Novel atom-economic synthesis of thioselenophosphinates via three-component reaction between secondary phosphine sulfides, elemental selenium, and amines

Article abstract of DOI:10.1080/17415993.2011.628993

An efficient, general, and atom-economic synthesis of organoammonium thioselenophosphinates has been developed by exploiting a three-component reaction between secondary phosphine sulfides, elemental selenium, and various amines. The reaction proceeds und

Full text of DOI:10.1080/17415993.2011.628993

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Novel atom-economic synthesis of
thioselenophosphinates via three-
component reaction between
secondary phosphine sulfides,
elemental selenium, and amines
Alexander V. Artem'ev a , Svetlana F. Malysheva a , Anastasiya O.
Korocheva a , Yuriy V. Gatilov b , Victor I. Mamatyuk b & Nina K.
Gusarova a
a A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences , 1 Favorsky Street, 664033 ,
Irkutsk , Russia
b N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch, Russian Academy of Sciences , 9 Lavrentiev
Avenue, 630090 , Novosibirsk , Russia
Published online: 02 Nov 2011.
To cite this article: Alexander V. Artem'ev , Svetlana F. Malysheva , Anastasiya O. Korocheva ,
Yuriy V. Gatilov , Victor I. Mamatyuk & Nina K. Gusarova (2011) Novel atom-economic synthesis
of thioselenophosphinates via three-component reaction between secondary phosphine
sulfides, elemental selenium, and amines, Journal of Sulfur Chemistry, 32:6, 599-610, DOI:
10.1080/17415993.2011.628993
To link to this article: http://dx.doi.org/10.1080/17415993.2011.628993
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Journal of Sulfur Chemistry
Vol. 32, No. 6, December 2011, 599–610
Novel atom-economic synthesis of thioselenophosphinates via
three-component reaction between secondary phosphine
sulfides, elemental selenium, and amines
Alexander V. Artem’eva, Svetlana F. Malyshevaa, Anastasiya O. Korochevaa, Yuriy V. Gatilovb,
Victor I. Mamatyukb and Nina K. Gusarovaa*
aA.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky
Street, 664033 Irkutsk, Russia; bN.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian
Branch, Russian Academy of Sciences, 9 Lavrentiev Avenue, 630090 Novosibirsk, Russia
(Received 18 August 2011; final version received 19 September 2011)
An efficient, general, and atom-economic synthesis of organoammonium thioselenophosphinates has been
developed by exploiting a three-component reaction between secondary phosphine sulfides, elemental
selenium, and various amines. The reaction proceeds under mild conditions (70–75 ◦C, 1 h, EtOH) to
afford thioselenophosphinates in 77–94% yields.
R2
N
R4
R2
R1
R1
S
H
R1
R1
Se
S
70–75oC, 1h
EtOH
R4
N
H
R3
P
+
Se
+
P
R3
77–94%
R1 = aryl, arylalkyl, hetarylalkyl
R2, R3, R4 = H, Et, Bu, Bn, All, Ph, HO(CH2)2, (R)-CH2CH(OH)Et
Keywords: amines; secondary phosphine sulfides; elemental selenium; thioselenophosphinates; three-
component reaction
1. Introduction
The salts of thioselenophosphinic acids are convenient models for the investigation of S,Se-
ambident dual reactivity (almost unexplored so far (1)), which is specific for the conjugate
− −
anionic triads of “S X Se” type [X = carbon (2) or phosphorus (3)]. Furthermore, thiose-
lenophosphinates are employed as key starting compounds for access to both S- and Se-esters
of thioselenophosphinic acids (1) as well as versatile S-and/or Se-donor ligands for the design
of metal complexes (4). The latter are high-potential single-source precursors for the fabrication
*Corresponding author. Email: gusarova@irioch.irk.ru
ISSN 1741-5993 print/ISSN 1741-6000 online
© 2011 Taylor & Francis
http://dx.doi.org/10.1080/17415993.2011.628993
http://www.tandfonline.com

600 A.V. Artem’ev et al.
of nanosized semiconducting metal sulfides and/or selenides, having a wide range of remarkable
properties (5).
The most conventional approach to the synthesis of thioselenophosphinates is based on two
mutually complementary reactions (Scheme 1): condensation of selenophosphinic chlorides
R2P(Se)Cl with sodium hydrosulfide (4c,d, 6) (Pathway a) or interaction of thiophosphinic
chlorides R2P(S)Cl with sodium hydroselenide (6) (Pathway b).
Also, sodium diethylthioselenophosphinate was synthesized by the reaction of tetraethyldiphos-
phine disulfide with sodium selenide and elemental selenium in low yield (6b) (Scheme 2).
Alternative synthesis of thioselenophosphinic acid salts involves the reaction of primary or sec-
ondary amines with S-(thioacyl)thioselenophosphinates prepared from diphenylselenophosphinic
chloride and cesium dithiocarboxylates (7) (Scheme 3).
A more modern route to thioselenophosphinates includes the following procedure (1)
(Scheme 4), which involves as the key step the reaction of tetraalkylammonium fluoride
with S-2-(trimethylsilyl)ethyl thioselenophosphinates. The latter were prepared in several
steps from phenyldichlorophosphine, Grignard reagents, elemental selenium, and lithium 2-
(trimethylsilyl)ethanethiolate (1).
Clearly, the aforementioned methods have significant drawbacks such as the multistage
character, difficulty in preparing starting compounds, the need for anhydrous conditions, low
temperatures, and long reaction times.
