Rapid and convenient one-pot method for the preparation of alkali metal phosphinodiselenoates

Article abstract of DOI:10.1055/s-0029-1218786

Alkali metal phosphinodiselenoates, R₂PSe₂M (R=aralkyl, hetaralkyl, Ph; M=Li, Na, K, Rb, Cs), were synthesized in high yields (up to 98%) by a three-component reaction of a secondary phosphine, elemental selenium, and an alkali metal hydroxide under mild conditions (ethanol, room temperature, 5 min). Georg Thieme Verlag Stuttgart · New York.

Full text of DOI:10.1055/s-0029-1218786

PAPER
2463
Rapid and Convenient One-Pot Method for the Preparation of Alkali Metal
Phosphinodiselenoates
A
lkali Metal Phosp
l
hinodi
e
selenoatesxander V. Artem’ev, Svetlana F. Malysheva, Nina K. Gusarova, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky St., 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: boris_trofimov@irioch.irk.ru
Received 19 March 2010; revised 29 March 2010
for preparing esters of phosphinodiselenoic acids,15 which
Abstract: Alkali
metal
phosphinodiselenoates,
R2PSe2M
are efficient iniferters16 and potential pesticides.17
(R = aralkyl, hetaralkyl, Ph; M = Li, Na, K, Rb, Cs), were synthe-
sized in high yields (up to 98%) by a three-component reaction of a
secondary phosphine, elemental selenium, and an alkali metal hy-
droxide under mild conditions (ethanol, room temperature, 5 min).
Conventional syntheses of alkali metal phosphinodisele-
noates are laborious, require many steps, and require the
use of aggressive and poisonous phosphorus halides and
flammable unstable organometallic compounds as reac-
tants.18 Moreover, these methods have been limited to
preparations of lithium, sodium, and potassium phosphin-
odiselenoates.18
Key words: phosphorus, selenium, alkali metals, three-component
reactions, phosphinodiselenoates, alkali metal salts
Phosphinodithioates are widely used as lubricant oil
additives1 and extraction agents for separation proce-
dures.2 In addition, they have been shown to exhibit a
broad variety of coordination patterns, leading to a wide
range of molecular and supramolecular structures.3 Re-
cently, the chemistry of the phosphinodithioate ana-
logues, the phosphinodiselenoates, has attracted particular
attention because of their potential and actual applications
as single-source precursors (SSPs) of magneto-optically
and photochemically active materials,4 ligands for metal
complexes,5 promising extractants for heavy elements,6
potential pharmaceuticals,7 and proton conductors. For
example, heavy metal phosphinodiselenoates are now
used as efficient SSPs for the preparation of nanoparticles
of metal phosphides or selenides that possess many
unique properties.8 Nickel dialkylphosphinodiselenoates
are used for the synthesis of nickel phosphide or nickel se-
lenide nanoparticles.9 Silver phosphinodiselenoate is used
as an SSP for the production of silver selenide nano-
films.10 Europium phosphinodiselenoates are actively
used to produce europium selenide nanocrystals that show
remarkable magneto-optical properties.11 Nanorods of
zinc selenide exhibiting semiconductive properties have
been synthesized from zinc phosphinodiselenoate.12 In
2010, O’Brien et. al.13 described a one-pot synthesis of
nanoparticles of cobalt diselenide, cobalt phosphide, or
dicobalt phosphide from cobalt phosphinodiselenoates,
[Co(Se2PR2)2].
In 2009, a brief report appeared on the synthesis of potas-
sium diphenylphosphinodiselenoate from a metalated
diphenylphosphine (Ph2PK) by treatment with elemental
selenium in tetrahydrofuran at room temperature for sev-
en hours under an inert atmosphere.11c The method is te-
dious, requires an especially pure anhydrous solvent, and
permits only the preparation of the potassium salt.11c
One of the most convenient approaches for the synthesis
of alkali metal phosphinodiselenoates involves the reac-
tion of a secondary phosphine selenide with elemental se-
lenium and an alkali metal hydroxide.19
Here we report, for the first time, a three-component reac-
tion of a secondary phosphine with two equivalents of el-
emental selenium and an alkali metal hydroxide. The
realization of such reaction was problematic, since sec-
ondary phosphines are known to react with two equiva-
lents
of
elemental
selenium
to
furnish
bis(diorganoselenophosphoryl)selenides20 (Scheme 1).
Se Se
R
+
2 Se
P
H
R
P
P
R
– H2Se
Se
R
R
R
R = Ph(CH2)2 etc.
Scheme 1 Reaction of secondary phosphines with elemental seleni-
um
As our experiments showed, however, the secondary
phosphines 1–10 reacted readily and unusually rapidly (5
min) with elemental selenium and alkali metal hydroxides
MOH (M = Li, Na, K, Rb, Cs) in ethanol at room temper-
ature to afford the corresponding phosphinodiselenoates
11a–p in high yields (Table 1).
