lett. 2008,
49, 5137.
8. Lobana, T. S.; Wang, J.-C.; Liu, C. W. Coord. Chem. Rev. 2007, 251, 91.
9. (a) Muller, A.; Rao, V. V. K.; Christophliemk, P. J. Inorg. Nucl. Chem. 1974, 36,
472; (b) Muller, A.; Christophliemk, P.; Rao, V. V. K. J. Inorg. Nucl. Chem. 1972,
34, 345; (c) Muller, A.; Christophliemk, P.; Rao, V. V. K. Chem. Ber. 1971, 104,
1905.
10. Pilkington, M. J.; Slawin, A. M. Z.; Williams, D. J.; Woollins, J. D. Polyhedron
1991, 10, 2641.
11. Nguyen, C. Q.; Adeogun, A.; Afzaal, M.; Malik, M. A.; O’Brien, P. Chem. Commun.
2006, 2182.
12. (a) Trofimov, B. A.; Brandsma, L.; Arbuzova, S. N.; Malysheva, S. F.; Gusarova, N.
K. Tetrahedron Lett. 1994, 35, 7647; (b) Gusarova, N. K.; Malysheva, S. F.;
Kuimov, V. A.; Belogorlova, N. A.; Mikhailenko, V. L.; Trofimov, B. A. Mendeleev
Commun. 2008, 18, 260.
13. Gusarova, N. K.; Shaukhudinova, S. I.; Kazantseva, T. N.; Malysheva, S. F.;
Sukhov, B. G.; Belogorlova, N. A.; Dmitriev, V. I.; Trofimov, B. A. Russ. J. Gen.
Chem. 2002, 72, 399.
3027, 3004, 2955, 2929, 2910, 2858, 2834, 2595, 2545, 1610, 1582, 1512, 1463,
1440, 1420, 1397, 1318, 1246, 1176, 1130, 1032, 945, 817, 789, 736, 722, 708,
543, 528, 481, 467, 437, 400. 1H NMR (400.13 MHz, CDCl3, ppm), d: 2.42–2.66
(m, 4H, CH2P), 2.85–3.11 (m, 12H, CH2P, CH2Ph), 3.76 (s, 12H, MeO), 6.8–7.11
(m, 16H, C6H4). 13C NMR (100.62 MHz, CDCl3, ppm), d: 28.61, 29.07 (CH2Ph),
38.31, 38.46, 38.65 and 38.97 (CH2P), 55.29 (MeO), 114.19 (C-2 in C6H4),
3
129.45 (C-3 in C6H4), 131.47 (d, JCP = 16.9 Hz, C-1 in C6H4), 158.42 (C-4 in
1
C6H4). 31P NMR (161.98 MHz, CDCl3, ppm), d: 55.94 (+ satellites: JP–
1
2
Se = 378.8 Hz, JP=Se = 746.0 Hz, JPP = 19.6 Hz). 77Se NMR (76.31 MHz, CDCl3,
1
1
ppm), d: À140 (d, JP=Se = 746.0 Hz, P@Se), 284 (t, JP–Se = 378.5 Hz, P–Se–P).
Calcd for C36H44O4P2Se3: C, 51.50; H, 5.28; P, 7.38; Se, 28.21. Found: C, 51.44;
H, 5.30; P, 7.26; Se, 28.11.
