Facile atom-economic synthesis of ammonium diselenophosphinates via three-component reaction of secondary phosphines, elemental selenium, and ammonia

Article abstract of DOI:10.1055/s-0029-1218729

The three-component reaction between secondary phosphines, R₂PH [R=Ph(CH₂)₂, PhCHMeCH₂, PhCH₂CHMe, 4-t-BuC₆H₄(CH₂)₂, 4-MeOC ₆H₄(CH₂)₂, 2-furyl(CH ₂)₂, 4-pyridyl(CH₂)₂, 6-Me-3-pyridyl(CH₂)₂, Ph], elemental selenium, and ammonia proceeds under mild conditions (EtOH-H₂O, 53-55 C or EtOH, r.t., 10 min) without the formation of byproducts to give the first representatives of ammonium diselenophosphinates in high yields (up to 96%). Georg Thieme Verlag Stuttgart - New York.

Full text of DOI:10.1055/s-0029-1218729

PAPER
1777
Facile Atom-Economic Synthesis of Ammonium Diselenophosphinates via
Three-Component Reaction of Secondary Phosphines, Elemental Selenium,
and Ammonia
Synthesis of
A
mm
l
onium
e
D
iselenoph
x
osphinates ander V. Artem’ev, Svetlana F. Malysheva, Nina K. Gusarova, Nataliya A. Belogorlova, Boris A. Trofimov*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk,
Russian Federation
Fax +7(3952)419346; E-mail: boris_trofimov@irioch.irk.ru
Received 25 February 2010; revised 9 March 2010
phosphinates represents a facile route to the correspond-
Abstract: The three-component reaction between secondary
phosphines, R2PH [R = Ph(CH2)2, PhCHMeCH2, PhCH2CHMe,
4-t-BuC6H4(CH2)2, 4-MeOC6H4(CH2)2, 2-furyl(CH2)2, 4-py-
ridyl(CH2)2, 6-Me-3-pyridyl(CH2)2, Ph], elemental selenium, and
ing Se-esters of diselenophosphinates14a [R1 P(Se)SeR2],
2
showing the properties of efficient reversible addition
fragmentation transfer polymerization (RAFT) agents.15
ammonia proceeds under mild conditions (EtOH–H2O, 53–55 °C or
At the same time, the data on ammonium salts of disele-
EtOH, r.t., 10 min) without the formation of byproducts to give the
first representatives of ammonium diselenophosphinates in high
yields (up to 96%).
nophosphinic
acids
[phosphinodiselenoic
acids,
NH4(Se2PR2)] are absent in literature. One can expect that
ammonium diselenophosphinates would be more conve-
nient reagents compared to alkylammonium or alkali met-
als salts. For example, ammonium diselenophosphinates
might be employed as efficient synthetic equivalents of
Key words: secondary phosphines, elemental selenium, ammonia,
three-component reaction, diselenophosphinates, ammonium salts,
phosphinodiselenoic acid
the
corresponding
diselenophosphinic
acids
[R2P(Se)SeH], because the gaseous ammonia evolved
(unlike amines or alkali metal hydroxides) is readily re-
moved from the reaction mixture.
At present, only salts of alkali metals [M(Se2PR2)]
(M = Li,1 Na,2 K,3,4 Li-Cs5) and alkylammonium
[(alkyl)nNH4–n(Se2PR2)] (n = 3,6 1–37) are known as the
starting source for diselenophosphinate anions. The latter
represent convenient intermediates for the synthesis of
heavy metal diselenophosphinates, which are intensively
used as single-source precursors (SSPs) for the prepara-
tion of nano-sized metal phosphides or selenides (Zn, Cd,
Ni, Co, Ag, In, Eu, etc.) possessing unique magneto-opti-
cal, electrical, and other properties.8 For example, nickel
phosphides (Ni2P and Ni12P5) or nickel selenide (NiSe)
nanoparticles were prepared from nickel(II) dialkyldisele-
nophosphinates, [Ni(Se2PR2)2], by thermolysis in tri-
Here, we report an atom-economic synthesis of the first
representatives of ammonium diselenophosphinates via
the three-component reaction of secondary phosphines
with elemental selenium and ammonia.