The convenient syntheses of heavy metal phosphinodise-
lenoates are based on the reactions of alkali metal phos-
phinodiselenoates with heavy metal halides.5,9,12–14 Alkali
metal phosphinodiselenoates are also key intermediates
The reaction is general in character in that its efficiency is
retained even when such sterically hindered secondary
phosphines as 2–4 and 6 are used, and the phosphinodise-
lenoates 11a–n are all obtained in high yield. The gener-
SYNTHESIS 2010, No. 14, pp 2463–2467
Advanced online publication: 12.05.2010
DOI: 10.1055/s-0029-1218786; Art ID: Z07210SS
x
x.
x
x
.
2
0
1
0
© Georg Thieme Verlag Stuttgart · New York

2464
A. V. Artem’ev et al.
PAPER
R2
Table 1 Synthesis of Phosphinodiselenoates from Secondary Phos-
phines, Elemental Selenium, and Alkali Metal Hydroxides
R2
R3
R3
R1
R1
R1
KOH
R
R
R
Se
Pred
PH3/H2
P
H
EtOH, r.t.
5 min
H2O–toluene
+
H
2 Se
+
MOH
P
M
KOH–DMSO(H2O)
P
Se
R3
R
R2
R1 = aryl, hetaryl
R2, R3 = H, Me
1–10
11a–p
1–9
Entry Phos-
phinea
R
MOH
Product Yield
(%)b
Scheme 2 One-step synthesis of the initial secondary phosphines
from red phosphorus and vinylarenes or vinylhetarenes
1
2
3
4
5
6
7
8
1
1
1
1
1
2
2
3
(CH2)2Ph
LiOH
NaOH
KOH
11a
11b
11c
11d
11e
11f
93
97
95
92
98
88
97
81
K, Rb, or Cs) phosphinodiselenoates in high yields from
readily available secondary phosphines, elemental seleni-
um, and alkali metal hydroxides under environmentally
friendly conditions (commercial ethanol as a nontoxic re-
coverable solvent, room temperature, 5 min). The salts
that are obtained can serve as SSPs for the preparation of
magneto-optical and semiconducting nanomaterials,
ligands for the design of coordination structures, extract-
ants for heavy elements, or reactive building blocks for
synthesis.
(CH2)2Ph
(CH2)2Ph
(CH2)2Ph
RbOH
CsOH
KOH
(CH2)2Ph
CH2CH(Me)Ph
CH2CH(Me)Ph
CH(Me)CH2Ph
RbOH
KOH
11g
11h
The H, 13C, 31P, and 77Se NMR spectra were recorded on Bruker
1
9
4
5
6
7
KOH
KOH
KOH
CsOH
11i
11j
11k
11l
92
89
94
96
DPX 400 and Bruker AV-400 spectrometers at 400.13, 100.61,
161.98, and 76.31 MHz, respectively, and are referenced to H3PO4
(31P NMR) or Me2Se (77Se NMR). IR spectra were recorded on a
Bruker IFS 25 instrument. All melting points were measured on a
Kofler micro hot-stage apparatus. Secondary phosphines 1–9 were
prepared from red phosphorus and styrene,21a a-methylstyrene,21a b-
methylstyrene, 4-tert-butylstyrene,21b 4-methoxystyrene, 2-vinyl-
naphthalene,23 4-vinylpyridine,22 2-methyl-5-vinylpyridine22 or 2-
vinylfuran,21a as described in the literature. Ph2PH (10) was a com-
mercial product (Aldrich). Commercial EtOH was used as the reac-
tion solvent. All steps of the syntheses were carried out under an
argon atmosphere.
t-Bu
10
11
12
MeO
N
Alkali Metal Phosphinodiselenoates (11a–p); General Proce-
dure
13
14
8
9
NaOH
CsOH
11m
11n
93
96
A soln of MOH·nH2O (n = 0 for Li and Na; n = 0.5 for K; n = 1 for
Rb and Cs; 1.0 mmol) in EtOH (5 mL) and amorphous grey Se
(0.158 g, 2.0 mmol) were added sequentially to a soln of the second-
ary phosphine 1–10 (1.05 mmol) in EtOH (6 mL) at r.t. under Ar.
The suspension was stirred vigorously at r.t. until the Se residue
completely dissolved (~5 min), and the colorless soln was filtered
and concentrated. The residue was ground in Et2O (10 mL), and the
solvent was decanted to give a white crystalline powder that was
washed with Et2O (1 × 10 mL) and dried in vacuo (1 Torr, 35–
40 °C).
N
O
15
16
10
10
Ph
KOH
11o
11p
92
94
Ph
CsOH
a Reaction conditions: phosphine 1–10 (1.05 mmol), Se (2.0 mmol),
MOH (1.0 mmol), EtOH, r.t., 5 min.
Lithium Bis(2-phenylethyl)phosphinodiselenoate (11a)
White powder; yield: 0.378 g (93%); mp 99–100 °C (Et2O).
b Yield of the isolated product.