Currently, the most convenient approach to thioselenophosphinates is their one-pot synthesis
from secondary phosphines, selenium, sulfur, and aliphatic amines (8) (Scheme 5). This method
is triggered by the oxidation of secondary phosphines by elemental selenium to give secondary
phosphine selenides. The latter, without isolation, interact with elemental sulfur and amines in
a three-component-type reaction to afford the target thioselenophosphinates. It should be noted
that only very simple amines were used in this reaction (8).
R
R
Se
Cl
0°C
Pathway a:
+
NaHS
P
30 min
R
R
Se
S
P
Na
R
R
S
0°C
R = Et, Ph
40–78%
Pathway b:
P
+
NaHSe
30 min
Cl
Scheme 1. Synthesis of thioselenophosphinates via condensation of chalcophosphinic chlorides
with sodium hydrochalcogenides.
Et
Et
Se
S
200°C
2 h
S S
+
Na2Se
+
Se
P
Na
Et2P PEt2
35%
Scheme 2. Synthesis of sodium diethylthioselenophosphinate from tetraethyldiphosphine
disulfide, sodium selenide and elemental selenium.
Ph
Ph
Se
S
Ph
Ph
Se
Cl
S
S
Ph
Ph
Se
S
R
S
R'2NH
0°C
P
P
+
R
Cs
H2NR'2
P
r.t., 6–24h
68–91%
R' = H, Et, Ph, Cy
14–80%
Scheme 3. Multi-step synthesis of organoammonim thioselenophosphinates.

Journal of Sulfur Chemistry 601
1) RMgX
2) Me3Si(CH2)2SLi
R
Se
[Alk4N]F
R
Se
S
3) Se
P
PhPCl2
P
NAlk4
–78 oC to r.t., 2 h
Ph
SCH2CH2SiMe3 0°C, 2 h
66–78%
Ph
90–94%
R = Ph, i-Pr, t-Bu;
Alk = Me, Bu
Scheme 4. Multi-step synthesis of tetraalkylammonium thioselenophosphinates.
1/8 S8 + NR'3
70°C, 20 min
R
R
Se
S
Se
R
R
Se
H
R2PH
P
P
HNR'3
40°C, 20 min
76–94%
R = Ph, arylalky, hetarylalkyl
R' = H, Et, Pr, All
Scheme 5. One-pot synthesis of thioselenophosphinates from secondary phosphines, elemental
selenium, sulfur, and amines.
Herein, we report on a new general and efficient synthesis of organoammonium thioselenophos-
phinates via a three-component reaction between secondary phosphine sulfides, elemental
selenium, and diverse amines. This reaction, apart from its fundamental importance, has a practical
value because the application of secondary phosphine sulfides are experimentally more convenient
than that of secondary phosphines, especially in the cases when the latter demonstrate propensity
to oxidize upon exposure to air. It should be noted that the secondary phosphine sulfides as starting
materials are now easily accessible (9) in one step from cheap red phosphorus, elemental sulfur,
and vinylarenes or vinylhetarenes, e.g. styrenes, vinylpyridines, or 2-vinylfurane.
2. Results and discussion
Our experiments have shown that secondary phosphine sulfides 1a–g react readily with elemen-
tal selenium and various amines in the molar ratio 1:1:1.1 (70–75 ◦C, 1 h, ethanol) to afford
thioselenophosphinates 2a–n in 77–94% yields (Scheme 6, Table 1).
The generality of the three-component reaction is illustrated with respect to various sec-
ondary phosphine sulfides and includes a wide range of functionally unsaturated and optically
active amines. In addition, the reaction occurs under mild and eco-friendly conditions, which are
amenable to scale-up.
Significantly, thethree-componentreactionofbis(pyridylethyl)phosphinesulfides1dand e with
elemental selenium and allylamine or diethylamine (Entries 8–11, Table 1) proceeds chemose-
lectively to give exclusively salts 2h–k, i.e. the pyridine moiety as an alternative N-base remains
intact.
R2
N
R4
R2
R3
R1
R1
S
H
R1
R1
Se
S
70–75°C, 1 h
EtOH
R3
P
+
Se
+
R4
N
P
H
1a–g
2a–n
Scheme 6. Efficient atom-economic synthesis of organoammonium thioselenophosphinates via
a three-component reaction between secondary phosphine sulfides, elemental selenium, and
amines.

602 A.V. Artem’ev et al.
Table 1. Synthesis of thioselenophosphinates from secondary phosphine sulfides, elemental selenium, and amines.
Entry
1
Phosphine sulfide
R1
Amine
Et2NH
Product
Yield (%)a
1a
Ph(CH2)2
2a
94
2
1a
Ph(CH2)2
2b
82
O
NH
3
4
1a
1a
Ph(CH2)2
Ph(CH2)2
HO(CH2)2NH2
H2N Me
2c
77
79
2d
OH
5
6
1a
1b
Ph(CH2)2
PhNH2
2e
2f
85
88
Et2NH
Pr2NH
MeO
7
8
1c
2g
2h
78
82
t-Bu
1d
AllNH2
N
N
9
10
11
1d
1e
1e
Et2NH
AllNH2
Et2NH
2i
2j
77
84
88
Me
Me
N
N
2k
12
1f
Bn2NH
2l
87
O
13
14
1g
1g
Ph
Ph
Bu2NH
Et3N
2m
2n
82
85
Note: aIsolated yield.
At sametime, wehavefound thatsecondary phosphinesulfide 1e reactswithelementalselenium
in a 1:1 molar ratio to form salt 2o in 84% yield, which is the first representative of zwitterionic
thioselenophosphinates (Scheme 7). This two-component reaction proceeds under harsher con-
ditions (90–95 ◦C, 1 h, dioxane) than required in the three-component reactions discussed above
(Table 1).