Bis[di(2-naphthylethyl)selenophosphoryl]selenide 2d: yellow powder, yield
0.345 g (75%), mp 110–114 °C (hexane). IR (KBr, m
/cmÀ1): 3050, 3020, 2924,
2855, 2330, 1957, 1800, 1634, 1597, 1506, 1445, 1367, 1277, 1125, 1018, 996,
950, 895, 858, 817, 796, 746, 477. 1H NMR (400.13 MHz, CDCl3, ppm), d: 2.71–
2.88 (m, 4H, CH2P), 3.12–3.38 (m, 12H, CH2P, CH2Naphth), 7.25–7.81 (m, 28H,
Naphth). 13C NMR (100.62 MHz, CDCl3, ppm), d: 30.20 (CH2Ph), 38.1 (d,
1JPC = 32.0 Hz, CH2P), 125.77, 126.34, 126.88, 127.64. 127.76. 128.59. 132.33,
3
133.60 (Naphth), 136.83–137.0 (d, JCP = 16.9 Hz, C-1 in Naphth). 31P NMR
(161.98 MHz, CDCl3, ppm), d: 55.55 (+ satellites: 1JP–Se = 378.7 Hz,
2
1JP=Se = 749.1 Hz, JP,P = 20.1 Hz). 77Se NMR (76.31 MHz, CDCl3, ppm), d: À138
1
1
14. General procedure for the preparation of bis(diorganoselenophosphoryl)selenides
(d, JP=Se = 749.4 Hz, P@Se), 285 (t, JP–Se = 378.3 Hz, P–Se–P). Calcd for
C48H44P2Se3: C, 62.69; H, 4.82; P, 6.74; Se, 25.76. Found: C, 62.50; H, 4.91; P,
6.61; Se, 25.81.
2a–d from secondary phosphines and elemental selenium. To
a solution of
secondary phosphine 1a–d (1.0 mmol) in toluene (8 mL), amorphous grey
selenium (0.158 g, 2.0 mmol) was added at 85 °C under argon. The suspension
was stirred for 3 h at 85 °C. The solvents were removed under reduced pressure
and the residue was washed with cold hexane (3 Â 5 mL), dried in vacuo
(1 Torr, rt) to give compounds 2a–d.
15. Procedure for the preparation of bis[di(2-phenethyl)selenophosphoryl]diselenide. A
solution of iodine (0.127 g, 0.5 mmol) in EtOH (10 mL) was added to a solution
of potassium bis(2-phenylethyl)diselenophosphinate (0.438 g, 1.0 mmol) in
H2O (10 mL) at rt under argon. The reaction mixture was stirred for 10 min,
diluted with H2O (30 mL) and extracted with toluene (2 Â 25 mL). The toluene
extract was dried over K2CO3 and concentrated in vacuo to 10 mL. The
remaining solution was diluted with hexane (15 mL) and kept overnight at 5–
10 °C. The solvents were removed from the precipitate by decanting. The
residue was washed with cold hexane (1 Â 5 mL), dried in vacuo (1 Torr, rt) to
give 0.323 g (81%) of bis[di(2-phenethyl)selenophosphoryl]diselenide as
Bis[di(2-phenethyl)selenophosphoryl]selenide 2a: yellow powder, yield 0.331 g
(92%), mp 112–114 °C (hexane). IR (KBr,
m
/cmÀ1): 3059, 3023, 2917, 2890,
2855, 1949, 1878, 1805, 1640, 1599, 1492, 1447, 1389, 1329, 1269, 1211, 1133,
1019, 1006, 938, 901, 825, 743, 699, 571, 501, 454. 1H NMR (400.13 MHz,
CDCl3, ppm), d: 2.61–2.69 (m, 4H, CH2P), 3.05–3.14 (m, 12H, CH2P, CH2Ph),
7.19–7.30 (m, 20H, Ph). 13C NMR (100.62 MHz, CDCl3, ppm), d: 29.53 (CH2Ph),
1
37.88 (d, JPC = 32.0 Hz, CH2P), 126.32 (C-p, Ph), 128.04 (C-o, Ph), 128.40 (C-m,
orange–red crystals, mp 117–118 °C (hexane–toluene). IR (KBr, m
/cmÀ1):
3
Ph), 139.09 (d, JP,C = 18.0 Hz, C-i, Ph). 31P NMR (161.98 MHz, CDCl3, ppm), d:
3060, 3020, 2919, 2888, 2854, 1951, 1878, 1806, 1644, 1590, 1491, 1444,
1387, 1330, 1270, 1210, 1131, 1020, 1005, 939, 906, 825, 745, 670, 570, 507,
458. 1H NMR (400.13 MHz, CDCl3, ppm), d: 2.78–2.91 (m, 8H, CH2P), 3.23–3.33
(m, 8H, CH2Ph), 7.37–7.48 (m, 20H, Ph). 13C NMR (100.62 MHz, CDCl3, ppm), d:
29.74 (CH2Ph), 38.04 (d, 1JPC = 32.0 Hz, CH2P), 126.61 (C-p, Ph), 128.29 (C-o, Ph),
56.04 (+ satellites: 1JP–Se = 378.5 Hz, 1JP@Se = 749.2 Hz, 2JP,P = 19.1 Hz). 77Se NMR