IR (KBr): 3066, 3023, 2921, 2848, 1948, 1880, 1805, 1743, 1619,
1601, 1584, 1495, 1453, 1441, 1398, 1318, 1265, 1209, 1190, 1178,
1155, 1123, 1065, 1029, 1004, 953, 925, 912, 835, 777, 764, 741,
725, 697, 568, 513, 479, 417 cm–1.
ality and efficiency of the approach were further
demonstrated by the synthesis of the potassium and rubid-
ium salts of diphenylphosphinodiselenoic acid (11o and
11p, respectively) from diphenylphosphine (10).
1H NMR (400.13 MHz, D2O): d = 2.11–2.17 (m, 4 H, CH2P), 2.60–
The choice of the initial secondary phosphines 1–9 was 2.67 (m, 4 H, CH2Ph), 6.96–7.01 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 29.78 (CH2Ph), 42.08 (d,
1JCP = 35.4 Hz, CH2P), 125.58 (p-C), 127.77 (o-C), 128.03 (m-C),
140.77 (d, 3JCP = 16.0 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 26.66 (s + d satellites, 1JPSe = 556
Hz).
not arbitrary; these phosphines are readily available in one
step by treatment of red phosphorus with vinylarenes or
vinylhetarenes (e.g., styrenes,21 vinylpyridines,22 2-vinyl-
naphthalene,23 or 2-vinylfuran21a) (Scheme 2).
In summary, we have developed a one-pot, general, and
efficient method for the synthesis of alkali metal (Li, Na,
77Se NMR (76.31 MHz, D2O): d = –67 (d, 1JPSe = 556 Hz).
Synthesis 2010, No. 14, 2463–2467 © Thieme Stuttgart · New York

PAPER
Alkali Metal Phosphinodiselenoates
2465
Anal. Calcd for C16H18LiPSe2: C, 47.32; H, 4.47; P, 7.63; Se, 38.88.
Found: C, 47.36; H, 4.55; P, 7.57; Se, 38.73.
1180, 1159, 1144, 1123, 1066, 1027, 1008, 955, 929, 913, 862, 834,
753, 737, 712, 696, 571, 561, 519, 495, 483, 417 cm–1.
1H NMR (400.13 MHz, D2O): d = 2.42–2.46 (m, 4 H, CH2P), 2.92–
Sodium Bis(2-phenylethyl)phosphinodiselenoate (11b)
White powder; yield: 0.410 g (97%); mp 182–184 °C (Et2O).
2.94 (m, 4 H, CH2Ph), 7.22–7.31 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 30.61 (CH2Ph), 42.94 (d,
1JCP = 35.6 Hz, CH2P), 126.47 (p-C), 128.65 (o-C), 128.92 (m-C),
141.70 (d, 3JCP = 15.8 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 26.92 (s + d satellites, 1JPSe = 555
Hz).
IR (KBr): 3086, 3058, 3023, 2926, 2865, 1944, 1653, 1635, 1601,
1581, 1562, 1540, 1494, 1477, 1452, 1443, 1396, 1320, 1265, 1207,
1190, 1167, 1124, 1093, 1067, 1029, 1006, 951, 924, 907, 881, 834,
762, 739, 724, 696, 668, 618, 596, 568, 555, 512, 481, 434, 413
cm–1.
1H NMR (400.13 MHz, D2O): d = 2.19–2.26 (m, 4 H, CH2P), 2.69–
2.76 (m, 4 H, CH2Ph), 6.94–7.08 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 30.68 (CH2Ph), 42.91 (d,
1JCP = 35.9 Hz, CH2P), 126.28 (p-C), 128.52 (o-C), 128.73 (m-C),
141.43 (d, 3JCP = 16.1 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 26.83 (s + d satellites, 1JPSe = 559
Hz).
77Se NMR (76.31 MHz, D2O): d = –69 (d, 1JPSe = 555 Hz).
Anal. Calcd for C16H18CsPSe2: C, 36.11; H, 3.41; P, 5.82; Se, 29.68.
Found: C, 36.20; H, 3.35; P, 5.73; Se, 29.77.
Potassium Bis(2-phenylpropyl)phosphinodiselenoate (11f)
White powder; yield: 0.410 g (88%); mp 198–200 °C (Et2O).
IR (KBr): 3081, 3060, 3025, 2958, 2923, 2868, 1948, 1880, 1811,
1756, 1734, 1698, 1639, 1601, 1493, 1480, 1450, 1370, 1394, 1312,
1283, 1234, 1197, 1182, 1148, 1087, 1075, 1061, 1048, 1028, 1005,
994, 911, 882, 845, 829, 764, 746, 730, 700, 677, 563, 545, 533,
490, 462, 445 cm–1.
77Se NMR (76.31 MHz, D2O): d = –61 (d, 1JPSe = 559 Hz).
Anal. Calcd for C16H18NaPSe2: C, 45.52; H, 4.30; P, 7.34; Se, 37.40.
Found: C, 45.56; H, 4.35; P, 7.43; Se, 37.43.