The newly synthesized thioselenophosphinates 2a–o are air-stable colorless crystalline pow-
ders soluble in polar solvents. Their structures have been proved by multinuclear NMR (1H, 13C,
31P, and 77Se) and IR spectroscopy. In addition, one of thioselenophosphinates, namely diethylam-
monium salt 2a, was structurally characterized by single-crystal X-ray crystallography. Figure 1
shows a molecular structure of compound 2a, which crystallized in the orthorhombic crystal sys-
tem with space group Pna1. In thioselenophosphinate anion, the phosphorus atom is attached to
the selenium and sulfur atoms in a distorted tetrahedral geometry. As expected, sulfur and sele-
nium atoms are disordered over two positions (0.620:0.380). It should be noted that such disorder
of chalcogen atoms is specific for many thioselenophosphinates (1,8,10), except for tellurium

Journal of Sulfur Chemistry 603
Me
H
Me
N
N
N
N
Se
P
S
S
H
90–95°C, 1 h
Dioxane
+
Se
P
Me
Me
1e
2o
(84%)
Scheme 7. Atom-economic synthesis of zwitterionic thioselenophosphinate 2o.
−
Figure 1. X-ray crystal structure of thioselenophosphinate 2a showing the hydrogen bonding interactions of N H · · ·
S(Se). The sulfur and selenium atoms are disordered over two positions (0.620:0.380).
−
−
(11a) and thallium (11b) diethylthioselenophosphinates. The values of the P S and P Se bond
lengths in 2a are similar to literature ones (3,8,10). In the solid state of diethylammonium salt 2a,
−
there is an N H· · · Ch (Ch = S, Se) hydrogen bonding interaction (Figure 1), with the H· · · Ch
bond distances equal to 2.44–2.71Å.
One of the tentative pathways of thioselenophosphinate 2a–n formation (Scheme 8) includes
the deprotonation of the starting secondary phosphine sulfide 1 by the amine to generate the
P, S-ambident thiophosphinite anion A (stage 1), which further reacts (as an P-nucleophile) with
elemental selenium to provide thiselenophosphinate 2 (Stage 2).
Alternatively, this three-component reaction (Scheme 9) might start from the oxidation of
secondary phosphine sulfide 1, existing in two tautomeric forms, by elemental selenium to give
R1
R1
S
H
R1
R1
R1
R1
S
stage 1
Se
P
+
NR2R3R4
P
S
P
Stage 2
- [HNR2R3R4]+
Se
2
A
1
Scheme 8. Plausible pathway for the three-component reaction between secondary phosphine
sulfides, amines, and selenium.

604 A.V. Artem’ev et al.
R1
R1
S
R1
R1
SH
Se
R1
R1
S
H
R1
R1
Stage 1
P
P
P
P
SH
+ Se
SeH
B
1
Stage 2
R1
R1
S
P
HNR2R3R4
B
+
NR2R3R4
Se
2
Scheme 9. Alternative mechanism of the three-component reaction via thioselenophosphinic
acid B formation.
Ph
Ph
Ph
Ph
Ph
Ph
S
S
S
H
Toluene
P
P
P
+
Se
80–90°C, 0.5 h
Se
82%
Scheme 10. Chemoselective reaction between secondary phosphine sulfide and elemental
selenium.
thioselenophosphinic acid B (Stage 1). The latter is deprotonated by the corresponding amine to
afford salt 2 (Stage 2).
However, it has been found that secondary phosphine sulfides react with elemental selenium
(1:1 molar ratio, toluene, 80–90 ◦C, 0.5 h) to furnish bis[diorganothiophosphoryl]selenides in
high yield instead of the anticipated acids B (Scheme 10). The results of the unprecedented
chemoselective reaction will be published elsewhere.
But despite of this, the mechanism of three-component reaction still needs to be elucidated. At
the moment, due to the lack of additional experimental data, it is impossible to assess with any
confidence that the tentative pathway presented in Scheme 8 is correct.
3. Conclusion
In summary, we have developed a novel general and efficient atom-economic synthesis of
diverse organoammonium thioselenophosphinates via three-component reaction between sec-
ondary phosphine sulfides, elemental selenium, and amines. The reaction readily proceeds in
ethanol (“green” solvent) at 70–75 ◦C within 1 h, the product yields reaching 94%. The resulting
thioselenophosphinates are prospective ligands for the design of metal complexes as well as highly
reactive building blocks for numerous chemical transformations in organic synthesis. The results
represent a novel principal contribution to both theoretical and synthetic chemistry of secondary
phosphine sulfides and thioselenophosphinates.
4. Experimental
4.1. General
Melting points (uncorrected) were measured on a Kofler micro hot-stage apparatus. The micro-
analyses were performed on a Flash EA 1112 Series elemental analyzer. The optical activity of salt
2d was determined on a PolamatA instrument. Fourier transform IR spectra were run on a Bruker
Vertex 70 instrument. The 1H, 13C, 31P, and 77Se NMR spectra were recorded on a Bruker AV-400

Journal of Sulfur Chemistry 605
spectrometer (400.13, 100.61, 161.98, and 76.31 MHz, respectively) and referenced to H3PO4
(31P NMR) and Me2Se (77Se NMR). Chemical shifts (δ) are expressed in ppm downfield from
hexamethyldisiloxane, CHCl3, or DMSO-d6 as internal standards. All steps of the experiment
were carried out in argon atmosphere.