The initial secondary phosphines are readily available
from the reaction of red phosphorus and arylethenes or
hetarylethenes (styrenes,16 vinylpyridines,17 or 2-vinyl-
furan16a) in one preparative step.
As our experiments have showed, secondary phosphines
1–9 react readily with elemental selenium and aqueous
ammonia solution (EtOH–H2O, 53–55 °C, 10 min, Meth-
od A) or with liquid ammonia (EtOH, r.t., 10 min, Method
B) to afford ammonium diselenophosphinates 10a–i in
high yields (76–96%) (Table 1).
octylphosphine as
a
coordinating solvent.9 Silver
diselenophosphinate, [Ag(Se2Pi-Pr2)], was employed as a
SSP to obtain silver selenide (Ag2Se) nanofilms via aero-
sol-assisted chemical vapor deposition.10 Europium dise-
lenophosphinate, [Eu(Se2PPh2)3], was used for the
synthesis of europium selenide (EuSe) nanocrystals, the
starting block for the design of novel remarkable magne-
to-optical nanomaterials.3 Nanorods of zinc selenide
(ZnSe) exhibiting semiconductive properties were synthe-
sized from zinc diselenophosphinate, [Zn(Se2Pi-Pr2)2].6
The reaction involves no formation of byproducts and,
hence, is completely atom-economic and ‘green’ (ethanol,
a nontoxic recoverable solvent, is used).
The tentative mechanism of the formation of diseleno-
phosphinates can be presented as follows (Scheme 1). In
the first stage (1), the secondary phosphine A reacts with
one equivalent of elemental selenium to give secondary
phosphine selenide B. The latter is deprotonated by am-
monia to afford P,Se-ambident selenophosphinite anion C
(stage 2), which further reacts with second equivalent of
elemental selenium to provide the diselenophosphinate
anion D (stage 3).
In addition, the diselenophosphinates of alkali metals and
alkylammoniums are ligands for metal complexes,11
promising extractants of heavy, rare, and transuranium
elements,12 potential biologically active compounds,13
as well as the building blocks for organic and elemento-
organic synthesis.14 For instance, alkylation of diseleno-
SYNTHESIS 2010, No. 11, pp 1777–1780
Advanced online publication: 12.04.2010
DOI: 10.1055/s-0029-1218729; Art ID: Z04610SS
x
x.
x
x
.
2
0
1
0
The synthesized salts 10a–i are powders, stable under an
argon blanket, and well soluble in organic solvents (alco-
© Georg Thieme Verlag Stuttgart · New York

1778
A. V. Artem’ev et al.
PAPER
hols, dioxane, THF, DMSO). In addition, these salts can
be easily prepared as crystals by recrystallization from
ethanol, diethyl ether, or hexane.
Table 1 Synthesis of Ammonium Diselenophosphinates from Sec-
ondary Phosphines, Elemental Selenium, and Ammoniaa
R
R
R
Se
Se
solvent
10 min
+
2 Se
+
NH3
P
H
NH4
P
The structures of compounds 10a–i were identified by
multinuclear (1H, 13C, 31P, and 77Se) NMR and their com-
position was confirmed by elemental analysis data. Equiv-
alency of selenium atoms in salts 10a–i follows from 77Se
and 31P NMR data. For example, in the 77Se NMR spectra,
a doublet (1JPSe = 564–640 Hz) is present; in the 31P NMR
spectra, a singlet with one typical satellite pair is observed
(1JPSe = 564–640 Hz). The 1JPSe value (564–640 Hz) is in-
termediate between the coupling constant values for P–Se
and P=Se moieties (200–600 and 800–1200 Hz,
respectively18), thus corresponds to the 1.5 order of the
phosphorus–selenium bond.