1H NMR (400.13 MHz, D2O): d = 0.98 and 1.05 (d, 3JHH = 7.1 Hz,
3JHH = 7.3 Hz, 6 H, Me), 1.84–1.98 (m, 2 H, CH2P), 2.05–2.19 (m,
2 H, CH2P), 3.02–3.14 (m, 2 H, CHPh), 6.79–6.95 (m, 10 H, Ph).
Potassium Bis(2-phenylethyl)phosphinodiselenoate (11c)
White powder; yield: 0.416 g (95%); mp 209–211 °C (Et2O).
IR (KBr): 3080, 3060, 3017, 2997, 2945, 2928, 2902, 2861, 1653,
1598, 1579, 1494, 1452, 1443, 1397, 1365, 1333, 1318, 1264, 1206,
1193, 1178, 1158, 1124, 1066, 1028, 1007, 956, 925, 912, 902, 862,
835, 774, 763, 752, 738, 712, 697, 572, 564, 521, 496, 484, 422
cm–1.
1H NMR (400.13 MHz, D2O): d = 2.13–2.19 (m, 4 H, CH2P), 2.61–
2.68 (m, 4 H, CH2Ph), 6.80–6.88 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 30.92 (CH2Ph), 42.99 (d,
1JCP = 35.4 Hz, CH2P), 126.27 (p-C), 128.45 (o-C), 128.71 (m-C),
141.32 (d, 3JCP = 15.9 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 26.45 (s + d satellites, 1JPSe = 557
Hz).
3
13C NMR (100.61 MHz, D2O): d = 23.91 and 24.32 (d, JCP = 9.2
and 9.0 Hz, Me), 37.37 and 37.50 (CHPh), 49.50 and 49.72 (d,
1JCP = 34.6 and 35.0 Hz, CH2P), 126.24 (p-C), 127.25 and 127.36
(o-C), 128.58 (m-C), 147.36 and 147.45 (d, 3JCP = 12.5 and 12.0 Hz,
ipso-C).
31P NMR (161.98 MHz, D2O): d = 25.85 and 27.03 (ratio 1:2) (s +
d satellites, 1JPSe = 557 and 559 Hz).
77Se NMR (76.31 MHz, D2O): d = –64, –28, and –6 (d, 1JPSe = 564,
557, and 559 Hz).
Anal. Calcd for C18H22KPSe2: C, 46.36; H, 4.75; P, 6.64; Se, 33.86.
Found: C, 46.31; H, 4.69; P, 6.48; Se, 33.71.
77Se NMR (76.31 MHz, D2O): d = –63 (d, 1JPSe = 557 Hz).
Rubidium Bis(2-phenylpropyl)phosphinodiselenoate (11g)
White powder; yield: 0.497 g (97%); mp 180–182 °C (Et2O).
Anal. Calcd for C16H18KPSe2: C, 43.84; H, 4.14; P, 7.07; Se, 36.03.
Found: C, 43.90; H, 4.17; P, 7.19; Se, 36.10.
IR (KBr): 3091, 3069, 3028, 2961, 2924, 2870, 1953, 1886, 1812,
1750, 1630, 1611, 1491, 1450, 1397, 1312, 1232, 1195, 1152, 1084,
1038, 1020, 1002, 910, 841, 804, 761, 701, 672, 534, 492, 460 cm–1.
Rubidium Bis(2-phenylethyl)phosphinodiselenoate(11d)
White powder; yield: 0.446 g (92%); mp 202–204 °C (Et2O).
1H NMR (400.13 MHz, D2O): d = 1.32 and 1.39 (d, 6 H, 3JHH = 6.7
Hz, Me), 2.17–2.32 (m, 2 H, CH2P), 2.39–2.52 (m, 2 H, CH2P),
3.35–3.48 (m, 2 H, CHPh), 7.15–7.28 (m, 10 H, Ph).
IR (KBr): 3086, 3059, 3020, 2945, 2927, 2889, 2855, 1948, 1873,
1641, 1598, 1582, 1493, 1452, 1442, 1396, 1314, 1265, 1206, 1193,
1181, 1163, 1124, 1066, 1027, 1007, 955, 913, 862, 834, 763, 753,
737, 712, 696, 669, 571, 563, 520, 484, 420 cm–1.
1H NMR (400.13 MHz, D2O): d = 2.21–2.28 (m, 4 H, CH2P), 2.71–
2.78 (m, 4 H, CH2Ph), 6.99–7.08 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 30.27 (CH2Ph), 42.52 (d,
1JCP = 35.8 Hz, CH2P), 125.92 (p-C), 128.15 (o-C), 128.37 (m-C),
141.06 (d, 3JCP = 16.2 Hz, ipso-C).
3
13C NMR (100.61 MHz, D2O): d = 23.49 and 23.84 (d, JCP = 9.7
and 9.2 Hz, Me), 36.96 and 37.05 (CHPh), 49.04 and 49.31 (d,
1JCP = 32.6 and 35.3 Hz, CH2P), 125.88 (p-C), 126.86 and 126.97
(o-C), 128.21 (m-C), 147.04 and 147.10 (d, 3JCP = 11.3 and 11.9 Hz,
ipso-C).