Brand ethanol (96%) was used in the reaction as a solvent. Diethyl ether and dioxane were
distilled over metal sodium before use. Secondary phosphine sulfides 1a–f were prepared
from red phosphorus, elemental sulfur, and styrene (9a), 4-methoxystyrene, 4-tert-butylstyrene
(9c), 2-vinylpyridine (9a), 5-vinyl-2-methylpyridine (9b), or 2-vinylfurane as described in
the literature. Diphenylphosphine sulfide (1g) was prepared by the oxidation of commercial
diphenylphosphine (Aldrich) with powdered sulfur in ethanol. Amines were distilled over pow-
dered potassium hydroxide prior to use. Optically activity (R)-1-aminobutano-2-ol was employed
as the commercial product (Aldrich) without further purification. Room temperature refers to
20–25 ◦C.
4.2. X-ray crystallography of compound 2a
Single crystals of thioselenophosphinate 2a suitable for X-ray diffraction were obtained by
slow evaporation of its ethanol solution at 3–5 ◦C. X-ray data were measured at 150(2) K on
a Bruker Kappa Apex II diffractometer with graphite monochromated MoKα radiation using
ϕ, ω scans (θ < 30 ◦). A correction for absorption was made using SADABS program (trans-
mission 0.25–0.34). The structure was solved by direct methods and refined by a full matrix
least-squares anisotropic procedure using SHELXTL97 programs (12). The parameters of the
hydrogen atoms were given geometrically. The final indexes are wR2 = 0.1178, S = 1.081 for
all 6348 F2 and R1 = 0.0427 for 4924 Fo > 4σ (239 parameters, 1 restrains, racemic twin-
ning 17(1)%). CCDC-832002 contains the supplementary crystallographic data for this paper.
These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Crystal data and structural refinement for 2a: [C16H18PSSe]−, [C4H12N]+, M = 426.44, crys-
tal class orthorhombic, space group Pna21, a = 15.1349(13), b = 22.694(2), c = 6.3965(5)Å,
V = 2197.0(3)Å3, Z = 4, dc = 1.289 g/cm3, μ(MoKa) = 1.879 mm−1, crystal size 0.05 ×
0.09 × 0.45 mm. Selected bond lengths (Å): Se1–P1 2.1206(9), Se2–P1 2.030(6), S1–P1 2.115(9),
S2–P1 2.034(2), P1–C1 1.793(3), P1–C9 1.835(3). The sulfur and selenium atoms are disordered
over two positions (0.620:0.380).
4.3. General procedure for the synthesis of thioselenophosphinate 2a–n
The amine (1.1 mmol) was added to a suspension of powdered gray selenium (0.079 g, 1.0 mmol)
inasolutionofsecondaryphosphinesulfide 1a–g (1.0 mmol)inEtOH(10 ml)atroomtemperature.
The suspension was stirred at 70–75 ◦C until dissolution of selenium (∼1 h) to give a transparent
solution.Thesolventswereremovedunderreducedpressureandtheresiduewaswashedwithether
(2 × 10 ml) and dried in vacuo (1 Torr, 45 ◦C) to afford the corresponding thioselenophosphinate
2a–n.
4.3.1. Diethylammonium bis(2-phenethyl)thioselenophosphinate (2a)
White powder; yield: 0.40 g (94%); m.p. 154–156 ◦C. IR (KBr, ν, cm−1): 3449, 3057, 3024,
2937, 2841, 2788, 2495, 1949, 1806, 1600, 1536, 1496, 1451, 1400, 1384, 1332, 1266, 1195,
1159, 1124, 1063, 1047, 1019, 950, 934, 903, 872, 764, 750, 723, 697, 588, 552, 495, 477, 434.
1H NMR (400.13 MHz, CDCl3): δ = 1.55 (t, 3JHH = 7.4 Hz, 6 H, Me), 2.45–2.52 (m, 4 H, CH2P),

606 A.V. Artem’ev et al.
3.09–3.16 (m, 4 H, CH2Ph), 3.18–3.24 (m, 4 H, CH2N), 7.19–7.33 (m, 10 H, Ph), 8.77 (br. s,
2 H, HN). 13C NMR (100.61 MHz, CDCl3): δ = 11.4 (Me), 30.2 (CH2Ph), 41.2 (CH2N), 43.9
1
3
(d, JCP = 42.9 Hz, CH2P), 125.9 (p-CPh), 128.3 (o,m-CPh), 141.7 (d, JCP = 17.2 Hz, i-CPh).
31P NMR (161.98 Hz, CDCl3): δ = 48.14 (s, JPSe = 565 Hz). 77Se NMR (76.31 Hz, CDCl3):
1
δ = −72 (d, 1JPSe = 565 Hz). Anal. Calcd for C20H30NPSSe: C, 56.33; H, 7.09; P, 7.26; S, 7.52;
Se, 18.52. Found: C, 56.28; H, 7.18; P, 7.21; S, 7.37; Se, 18.41.
4.3.2. Morpholin-4-ium bis(2-phenethyl)thioselenophosphinate (2b)
White powder; yield: 0.36 g (82%); m.p. 143–145 ◦C. IR (KBr, ν, cm−1): 3450, 3082, 3061,
2999, 2975, 2926, 2864, 2807, 2703, 2639, 2473, 1951, 1813, 1600, 1581, 1496, 1453, 1442,
1392, 1371, 1304, 1231, 1206, 1179, 1166, 1127, 1103, 1066, 1041, 1020, 946, 911, 871, 828,
769, 742, 729, 707, 698, 592, 559, 500, 438, 421. 1H NMR (400.13 MHz, CDCl3): δ = 2.30–2.37
(m, 4 H, CH2P), 2.91–2.98 (m, 4 H, CH2Ph), 3.27–3.30 (m, 4 H, CH2N), 3.88–3.90 (m, 4 H,
CH2O), 7.06–7.19 (m, 10 H, Ph), 8.40 (br. s, 2 H, HN). 13C NMR (100.61 MHz, CDCl3): δ = 30.5
(CH2Ph), 43.3 (CH2N), 43.6 (d, 1JCP = 42.1 Hz, CH2P), 64.0 (CH2O), 126.1 (p-CPh), 128.3 (o-
CPh), 128.5 (m-CPh), 141.2 (d, 3JCP = 16.5 Hz, i-CPh). 31P NMR (161.98 Hz, CDCl3): δ = 48.70
1
1
(s, JPSe = 558 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = −70 (d, JPSe = 558 Hz). Anal. Calcd
for C20H28NOPSSe: C, 54.54; H, 6.41; N, 3.18; P, 7.03; S, 7.28; Se, 17.93. Found: C, 54.46; H,
6.51; N, 3.04; P, 6.84; S, 7.19; Se, 18.03.