R
1–9
10a–i
Entry Phosphine R
Methodb Product Yieldc
(%)
A
B
94
96
1
2
3
4
1
2
3
4
10a
10b
10c
10d
A
B
87
85
In summary, a novel three-component reaction between
secondary phosphines, elemental selenium, and ammonia
affords cleanly the corresponding ammonium salts of di-
selenophosphinic acids (a new family of diselenophos-
phinates) in high yields. The generality and preparative
efficiency of the atom-economic (‘green’) method devel-
oped has been demonstrated by the synthesis of ammoni-
um salts of diselenophosphinic acids bearing aralkyl-,
hetaralkyl-, and aryl substituents. The salts synthesized
are promising intermediates in the production of conduct-
ing nanomaterials and SSPs of semiconducting thin films
and precursors for the design of bioactive products, as
well as building blocks for diverse phosphorus–selenium
organic compounds.
A
B
76
88
A
B
89
88
5
6
7
5
6
7
10e
10f
10g
MeO
A
95
N
A
B
93
95
N
A
B
92
92
All steps of the experiment were carried out under a dry inert atmo-
sphere (argon). Brand EtOH was used in the reaction as a solvent
without additional purification. Secondary phosphines 1–8 were
prepared from styrene,16a a-methylstyrene,16a b-methylstyrene, 4-
tert-butylstyrene,16b 4-methoxystyrene, 4-vinylpyridine,17 2-meth-
yl-5-vinylpyridine,17 or 2-vinylfuran16a and red phosphorus as de-
scribed in the literature. Diphenylphosphine (9) was employed as
8
9
8
9
10h
10i
O
A
B
94
89
a The ratio of phosphine 1–9/Se/NH3 was 1:2:1.6.
1
b Method A: 25% aq NH3 soln, EtOH–H2O, 53–55 °C; Method B: liq-
uid NH3, EtOH, r.t.
commercial product (Aldrich, 2009). The H, 13C, 31P, and 77Se
NMR spectra were recorded on Bruker DPX 400 and Bruker AV-
400 spectrometers (400.13, 100.61, 161.98, and 76.31 MHz, respec-
tively) and referenced to H3PO4 (31P NMR) and Me2Se (77Se NMR).
IR spectra were run on a Bruker IFS 25 instrument. Melting points
were measured on a Kofler micro hot stage apparatus.
c All yields refer to isolated products.
Se
H
Se
(1)
(2)
P
P
H
A
Ammonium Diselenophosphinates 10a–c,e–i; General Proce-
dure (Method A)
B
Se
Se
H
To a soln of the secondary phosphine 1–3, 5–9 (1.0 mmol) in EtOH
(10 mL), 25% aq NH3 soln (~0.12 mL, 1.6 mmol) and amorphous
grey selenium (0.158 g, 2.0 mmol) were consecutively added at r.t.
under argon. The suspension was vigorously stirred at 53–55 °C un-
til the selenium had dissolved completely (~10 min). The colorless
transparent soln formed was filtered, EtOH and H2O were removed
under reduced pressure, and the residue was ground in hexane (10
mL). The latter was decanted, the white powder formed was washed
with hexane (10 mL) and dried in vacuo (35–40 °C/1.33 mbar) to
afford the corresponding salt 10a–c,e–i.
NH4
+
+
NH3
P
P
Se
P
C
B
Se
Se
Se
C
P
(3)
D
Scheme 1 Probable mechanism of formation of ammonium dise-
lenophosphinates
Ammonium Diselenophosphinates 10a,b,d,e,g–i; General Pro-
cedure (Method B)
To a soln of the secondary phosphine 1, 2, 4, 5, 7–9 (1.0 mmol) in
EtOH (10 mL), liquid NH3 (~0.04 mL, 1.6 mmol) and amorphous
grey selenium (0.158 g, 2.0 mmol) were consecutively added at r.t.
Synthesis 2010, No. 11, 1777–1780 © Thieme Stuttgart · New York

PAPER
Synthesis of Ammonium Diselenophosphinates
1779
under argon. The suspension was vigorously stirred at r.t. until the
selenium had dissolved completely (~10 min). The colorless trans-
parent soln formed was filtered, the solvent was removed under re-
duced pressure, and the residue was ground in hexane (10 mL). The
latter was decanted, the white powder formed was washed with hex-
ane (10 mL) and dried in vacuo (35–40 °C/1.33 mbar) to afford the
corresponding salt 10a,b,d,e,g–i.