31P NMR (161.98 MHz, D2O): d = 24.88 and 26.01 (ratio 3:1) (s +
d satellites, 1JPSe = 557 Hz and 550 Hz).
31P NMR (161.98 MHz, D2O): d = 26.63 (s + d satellites, 1JPSe = 559
Hz).
77Se NMR (76.31 MHz, D2O): d = –62, –26, and –6 (d, 1JPSe = 564,
557 and 550 Hz).
77Se NMR (76.31 MHz, D2O): d = –62 (d, 1JPSe = 559 Hz).
Anal. Calcd for C18H22RbPSe2: C, 42.17; H, 4.32; P, 6.04; Se, 30.80.
Found: C, 42.25; H, 4.34; P, 6.10; Se, 30.66.
Anal. Calcd for C16H18PRbSe2: C, 39.65; H, 3.74; P, 6.39; Se, 32.58.
Found: C, 39.66; H, 3.81; P, 6.48; Se, 32.49.
Potassium Bis(1-methyl-2-phenylethyl)phosphinodiselenoate
(11h)
White powder; yield: 0.378 g (81%); mp >200 °C (dec.)
Cesium Bis(2-phenylethyl)phosphinodiselenoate (11e)
White powder; yield: 0.520 g (98%); mp 187–189 °C (Et2O).
IR (KBr): 3102, 3081, 3061, 3024, 3000, 2961, 2860, 1601, 1582,
1494, 1452, 1359, 1336, 1315, 1286, 1204, 1170, 1158, 1092, 1049,
IR (KBr): 3097, 3080, 3059, 3021, 2997, 2946, 2926, 2898, 2855,
1654, 1597, 1579, 1493, 1453, 1441, 1396, 1315, 1265, 1206, 1193,
Synthesis 2010, No. 14, 2463–2467 © Thieme Stuttgart · New York

2466
A. V. Artem’ev et al.
PAPER
1028, 990, 913, 898, 862, 825, 756, 705, 682, 621, 574, 536, 503,
488, 425 cm–1.
1H NMR (400.13 MHz, D2O): d = 0.80, 0.85 and 0.90 (d, 3JHH = 6.8
and 6.3 Hz, 6 H, Me), 2.05–2.18 and 2.32–2.44 (m, 4 H, CH2Ph),
3.02–3.08 and 3.21–3.27 (m, 2 H, CHP), 6.95–7.09 (m, 10 H, Ph).
1H NMR (400.13 MHz, DMSO-d6): d = 2.35–2.42 (m, 4 H, CH2P),
3.11–3.18 (m, 4 H, CH2Naphth), 7.34–7.45, 7.65 and 7.77–7.83 (m,
14 H, Naphth).
13C NMR (100.61 MHz, DMSO-d6): d = 31.43 (CH2Naphth), 45.33
1
(d, JCP = 36.6 Hz, CH2P), 125.60–133.79 (Naphth), 140.79 (d,
3JCP = 15.8 Hz, Naphth).
13C NMR (100.61 MHz, D2O): d = 15.85 and 15.97 (Me), 39.50
1
(CH2Ph), 42.68 and 42.74 (d, JCP = 30.8 and 33.4 Hz, CHP),
31P NMR (161.98 MHz, DMSO-d6): d = 23.76 (s + d satellites,
128.60 and 128.70 (p-C), 130.96 and 131.01 (o-C), 131.86 (m-C),
1JPSe = 613 Hz).
142.60 and 142.67 (d, 3JCP = 14.7 and 16.6 Hz, ipso-C).
77Se NMR (76.31 MHz, DMSO-d6): d = –36 (d, 1JPSe = 613 Hz).
31P NMR (161.98 MHz, D2O): d = 67.67 and 67.79 (ratio 1:2) (s +
d satellites, 1JPSe = 571 and 569 Hz).
77Se NMR (76.31 MHz, D2O): d = –158 (d, 1JPSe = 569 Hz).
Anal. Calcd for C24H22KPSe2: C, 53.54; H, 4.12; P, 5.75; Se, 29.33.
Found: C, 53.58; H, 4.18; P, 5.63; Se, 29.43.
Cesium Bis[2-(6-methylpyridin-3-yl)ethyl]phosphinodisele-
noate (11l)
Yellowish powder; yield: 0.540 g (96%); mp 189–191 °C (dec.)
Anal. Calcd for C18H22KPSe2: C, 46.36; H, 4.75; P, 6.64; Se, 33.86.
Found: C, 46.31; H, 4.70; P, 6.50; Se, 33.69.
(Et2O).
Potassium Bis[2-(4-tert-butylphenyl)ethyl]phosphinodisele-
noate (11i)
IR (KBr): 3020, 3000, 2959, 2939, 2923, 2911, 2855, 1966, 1698,
1654, 1603, 1567, 1489, 1439, 1395, 1377, 1319, 1306, 1298, 1275,
1247, 1206, 1185, 1146, 1120, 1109, 1035, 1013, 1003, 985, 954,
932, 916, 858, 838, 793, 774, 739, 722, 705, 647, 542, 515, 482, 416
cm–1.