4.3.3. (2-Hydroxyethyl)ammonium bis(2-phenethyl)thioselenophosphinate (2c)
White powder; yield: 0.32 g (77%); m.p. 112–114 ◦C. IR (KBr, ν, cm−1): 3449, 3289, 3061,
3025, 2999, 2930, 2893, 1955, 1880, 1813, 1661, 1602, 1582, 1495, 1453, 1398, 1321, 1261,
1207, 1155, 1094, 1067, 1029, 1007, 945, 912, 846, 752, 699, 574, 508, 480, 415, 397. 1H NMR
(400.13 MHz, DMSO-d6): δ = 2.09–2.15 (m, 4 H, CH2P), 2.83–2.86 (m, 2 H, CH2N), 2.91–2.97
(m, 4 H, CH2Ph), 3.54–3.58 (m, 2 H, CH2O), 5.10 (br. s, 1 H, OH), 7.12–7.26 (m, 10 H, Ph),
7.64 (br. s, 3 H, HN). 13C NMR (100.61 MHz, DMSO-d6): δ = 30.7 (CH2Ph), 41.7 (CH2N), 45.6
(d, 1JCP = 42.7 Hz, CH2P), 57.9 (CH2O), 126.0 (p-CPh), 128.6 (o-CPh), 128.8 (m-CPh), 143.3 (d,
3JCP = 16.0 Hz, i-CPh). 31P NMR (161.98 Hz, DMSO-d6): δ = 48.93 (s, JPSe = 590 Hz). 77Se
1
NMR (76.31 Hz, DMSO-d6): δ = −55 (d, 1JPSe = 590 Hz). Anal. Calcd for C18H26NOPSSe: C,
52.17; H, 6.32; N, 3.38; P, 7.47; S, 7.74; Se, 19.05. Found: C, 51.58; H, 6.25; N, 3.27; P, 7.29; S,
7.69; Se, 19.12.
4.3.4. (R)-2-Hydroxybut-1-ylammonium bis(2-phenethyl)thioselenophosphinate (2d)
24
White powder; yield: 0.35 g (79%); >160 ◦C decomp.; [α]D = −6.94 (c 0.025, EtOH). IR (KBr,
ν, cm−1): 3422, 3192, 3055, 3024, 2967, 2927, 2593, 1804, 1749, 1601, 1580, 1494, 1474, 1453,
1374, 1323, 1260, 1245, 1213, 1192, 1155, 1122, 1055, 1036, 1022, 1000, 962, 947, 908, 837,
776, 761, 741, 715, 698, 594, 569, 557, 497, 439. 1H NMR (400.13 MHz, CDCl3): δ = 1.02 (t,
3JHH = 7.5 Hz, 3 H, Me), 1.69–1.90 (m, 2 H, CH2Me), 2.39–2.46 (m, 4 H, CH2P), 2.97–3.04
(m, 4 H, CH2Ph), 3.39–3.45 (m, 1 H, CHOH), 3.78–3.83 (m, 1 H, CH2N), 3.90–3.99 (m, 1 H,
CH2N), 6.45 (br. s, 4 H, HN, OH), 7.14–7.27 (m, 10 H, Ph). 13C NMR (100.61 MHz, CDCl3):
1
δ = 10.2 (Me), 23.0 (CH2Me), 30.4 (CH2Ph), 43.4 (d, JCP = 41.6 Hz, CH2P), 55.7 (CH2N),
3
60.8 (CHOH), 126.1 (p-CPh), 128.3 (o-CPh), 128.5 (m-CPh), 141.2 (d, JCP = 16.4 Hz, i-CPh).
31P NMR (161.98 MHz, CDCl3): δ = 48.52 (s, 1JPSe = 557 Hz). 77Se NMR (76.31 Hz, CDCl3):
1
δ = −60 (d, JPSe = 557 Hz). Anal. Calcd for C20H30NOPSSe: C, 54.29; H, 6.83; N, 3.17; P,
7.00; S, 7.25; Se, 17.85. Found: C, 54.20; H, 6.77; N, 3.08; P, 7.13; S, 7.06; Se, 17.80.