1
1
(76.31 MHz, CDCl3, ppm), d: À140 (d, JP@Se = 749.1 Hz, P@Se), 284 (t, JP–
Se = 378.4 Hz, P–Se–P). Calcd for C32H36P2Se3: C, 53.42; H, 5.04; P, 8.61; Se,
32.92. Found: C, 53.48; H, 5.10; P, 8.50; Se, 32.81.
3
Bis[di{2-(4-tert-butylphenethyl)}selenophosphoryl]selenide 2b: yellow powder,
128.64 (C-m, Ph), 139.33 (d, JP,C = 17.3 Hz, C-i, Ph). 31P NMR (161.98 MHz,
1
1
yield 0.392 g (83%), mp 195–197 °C (hexane). IR (KBr,
m
/cmÀ1): 3093, 3055,
CDCl3, ppm), d: 55.64 (+ satellites: JP–Se = 379 Hz, JP=Se = 747 Hz). Calcd for
C32H36P2Se4: C, 48.24; H, 4.54; P, 7.76; Se, 39.56. Found: C, 48.28; H, 4.50; P,
7.61; Se, 39.51.
3022, 2959, 2902, 2864, 1902, 1791, 1685, 1634, 1607, 1517, 1475, 1462, 1443,
1413, 1391, 1363, 1268, 1201, 1135, 1108, 1019, 942, 927, 852, 837, 813, 769,
740, 728, 669, 563, 519, 485, 429. 1H NMR (400.13 MHz, CDCl3, ppm), d: 1.27 (s,
36H, Me), 2.55–2.64 (m, 4H, CH2P), 2.96–3.09 (m, 12H, CH2P, CH2C6H4), 7.11–
7.29 (m, 16H, C6H4). 13C NMR (100.62 MHz, CDCl3, ppm), d: 29.02 (CH2C6H4),
16. (a) Sukhov, B. G.; Gusarova, N. K.; Ivanova, N. I.; Bogdanova, M. V.; Kazheva, O.
N.; Alexandrov, G. G.; D’yachenko, O. A.; Sinegovskaya, L. M.; Malysheva, S. F.;
Trofimov, B. A. J. Struct. Chem. 2005, 46, 1066; (b) Malysheva, S. F.; Artem’ev, A.
V.; Gusarova, N. K.; Timokhin, B. V.; Tatarinova, A. A.; Trofimov, B. A. Russ. J.
Gen. Chem. 2009, 79, 1617.
1
30.96 (Me), 34.04 (CMe), 37.89 (d, JPC = 31.9 Hz, CH2P), 125.27 (C-2 in C6H4),
3
127.75 (C-3 in C6H4), 136.02 (d, JPC = 16.5 Hz, C-1 in C6H4), 149.24 (C-4 in
1
C6H4). 31P NMR (161.98 MHz, CDCl3, ppm), d: 56.13 (+ satellites: JP–Se
=
17. Oliver Schön, Ph. D. Thesis. Ludwig-Maximilians-Universität München,
2007.
377.1 Hz, 1JP=Se = 744.8 Hz, 2JP,P = 17.6 Hz). 77Se NMR (76.31 MHz, CDCl3, ppm),