1H NMR (400.13 MHz, D2O): d = 2.16–2.22 (m, 10 H, CH2P, Me),
2.65–2.73 (m, 4 H, CH2Py), 6.90 (d, 2 H, Py), 7.29 (d, 2 H, Py), 7.97
(s, 2 H, Py).
13C NMR (100.61 MHz, D2O): d = 22.10 (Me), 27.14 (CH2Py),
42.04 (d, 1JCP = 36.0 Hz, CH2P), 123.53, 133.78 (d, 3JCP = 15.8 Hz,
Py), 137.41, 147.32 and 155.35 (Py).
31P NMR (161.98 MHz, D2O): d = 26.18 (s + d satellites, 1JPSe = 563
Hz).
White powder; yield: 0.506 g (92%); mp 185–187 °C (Et2O).
IR (KBr): 3092, 3055, 3023, 2961, 2903, 2865, 1905, 1793, 1627,
1516, 1462, 1439, 1393, 1363, 1268, 1202, 1136, 1108, 1067, 1018,
943, 875, 853, 839, 813, 770, 738, 663, 563, 517, 495 cm–1.
1H NMR (400.13 MHz, D2O): d = 1.26 (s, 18 H, Me), 2.37–2.53 (m,
4 H, CH2P), 2.86–3.04 (m, 4 H, CH2C6H4), 7.13–7.35 (m, 8 H,
C6H4).
13C NMR (100.61 MHz, D2O): d = 30.66 (CH2C6H4), 31.44 (Me3C),
1
32.38 (d, JCP = 41.7 Hz, CH2P), 34.39 (CMe3), 125.45 (C2 in
C6H4), 128.32 (C3 in C6H4), 138.04 (d, 3JCP = 15.7 Hz, C1 in C6H4,),
148.95 (C4 in C6H4).
31P NMR (161.98 MHz, D2O): d = 25.42 (s + d satellites, 1JPSe = 559
Hz).
77Se NMR (76.31 MHz, D2O): d = –68 (d, 1JPSe = 563 Hz).
77Se NMR (76.31 MHz, D2O): d = –65 (d, 1JPSe = 559 Hz).
Anal. Calcd for C16H20CsN2PSe2: C, 34.19; H, 3.59; P, 5.51; Se,
28.09. Found: C, 34.22; H, 3.65; P, 5.34; Se, 28.19.
Anal. Calcd for C24H34KPSe2: C, 52.36; H, 6.23; P, 5.63; Se, 28.69.
Found: C, 52.32; H, 6.30; P, 5.71; Se, 28.50.
Sodium Bis(2-pyridin-4-ylethyl)phosphinodiselenoate (11m)
White powder; yield: 0.394 g (93%); mp >200 °C (dec.).
PotassiumBis[2-(4-methoxyphenyl)ethyl]phosphinodiselenoate
(11j)
White powder; yield: 0.444 g (89%); mp 190–193 °C (Et2O).
IR (KBr): 3070, 3041, 3023, 2994, 2968, 2925, 2900, 1606, 1557,
1501, 1446, 1421, 1398, 1347, 1316, 1279, 1217, 1192, 1142, 1081,
1072, 999, 948, 878, 856, 843, 830, 808, 777, 757, 738, 724, 669,
581, 521, 484, 423, 414 cm–1.
1H NMR (400.13 MHz, D2O): d = 2.37–2.44 (m, 4 H, CH2P), 2.90–
2.97 (m, 4 H, CH2Py), 7.21 and 8.28 (d, 8 H, Py).
IR (KBr): 3057, 3027, 3000, 2955, 2932, 2909, 2834, 2057, 1883,
1610, 1583, 1512, 1463, 1443, 1371, 1300, 1266, 1244, 1179, 1130,
1099, 1060, 1032, 945, 878, 848, 814, 779, 729, 706, 672, 636, 548,
509, 491, 474, 456, 421, 411 cm–1.
1H NMR (400.13 MHz, D2O): d = 2.03–2.13 (m, 4 H, CH2P), 2.50–
2.60 (m, 4 H, CH2C6H4), 3.36 (s, 6 H, OMe), 6.49–6.80 (m, 8 H,
C6H4).
13C NMR (100.61 MHz, D2O): d = 29.98 (CH2Py), 41.51 (d,
1JCP = 37.7 Hz, CH2P), 124.38 and 148.50 (Py), 151.89 (d,
3JCP = 16.8 Hz, Py).
13C NMR (100.61 MHz, D2O): d = 29.19 (CH2C6H4), 42.27 (d,
1JCP = 34.5 Hz, CH2P), 54.64 (OMe), 113.36 (C2 in C6H4), 128.91
(C3 in C6H4), 133.10 (d, 3JCP = 15.0 Hz, C1 in C6H4,), 156.50 (C4
in C6H4).
31P NMR (161.98 MHz, D2O): d = 27.07 (s + d satellites, 1JPSe = 558
Hz).