Journal of Sulfur Chemistry 607
4.3.5. Anilinium bis(2-phenethyl)thioselenophosphinate (2e)
White powder; yield: 0.38 g (85%); m.p. 115–117 ◦C. IR (KBr, ν, cm−1): 3546, 3476, 3415, 3104,
3083, 3057, 3024, 2924, 2901, 2843, 1602, 1536, 1514, 1494, 1452, 1434, 1396, 1205, 1140, 1024,
1
941, 893, 829, 756, 739, 729, 709, 700, 687, 588, 573, 553, 526, 499, 476, 467, 431. H NMR
(400.13 MHz, CDCl3): δ = 2.42–2.51 (m, 4 H, CH2P), 2.95–3.05 (m, 4 H, CH2Ph), 5.90 (br. s,
3 H, HN), 7.13–7.35 (m, 15 H, Ph). 13C NMR (100.61 MHz, CDCl3): δ = 30.0 (CH2Ph), 42.4
(d, 1JCP = 38.9 Hz, CH2P), 122.1 (o-CPh), 126.1 and 127.3 (p-C, Ph), 128.2 (o-CPh), 128.4 and
3
129.9 (m-CPh), 140.7 (i-CPh), 140.8 (d, JCP = 17.7 Hz, i-CPh). 31P NMR (161.98 Hz, CDCl3):
δ = 50.35 (br. s). 77Se NMR (76.31 Hz, CDCl3): δ = −60 (d, 1JPSe = 595 Hz). Anal. Calcd for
C22H26NPSSe: C, 59.19; H, 5.87; N, 3.14; P, 6.94; S, 7.18; Se, 17.69. Found: C, 59.07; H, 5.76;
N, 3.20; P, 6.71; S, 7.12; Se, 17.52.
4.3.6. Diethylammonium bis[2-(4-methoxyphenyl)ethyl)]thioselenophosphinate (2f)
White powder; yield: 0.43 g (88%); m.p. 199–201 ◦C. IR (KBr, ν, cm−1): 2978, 2952, 2937, 2884,
2835, 2800, 2719, 1611, 1582, 1513, 1463, 1444, 1403, 1385, 1372, 1301, 1247, 1176, 1160, 1128,
1063, 1036, 1013, 949, 933, 872, 818, 786, 769, 754, 728, 577, 550, 528, 466, 449, 424. 1H NMR
3
(400.13 MHz, CDCl3): δ = 1.49 (t, 6 H, JHH = 7.3 Hz, MeCH2), 2.35–2.42 (m, 4 H, CH2P),
2.98–3.04 (m, 4 H, CH2Ar), 3.13–3.18 (m, 4 H, CH2N), 3.76 (s, 6 H, MeO), 6.80, and 7.13 (m,
8 H, Ar), 7.25 (s, 2 H, HN). 13C NMR (100.61 Hz, CDCl3): δ = 12.3 (MeCH2), 30.28 (CH2Ar),
1
42.1 (CH2N), 45.1 (d, JCP = 42.6 Hz, CH2P), 56.1 (MeO), 114.7 (C2Ar, C6Ar), 130.2 (C3Ar,
C5Ar), 134.7 (d, 3JCP = 17.2 Hz, C1Ar), 158.8 (C4Ar). 31P NMR (161.98 Hz, CDCl3): δ = 48.41
1
1
(s, JPSe = 576 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = −84 (d, JPSe = 576 Hz). Anal. Calcd
for C22H34NO2PSSe: C, 54.31; H, 7.04; N, 2.88; P, 6.37; S, 6.59; Se, 16.23. Found: C, 54.46; H,
7.19; N, 2.72; P, 6.24; S, 6.42; Se, 16.35.
4.3.7. Dipropylammonium bis[(4-tert-butyl)phenethyl]thioselenophosphinate (2g)
White powder; yield: 0.44 g (78%); m.p. 202–204 ◦C. IR (KBr, ν, cm−1): 3436, 3023, 2964, 2936,
2876, 2775, 2515, 1901, 1790, 1634, 1574, 1517, 1466, 1458, 1401, 1393, 1364, 1331, 1293, 1268,
1202, 1192, 1133, 1108, 1069, 1046, 1019, 951, 850, 837, 815, 767, 756, 730, 667, 579, 559, 518,
499, 456, 407. 1H NMR (400.13 MHz, CDCl3): δ = 1.08 (t, 3JHH = 7.5 Hz, 6 H, MeCH2), 1.31 (s,
18 H, Me3C), 1.92–1.98 (m, 4 H, CH2Me), 2.40–2.47 (m, 4 H, CH2P), 3.01–3.10 (m, 8 H, CH2Ar,
CH2N), 7.18–7.32 (m, 8 H, Ar), 8.56 (s, 2 H, HN). 13C NMR (100.61 MHz, CDCl3): δ = 11.6
1
(MeCH2), 19.7 (CH2Me), 29.9 (CH2Ar), 31.6 (Me3C), 34.6 (CMe3), 44.1 (d, JCP = 42.7 Hz,
CH2P), 48.3 (CH2N), 125.5 (C2Ar, C6Ar), 128.3 (C3Ar, C5Ar), 139.0 (d, 3JCP = 17.2 Hz, C1Ar),
148.9 (C4Ar). 31P NMR (161.98 Hz, CDCl3): δ = 48.10 (s, 1JPSe = 576 Hz). 77Se NMR (76.31 Hz,
CDCl3): δ = −82 (d, 1JPSe = 576 Hz). Anal. Calcd for C30H50NPSSe: C, 63.58; H, 8.89; N, 2.47;
P, 5.47; S, 5.66; Se, 13.93. Found: C, 63.64; H, 8.97; N, 2.33; P, 5.27; S, 5.51; Se, 14.01.