Anal. Calcd for C18H26NPSe2: C, 48.55; H, 5.89; N, 3.15; P, 6.96;
Se, 35.46. Found: C, 48.53; H, 5.97; N, 3.08; P, 6.61; Se, 35.27.
Ammonium Bis[2-(4-tert-butylphenylethyl]diselenophosphi-
nate (10d)
White powder; yield: 0.466 g (88%); mp 190–194 °C (hexane).
IR (KBr): 3451, 3092, 3055, 3023, 2961, 2903, 2865, 1905, 1793,
1627, 1516, 1495, 1462, 1439, 1393, 1363, 1268, 1202, 1136, 1108,
1067, 1018, 943, 875, 853, 839, 813, 770, 738, 663, 563, 517, 495
cm–1.
Ammonium Bis(2-phenylethyl)diselenophosphinate (10a)
White powder; yield: 0.400 g (96%); mp 217–219 °C (Et2O).
IR (KBr): 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,
606, 481, 413 cm–1.
1H NMR (DMSO-d6): d = 2.26–2.31 (m, 4 H, CH2Ph), 2.95–3.02
(m, 4 H, CH2P), 7.15–7.28 (m, 14 H, Ph, NH4).
13C NMR (DMSO-d6): d = 30.58 (d, 2JPC = 1.8 Hz, CH2Ph), 44.84
(d, 1JPC = 36.9 Hz, CH2P), 125.50 (p-C), 128.09 (o-C), 128.25 (m-
C), 142.50 (d, 3JPC = 16.4 Hz, ipso-C).
31P NMR (DMSO-d6): d = 24.29 (s + d satellites: 1JPSe = 616 Hz).
77Se NMR (DMSO-d6): d = –36 (d, 1JPSe = 616 Hz).
1H NMR (CDCl3): d = 1.35 (s, 18 H, Me), 2.59–2.66 (m, 4 H,
CH2P), 3.05–3.11 (m, 4 H, CH2C6H4), 7.13 (s, 4 H, NH4), 7.23–7.35
(m, 8 H, C6H4).
13C NMR (CDCl3): d = 30.05 (CH2C6H4), 31.43 (Me3C), 34.39
1
(CMe3), 43.15 (d, CH2P, JPC = 35.4 Hz), 125.45 (C2Ar, C6Ar),
3
128.32 (C3Ar, C5Ar), 138.03 (d, JPC = 16.2 Hz, C1Ar), 148.96
(C4Ar).
31P NMR (CDCl3): d = 26.75 (s + d satellites: 1JPSe = 640 Hz).
77Se NMR (CDCl3): d = –48 (d, 1JPSe = 640 Hz).
Anal. Calcd for C24H38NPSe2: C, 54.44; H, 7.23; N, 2.65; P, 5.85;
Se, 29.83. Found: C, 54.31; H, 7.29; N, 2.72; P, 5.80; Se, 29.75.
Anal. Calcd for C16H22NPSe2: C, 46.06; H, 5.31; N, 3.36; P, 7.42;
Se, 37.85. Found: C, 46.10; H, 5.29; N, 3.31; P, 7.31; Se, 37.75.
Ammonium Bis[2-(4-methoxyphenyl)ethyl)]diselenophosphi-
nate (10e)
Ammonium Bis(2-phenylpropyl)diselenophosphinate (10b)
White powder; yield: 0.425 g (89%); mp 180–184 °C (Et2O).
White powder; yield: 0.387 g (87%); mp 154–156 °C (Et2O).
IR (KBr): 3285, 3024, 2992, 2834, 2044, 1877, 1649, 1609, 1583,
1511, 1464, 1442, 1396, 1318, 1299, 1265, 1244, 1196, 1176, 1128,
1026, 951, 937, 876, 848, 812, 774, 736, 723, 709, 691, 638, 548,
520, 502, 484, 454, 421, 404 cm–1.
1H NMR (DMSO-d6): d = 2.19–2.26 (m, 4 H, CH2P), 2.86–2.93 (m,
4 H, CH2C6H4), 3.70 (s, 6 H, OMe), 6.81–7.11 (m, 12 H, C6H4,
NH4).