31P NMR (161.98 MHz, D2O): d = 28.26 (s + d satellites, 1JPSe = 566
Hz).
77Se NMR (76.31 MHz, D2O): d = –63 (d, 1JPSe = 566 Hz).
Anal. Calcd for C14H16N2NaPSe2: C, 39.64; H, 3.80; P, 7.30; Se,
37.23. Found: C, 39.55; H, 3.85; P, 7.19; Se, 37.17.
77Se NMR (76.31 MHz, D2O): d = –39 (d, 1JPSe = 558 Hz).
Cesium Bis[2-(2-furyl)ethyl]phosphinodiselenoate (11n)
White powder; yield: 0.492 g (96%); mp 200–202 °C (dec.) (Et2O)
Anal. Calcd for C18H22KO2PSe2: C, 43.38; H, 4.45; P, 6.22; Se,
31.69. Found: C, 43.31; H, 4.50; P, 6.34; Se, 31.71.
IR (KBr): 3156, 3117, 3104, 2952, 2932, 2895 2850, 1649, 1593,
1505, 1435, 1390, 1375, 1325, 1276, 1224, 1203, 1194, 1169, 1142,
1120, 1106, 1067, 1031, 1005, 964, 946, 936, 915, 901, 883, 820,
777, 725, 675, 643, 601, 493, 420, 402 cm–1.
Potassium bis[2-(2-naphthyl)ethyl]phosphinodiselenoate (11k)
Yellowish powder; yield: 0.506 g (94%); mp 192–194 °C (Et2O).
IR (KBr): 3049, 3016, 2936, 2891, 2848, 1699, 1629, 1598, 1507,
1435, 1393, 1366, 1273, 1197, 1185, 1164, 1125, 1017, 964, 948,
928, 902, 888, 860, 828, 817, 785, 766, 748, 737, 711, 689, 666,
637, 621, 546, 508, 478, 397 cm–1.
1H NMR (400.13 MHz, D2O): d = 2.34–2.42 (m, 4 H, CH2P), 2.86–
2.95 (m, 4 H, CH2Fur), 6.05–6.27 and 7.30 (m, 6 H, Fur).
Synthesis 2010, No. 14, 2463–2467 © Thieme Stuttgart · New York

PAPER
Alkali Metal Phosphinodiselenoates
2467
13C NMR (100.61 MHz, D2O): d = 23.74 (CH2Fur), 39.65 (d,
1JCP = 37.3 Hz, CH2P), 106.05 (C-3 in Fur), 111.12 (C-4 in Fur),
142.25 (C-5 in Fur), 155.28 (d, 3JCP = 18.5 Hz, C-2 in Fur).
31P NMR (161.98 MHz, D2O): d = 26.08 (s + d satellites, 1JPSe = 565
Hz).
(6) (a) Belova, V. V.; Egorova, N. S.; Kholkin, A. I.; Voshkin,
A. A. China Acad. J. 2005, 146. (b) Voshkin, A. A.;
Kostanian, A. E.; Belova, V. V.; Egorova, N. S.; Kholkin, A.
I. China Acad. J. 2005, 1473. (c) Egorova, N. S.; Belova, V.
V.; Voshkin, A. A.; Zhilov, V. I.; Kholkin, A. I. Russ. J.
Inorg. Chem. 2005, 50, 1902.
(7) Mashkovskii, M. D. Lekarstvennye sredstva
[Pharmaceuticals], Vol. 2; Medicina: Moscow, 1998, 360.
(8) (a) Afzaal, M.; O’Brien, P. J. Mater. Chem. 2006, 16, 1597.
(b) Afzaal, M.; Malik, M. A.; O’Brien, P. New J. Chem.
2007, 31, 2029. (c) Fan, D.; Afzaal, M.; Mallik, M. A.;
Nguyen, C. Q.; O’Brien, P.; Thomas, P. J. Coord. Chem.
Rev. 2007, 251, 1878. (d) Jie, G.-F.; Liu, P.; Zhang, S.-S.
Chem. Commun. 2010, 46, 1323. (e) Lesnyak, V.; Dubavik,
A.; Plotnikov, A.; Gaponik, N.; Eychmüller, A. Chem.
Commun. 2010, 46, 886. (f) Zhou, Y.; Riehle, F. S.; Yuan,
Y.; Schleiermacher, H.-F.; Niggemann, M.; Urban, G. A.;
Krüger, M. Appl. Phys. Lett. 2010, 96, 013304.
(9) Maneeprakorn, W.; Nguyen, C. Q.; Malik, M. A.; O’Brien,
P.; Raftery, J. Dalton Trans. 2009, 2103.
77Se NMR (76.31 MHz, D2O): d = –62 (d, 1JPSe = 565 Hz).
Anal. Calcd for C12H14CsO2PSe2: C, 28.15; H, 2.76; P, 6.05; Se,
30.84. Found: C, 28.27; H, 2.74; P, 5.88; Se, 30.77.
Potassium Diphenylphosphinodiselenoate (11o)
White powder; yield: 0.352 g (92%); mp 134–136 °C (Et2O).