4.3.8. Allylammonium bis[2-(pyrid-2-yl)ethyl]thioselenophosphinate (2h)
White powder; yield: 0.34 g (82%); m.p. 87–89 ◦C. IR (KBr, ν, cm−1): 3354, 3006, 2925, 2618,
2104, 1671, 1646, 1593, 1568, 1474, 1435, 1403, 1310, 1267, 1223, 1194, 1150, 1125, 1083, 1052,
993, 944, 890, 850, 759, 633, 602, 570, 507, 441. 1H NMR (400.13 MHz, CDCl3): δ = 2.49–2.55
3
(m, 4 H, CH2P), 3.26–3.32 (m, 4 H, CH2Py), 3.84 (d, JHH = 5.9 Hz, 2 H, CH2N), 5.38 (d,
3
3
=
=
=
JHH = 10.4 Hz, 1 H, CH2), 5.47 (d, JHH = 17.1 Hz, 1 H, CH2), 6.09–6.19 (m, 1 H, CH),
7.13 (t, 3JHH = 5.8 Hz, 2 H, Py), 7.22 (d, 3JHH = 7.7 Hz, 2 H, Py), 7.62 (t, 3JHH = 7.3 Hz, 2 H,

608 A.V. Artem’ev et al.
3
Py), 8.46 (d, JHH = 4.1 Hz, 2 H, Py), 8.71 (br. s, 3 H, HN). 13C NMR (100.61 MHz, CDCl3):
δ = 32.4 (CH2Py), 41.7 (CH2N), 42.7 (d, 1JCP = 43.6 Hz, CH2P), 121.4 ( CH2, C-5 in Py), 123.4
=
3
(C3Py), 130.1 ( CH), 137.1 (C4Py), 148.6 (C6Py), 161.4 (d, JCP = 17.0 Hz, C2Py). 31P NMR
=
(161.98 MHz, CDCl3): δ = 49.48 (s, 1JPSe = 580 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = −76
(d, 1JPSe = 580 Hz). Anal. Calcd for C17H24N3PSSe: C, 49.51; H, 5.87; N, 10.19; P, 7.51; S, 7.78;
Se, 19.15. Found: C, 49.60; H, 5.75; N, 10.01; P, 7.34; S, 7.87; Se, 19.21.
4.3.9. Diethylammonium bis[2-(pyrid-2-yl)ethyl]thioselenophosphinate (2i)
White powder; yield: 0.33 g (77%); m.p. 109–110 ◦C. IR (KBr, ν, cm−1): 3497, 2976, 2882,
2717, 2495, 1631, 1585, 1567, 1471, 1432, 1404, 1384, 1333, 1308, 1268, 1217, 1186, 1160,
1148, 1120, 1063, 1046, 1007, 992, 948, 883, 849, 758, 628, 590, 570, 562, 498, 431. 1H NMR
(400.13 MHz, CDCl3): δ = 1.18 (t, 3JHH = 7.3 Hz, 6 H, Me), 2.54–2.61 (m, 4 H, CH2P), 3.19–
3.24 (m, 4 H, CH2N), 3.26–3.33 (m, 4 H, CH2Py), 7.07–7.10 (t, 3JHH = 5.8 Hz, 2 H, Py), 7.22 (d,
3JHH = 7.7 Hz, 2 H, Py), 7.62 (t, 3JHH = 7.3 Hz, 2 H, Py), 8.46 (d, 3JHH = 4.1 Hz, 2 H, Py), 9.34
(br. s, 2 H, HN). 13C NMR (100.61 MHz, CDCl3): δ = 11.4 (Me), 32.7 (CH2Py), 41.8 (CH2N),
43.8 (d, 1JCP = 44.3 Hz, CH2P), 121.1 (C5Py), 123.0 (C3Py), 136.5 (C4Py), 148.8 (C6Py), 161.5
(d, 3JCP = 17.7 Hz, C2Py). 31P NMR (161.98 MHz, CDCl3): δ = 49.06 (s, 1JPSe = 578 Hz). 77Se
NMR (76.31 Hz, CDCl3): δ = −71 (d, 1JPSe = 578 Hz).Anal. Calcd for C18H28N3PSSe: C, 50.46;
H, 6.59; N, 9.81; P, 7.23; S, 7.48; Se, 18.43. Found: C, 50.38; H, 6.46; N, 9.71; P, 7.09; S, 7.34;
Se, 18.47.
4.3.10. Allylammonium bis[2-(2-methylpyrid-5-yl)ethyl]thioselenophosphinate (2j)
White powder; yield: 0.37 g (84%); m.p. 79–82 ◦C. IR (KBr, ν, cm−1): 3432, 2922, 1603, 1568,
1491, 1445, 1391, 1298, 1244, 1197, 1136, 1035, 991, 940, 855, 826, 775, 722, 652, 584, 540,
1
490, 410. H NMR (400.13 MHz, CDCl3): δ = 2.33–2.40 (m, 4 H, CH2P), 2.49 (s, 6 H, Me),
3
3
3.00–3.07 (m, 4 H, CH2Py), 3.80 (d, JHH = 5.9 Hz, 2 H, CH2N), 5.35 (d, JHH = 10.3 Hz, 1
3
=
=
=
H, CH2), 5.47 (d, JHH = 17.0 Hz, 1 H, CH2), 6.02–6.11 (m, 1 H, CH), 7.04 (d, 2 H, Py),
7.45 (d, 2 H, Py), 8.41 (br. s, 5 H, Py, HN). 13C NMR (100.61 MHz, CDCl3): δ = 23.6 (Me),
27.2 (CH2Py), 41.8 (CH2N), 43.5 (d, 1JCP = 42.9 Hz, CH2P), 121.4 ( CH2), 123.5 (C3Py), 130.0
=
(HC ), 134.7 (d, JCP = 17.0 Hz, C5Py), 137.3 (C4Py), 148.2 (C6Py), 155.2 (C2Py). 31P NMR
3
=
(161.98 MHz, CDCl3): δ = 48.18 (s, 1JPSe = 575 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = −65
(d, 1JPSe = 575 Hz). Anal. Calcd for C19H28N3PSSe: C, 51.81; H, 6.41; N, 9.54; P, 7.03; S, 7.28;
Se, 17.93. Found: C, 51.72; H, 6.33; N, 9.37; P, 6.89; S, 7.20; Se, 17.76.