IR (KBr): 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 cm–1.
1H NMR (DMSO-d6): d = 1.27–1.35 (m, 6 H, Me), 2.04–2.24 (m, 4
H, CH2P), 3.36–3.52 (m, 2 H, CH), 7.08–7.22 (m, 14 H, Ph, NH4).
3
13C NMR (DMSO-d6): d = 23.98, 24.37 (d, JPC = 5.2 Hz, Me),
13C NMR (DMSO-d6): d = 30.28 (CH2C6H4), 45.60 (d, 1JPC = 36.2
Hz, CH2P), 55.55 (OMe), 114.31 (C2Ar, C6Ar), 129.60 (C3Ar, C5Ar),
134.89 (d, 3JPC = 16.6 Hz, C1Ar), 157.86 (C4Ar).
31P NMR (DMSO-d6): d = 24.04 (s + d satellites: 1JPSe = 608 Hz).
77Se NMR (DMSO-d6): d = –35 (d, 1JPSe = 608 Hz).
37.02, 37.40 (CHPh), 52.22, 52.63 (d, 1JPC = 34.0, 35.0 Hz, CH2P),
125.01 (p-C), 127.52, 127.54 (o-C), 128.30 (m-C), 149.48, 149.60
(d, 3JPC = 12.4 Hz, ipso-C).
31P NMR (DMSO-d6): d = 22.94 (s + d satellites: JPSe = 607 Hz),
1
24.14 (satellites: 1JPSe = 612 Hz), the ratio of intensities is 52:48.
77Se NMR (DMSO-d6): d = –23.2, 23 (d, 1JPSe = 607 Hz).
Anal. Calcd for C18H26NO2PSe2: C, 45.30; H, 5.49; N, 2.93; P, 6.49;
Se, 33.09. Found: C, 45.15; H, 5.54; N, 2.90; P, 6.44; Se, 32.98.
Anal. Calcd for C18H26NPSe2: C, 48.55; H, 5.89; N, 3.15; P, 6.96;
Se, 35.46. Found: C, 48.50; H, 5.77; N, 3.11; P, 6.69; Se, 35.43.
Ammonium Bis[2-(4-pyridyl)ethyl]diselenophosphinate (10f)
Yellow powder; yield: 0.400 g (95%); mp >200 °C (dec.).
Ammonium Bis(1-methyl-2-phenylethyl)diselenophosphinate
(10c)
White powder; yield: 0.338 g (76%); mp 178–181 °C (Et2O).
IR (KBr): 3452, 2991, 2893, 2610, 2225, 2152, 2111, 1923, 1709,
1675, 1609, 1557, 1503, 1456, 1452, 1425, 1395, 1316, 1282, 1246,
1222, 1212, 1198, 1189, 1140, 1093, 1071, 1030, 1007, 948, 936,
880, 831, 802, 763, 748, 736, 703, 665, 585, 572, 519, 482, 423
cm–1.
1H NMR (DMSO-d6): d = 2.27–2.34 (m, 4 H, CH2P), 2.99–3.05 (m,
4 H, CH2Py), 7.08 (s, 4 H, NH4), 7.25 (d, 4 H, Py), 8.42 (d, 4 H, Py).
IR (KBr): 3251, 3078, 3060, 2955, 2864, 2760, 1947, 1880, 1805,
1635, 1604, 1580, 1493, 1450, 1390, 1306, 1284, 1233, 1195, 1181,
1148, 1085, 1074, 1047, 1028, 1005, 996, 912, 848, 829, 763, 747,
735, 701, 584, 560, 545, 530, 489, 460, 405 cm–1.
1H NMR (CDCl3): d = 1.19 (dd, 3JHH = 6.9 Hz, 3JPH = 7.8 Hz, 6 H,
Me), 2.51–2.57 (m, 2 H, CHP), 3.43–3.53 (m, 4 H, CH2Ph), 7.16–
7.28 (m, 14 H, Ph, NH4).
13C NMR (DMSO-d6): d = 30.54 (CH2Py), 43.94 (d, 1JPC = 37.5 Hz,
CH2P), 124.27, 149.79 (Py), 152.12 (d, 3JPC = 16.7 Hz, Py).