IR (KBr): 3052, 2079, 1819, 1628, 1471, 1429, 1395, 1335, 1299,
1171, 1122, 1086, 1060, 1027, 995, 748, 694, 587, 540, 478 cm–1.
1H NMR (400.13 MHz, D2O): d = 7.82–7.87 (m, 10 H, Ph).
13C NMR (100.61 MHz, D2O): d = 128.25 (d, 2JCP = 13.0 Hz, o-C),
4
3
131.01 (d, JCP = 3.0 Hz, p-C), 131.55 (d, JCP = 12.0 Hz, m-C),
140.07 (d, 1JCP = 65.9 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 21.61 (s + d satellites, 1JPSe = 583
Hz).
77Se NMR (76.31 MHz, D2O): d = 25 (d, JPSe = 583 Hz).
(10) Panneerselvam, A.; Nguyen, C. Q.; Malik, M. A.; O’Brien,
P.; Raftery, J. J. Mater. Chem. 2009, 19, 419.
(11) (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. (c) Kawai, T.; Hasegawa, Y.; Adachi, T. US
2009015919 A1, 2009.
(12) Nguyen, C. Q.; Afzaal, M.; Malik, M. A.; Helliwell, M.;
Raftery, J.; O’Brien, P. J. Organomet. Chem. 2007, 692,
2669.
Anal. Calcd for C12H10KPSe2: C, 37.71; H, 2.64; P, 8.10; Se, 41.32.
Found: C, 37.78; H, 2.70; P, 7.95; Se, 41.43.
Cesium Diphenylphosphinodiselenoate (11p)
White powder; yield: 0.447 g (94%); mp 224–226 °C (dec.)
(EtOH).
IR (KBr): 3044, 1967, 1903, 1815, 1660, 1567, 1475, 1433, 1328,
1300, 1176, 1157, 1126, 1089, 1065, 1024, 998, 971, 929, 848, 752,
742, 699, 700, 618, 540, 516, 473, 451, 428 cm–1.
(13) Maneeprakorn, W.; Malik, M. A.; O’Brien, P. J. Mater.
Chem. 2010, 20, 2329.
1H NMR (400.13 MHz, D2O): d = 7.35–7.86 (m, 10 H, Ph).
(14) For an example, see: Davies, R. P.; Francis, C. V.; Jurd, A.
P. S.; Martinelli, M. G.; White, A. J. P.; Williams, D.
J. Inorg. Chem. 2004, 43, 4802.
(15) (a) Kimura, T.; Murai, T. J. Org. Chem. 2005, 70, 952.
(b) Murai, T.; Kimura, T. Curr. Org. Chem. 2006, 10, 1963.
(16) Moon, J.; Nam, H.; Kim, S.; Ryu, J.; Han, C.; Lee, C.; Lee,
S. Tetrahedron Lett. 2008, 49, 5137.
13C NMR (100.61 MHz, D2O): d = 128.72 (d, 2JCP = 12.8 Hz, o-C),
4
3
131.11 (d, JCP = 2.8 Hz, p-C), 131.12 (d, JCP = 11.5 Hz, m-C),
140.50 (d, 1JCP = 64.6 Hz, ipso-C).
31P NMR (161.98 MHz, D2O): d = 21.79 (s + d satellites, 1JPSe = 582
Hz).
(17) Matolcsy, G.; Nádasy, M.; Andriska, V. Pesticide
Chemistry; Elsevier: Amsterdam, 1988.
77Se NMR (76.31 MHz, D2O): d = 27 (d, 1JPSe = 582 Hz).
Anal. Calcd for C12H10CsPSe2: C, 30.28; H, 2.12; P, 6.51; Se, 33.18.
Found: C, 30.19; H, 2.09; P, 6.55; Se, 33.11.
(18) For some examples, see: (a) Kuchen, W.; Metten, J.; Judat,
A. Chem. Ber. 1964, 97, 2306. (b) Kuchen, W.; Knop, B.
Angew. Chem., Int. Ed. Engl. 1965, 4, 244. (c) Kuchen, W.;
Hertel, H. Angew. Chem., Int. Ed. Engl. 1969, 8, 89.
(d) Davies, R. P.; Martinelli, M. G. Inorg. Chem. 2002, 41,
348.
(19) Trofimov, B. A.; Artem’ev, A. V.; Malysheva, S. F.;
Gusarova, N. K. J. Organomet. Chem. 2009, 694, 4116.
(20) Artem’ev, A. V.; Gusarova, N. K.; Malysheva, S. F.;
Ushakov, I. A.; Trofimov, B. A. Tetrahedron Lett. 2010, 51,
2141.
Acknowledgment
Financial support from the Russian Foundation for Basic Research
(Grant no. 08-03-00251) is gratefully acknowledged.
References
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(21) (a) Trofimov, B. A.; Brandsma, L.; Arbuzova, S. N.;
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Synthesis 2010, No. 14, 2463–2467 © Thieme Stuttgart · New York