31P NMR (DMSO-d6): d = 24.20 (s + d satellites: 1JPSe = 616 Hz).
77Se NMR (DMSO-d6): d = –51 (d, 1JPSe = 616 Hz).
13C NMR (CDCl3): d = 13.22, 14.74 (Me), 36.79 (CH2h), 39.68,
1
40.07 (d, JPC = 40.5, 41.5 Hz, CHP), 125.61 (p-C), 127.86 (o-C),
128.90, 129.02 (m-C), 139.46, 139.71 (d, 3JPC = 15.9, 17.1 Hz, ipso-
Anal. Calcd for C14H20N3PSe2: C, 40.11; H, 4.81; N, 10.02; P, 7.39;
Se, 37.67. Found: C, 40.04; H, 4.86; N, 10.11; P, 7.13; Se, 37.49.
C).
31P NMR (EtOH): d = 63.51, 63.85 (s + d satellites: 1JPSe = 585 Hz),
Ammonium Bis[2-(6-methyl-3-pyridyl)ethyl]diselenophosphi-
nate (10g)
Yellowish powder; yield: 0.425 g (95%); mp 178–180 °C (Et2O).
the ratio of intensities is 40:60.
77Se NMR (EtOH): d = –160, –158, –156 (d, 1JPSe = 584 Hz).
Synthesis 2010, No. 11, 1777–1780 © Thieme Stuttgart · New York

1780
A. V. Artem’ev et al.
PAPER
IR (KBr): 3450, 3001, 2920, 2861, 2115, 1955, 1890, 1678, 1657,
1639, 1604, 1569, 1495, 1473, 1441, 1393, 1325, 1298, 1278, 1246,
1207, 1189, 1171, 1139, 1113, 1094, 1037, 1011, 979, 950, 916,
856, 831, 790, 775, 741, 729, 717, 672, 652, 826, 543, 519, 512,
501, 484, 417 cm–1.
1H NMR (D2O): d = 2.12–2.19 (m, 10 H, CH2P, Me), 2.62–2.68 (m,
4 H, CH2Py), 6.87 (d, 2 H, Py), 7.26 (d, 2 H, Py), 7.93 (s, 2 H, Py).
13C NMR (D2O): d = 22.14 (Me), 27.31 (CH2Py), 42.22 (d,
1JPC = 35.9 Hz, CH2P), 123.88 (Py), 134.13 (d, 3JPC = 15.8 Hz, Py),
137.95, 147.09, 155.24 (Py).
31P NMR (D2O): d = 26.36 (s + d satellites: 1JPSe = 564 Hz).
77Se NMR (D2O): d = –63 (d, 1JPSe = 564 Hz).
(2) (a) Kuchen, W.; Metten, J.; Judat, A. Chem. Ber. 1964, 97,
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O’Brien, P.; Doi, T.; Hinatsu, Y.; Fujita, K.; Tanaka, K.;
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Anal. Calcd for C16H24N3PSe2: C, 42.96; H, 5.41; N, 9.39; P, 6.92;
Se, 35.31. Found: C, 42.93; H, 5.34; N, 9.21; P, 6.73; Se, 35.19.
Ammonium Bis[2-(2-furyl)ethyl]diselenophosphinate (10h)
White powder; yield: 0.365 g (92%); mp 147–150 °C (Et2O).
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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.
IR (KBr): 3288, 3106, 3058, 2933, 2898, 2759, 1716, 1643, 1597,
1505, 1435, 1384, 1327, 1276, 1225, 1204, 1195, 1170, 1143, 1122,
1108, 1069, 1031, 1007, 964, 947, 936, 914, 903, 883, 815, 790,
778, 725, 677, 641, 600, 492, 418, 402 cm–1.
1H NMR (DMSO-d6): d = 2.24–2.31 (m, 4 H, CH2P), 2.97–3.03 (m,
4 H, CH2Fur), 6.08–6.31, 7.47 (m, 6 H, H3furyl, H4furyl, H5furyl), 7.13
(s, 4 H, NH4).
1
13C NMR (DMSO-d6): d = 23.26 (CH2furyl), 41.02 (d, JPC = 38.0
Hz, CH2P), 104.73 (C3furyl), 110.30 (C4furyl), 141.11 (C5furyl),
155.50 (d, 3JPC = 20.2 Hz, C2furyl).
31P NMR (DMSO-d6): d = 23.01 (s + d satellites: 1JPSe = 607 Hz).
77Se NMR (DMSO-d6): d = –42 (d, 1JPSe = 607 Hz).
(9) Maneeprakorn, W.; Nguyen, C. Q.; Malik, M. A.; O’Brien,
P.; Raftery, J. Dalton Trans. 2009, 2103.
(10) Panneerselvam, A.; Nguyen, C. Q.; Malik, M. A.; O’Brien,
P.; Raftery, J. J. Mater. Chem. 2009, 19, 419.
(11) Lobana, T. S.; Wang, J.-C.; Liu, C. W. Coord. Chem. Rev.
2007, 251, 91.
(12) (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.
Anal. Calcd for C12H18NO2PSe2: C, 36.29; H, 4.57; N, 3.53; P, 7.80;
Se, 39.76. Found: C, 36.32; H, 4.51; N, 3.60; P, 7.68; Se, 39.85.
Ammonium Diphenyldiselenophosphinate (10i)
White powder; yield: 0.340 g (94%); mp 201–203 °C (Et2O).
IR (KBr): 3048, 2930, 2787, 1958, 1919, 1895, 1816, 1770, 1633,
1570, 1476, 1433, 1395, 1373, 1333, 1305, 1178, 1156, 1127, 1089,
1068, 1024, 997, 973, 923, 849, 742, 689, 618, 536, 516, 472, 444,
428 cm–1.
1H NMR (DMSO-d6): d = 7.13 (s, 4 H, NH4), 7.21–7.23 (m, 2 H,
Ph), 7.25–7.29 (m, 4 H, Ph), 8.01–8.06 (m, 4 H, Ph).
(13) Matolcsy, G.; Nadasy, M.; Andriska, V. Pesticide
Chemistry; Elsevier: Budapest, 1988.
(14) (a) Kimura, T.; Murai, T. J. Org. Chem. 2005, 70, 952.
(b) Murai, T.; Kimura, T. Curr. Org. Chem. 2006, 10, 1963.
(15) Moon, J.; Nam, H.; Kim, S.; Ryu, J.; Han, C.; Lee, C.; Lee,
S. Tetrahedron Lett. 2008, 49, 5137.
(16) (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.
(17) Gusarova, N. K.; Trofimov, B. A.; Malysheva, S. F.;
Shaukhudinova, S. I.; Belogorlova, N. A.; Arbuzova, S. N.;
Nepomnyashchikh, K. V.; Dmitriev, V. I. Russ. J. Gen.
Chem. 1997, 67, 65.
13C NMR (DMSO-d6): d = 126.66 (d, 2JPC = 11.5 Hz, o-C), 128.28
(d, 4JPC = 2.9 Hz, p-C), 130.72 (d, 3JPC = 11.0 Hz, m-C), 143.30 (d,
1JPC = 59.3 Hz, ipso-C).
31P NMR (DMSO-d6): d = 23.64 (s + d satellites: 1JPSe = 631 Hz).
77Se NMR (DMSO-d6): d = 15 (d, 1JPSe = 631 Hz).
Anal. Calcd for C12H14NPSe2: C, 39.91; H, 3.91; N, 3.88; P, 8.58;
Se, 43.73. Found: C, 39.84; H, 3.96; N, 3.71; P, 8.33; Se, 43.75.
Acknowledgment
Financial support from the Russian Foundation for Basic Research
(Grant no. 08-03-00251) is gratefully acknowledged.
(18) Duddeck, H. In Encyclopedia of Nuclear Magnetic
Resonance; Grant, D. M.; Harris, R. K., Eds.; Wiley: New
York, 1996, 4623.
References
(1) Davies, R. P.; Martinelli, M. G. Inorg. Chem. 2002, 41, 348.
Synthesis 2010, No. 11, 1777–1780 © Thieme Stuttgart · New York