4.3.11. Diethylammonium bis[2-(2-methylpyrid-5-yl)ethyl]thioselenophosphinate (2k)
White powder; yield: 0.40 g (88%); m.p. 112–114 ◦C. IR (KBr, ν, cm−1): 3459, 3001, 2950, 2787,
2717, 1600, 1567, 1492, 1446, 1396, 1385, 1305, 1277, 1247, 1195, 1160, 1145, 1064, 1030, 936,
850, 829, 778, 747, 723, 704, 645, 609, 584, 544, 532, 491, 440. 1H NMR (400.13 MHz, CDCl3):
3
δ = 1.14 (t, JHH = 7.3 Hz, 6 H, MeCH2), 2.30–2.37 (m, 4 H, CH2P), 2.44 (s, 6 H, MePy),
3.01–3.09 (m, 4 H, CH2Py), 3.14–3.20 (m, 4 H, CH2N), 7.02 (d, 2 H, Py), 7.47 (d, 2 H, Py),
8.43 (br. s, 5 H, Py, HN). 13C NMR (100.61 MHz, CDCl3): δ = 11.9 (MeCH2), 23.7 (MePy), 27.3
(CH2Py), 42.0 (CH2N), 43.3 (d, 1JCP = 42.5 Hz, CH2P), 123.4 (C3Py), 134.7 (d, 3JCP = 17.1 Hz,
C5Py), 137.2 (C4Py), 148.1 (C6Py), 155.2 (C2Py). 31P NMR (161.98 MHz, CDCl3): δ = 48.11 (s,
1
1JPSe = 577 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = −68 (d, JPSe = 577 Hz). Anal. Calcd for
C20H32N3PSSe: C, 52.62; H, 7.07; N, 9.21; P, 6.79; S, 7.02; Se, 17.30. Found: C, 52.55; H, 7.01;
N, 9.12; P, 6.67; S, 7.19; Se, 17.22.

Journal of Sulfur Chemistry 609
4.3.12. Dibenzylammonium bis[2-(2-furyl)ethyl]thioselenophosphinate (2l)
White powder; yield: 0.46 g (87%); m.p. 145–148 ◦C. IR (KBr, ν, cm−1): 3449, 3034, 2975, 2856,
2746, 2691, 2588, 2397, 1951, 1597, 1505, 1458, 1446, 1416, 1330, 1284, 1227, 1213, 1169, 1145,
1073, 1031, 1003, 956, 937, 910, 883, 842, 793, 756, 727, 692, 640, 598, 571, 482, 460, 444.
1H NMR (400.13 MHz, CDCl3): δ = 2.42–2.49 (m, 4 H, CH2P), 3.06–3.12 (m, 4 H, CH2Fur),
4.11 (s, 4 H, CH2N), 6.03, 6.27 and 7.29 (m, 6 H, Fur), 7.40–7.51 (m, 10 H, Ph), 9.98 (br. s, 2
H, HN). 13C NMR (100.61 MHz, CDCl3): δ = 23.0 (CH2Fur), 39.9 (d, 1JCP = 44.7 Hz, CH2P),
47.6 (CH2N), 105.1 (C3Fur), 110.2 (C4Fur), 129.5, 129.8 and 130.0 (Ph), 141.0 (C5Fur), 155.2
(d, 3JCP = 19.9 Hz, C2Fur). 31P NMR (161.98 MHz, CDCl3): δ = 48.54 (s, 1JPSe = 560 Hz). 77Se
NMR (76.31 MHz, CDCl3): δ = −55 (d, 1JPSe = 560 Hz). Anal. Calcd for C26H30NO2PSSe: C,
58.86; H, 5.70; N, 2.64; P, 5.84; S, 6.04; Se, 14.88. Found: C, 58.91; H, 5.76; N, 2.55; P, 5.72; S,
6.12; Se, 14.79.
4.3.13. Dibutylammonium diphenylthioselenophosphinate (2m)
White powder; yield: 0.35 g (82%); m.p. 192–194 ◦C. IR (KBr, ν, cm−1): 3490, 2968, 2848,
1813, 1674, 1571, 1537, 1477, 1453, 1434, 1391, 1333, 1303, 1271, 1179, 1152, 1130, 1093,
1068, 1026, 998, 974, 935, 890, 873, 801, 780, 750, 694, 649, 627, 608, 599, 562, 543, 522, 483,
456, 436. 1H NMR (400.13 MHz, CDCl3): δ = 0.98 (t, 3JHH = 7.4 Hz, 6 H, Me), 1.40–1.45 (m, 4
H, CH2Me), 1.67–1.80 (m, 4 H, CH2Et), 3.09–3.20 (m, 4 H, CH2N), 6.87–6.95 and 7.68–7.73 (m,
10 H, Ph), 10.14 (s, 2 H, HN). 13C NMR (100.61 Hz, CDCl3): δ = 10.2 (Me), 17.2 (CH2Me), 26.8
(CH2Et), 54.6 (CH2N), 127.3 (d, 2JCP = 12.9 Hz, i-CPh), 129.2 (d, 4JCP = 2.0 Hz, p-CPh), 130.7
(d, 3JCP = 11.8 Hz, M-CPh), 142.0 (d, 1JCP = 72.0 Hz, i-CPh). 31P NMR (161.98 MHz, CDCl3):
δ = 44.53 (s, 1JPSe = 602 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = 0 (d, 1JPSe = 602 Hz).Anal.
Calcd for C20H30NPSSe: C, 56.33; H, 7.09; N, 3.28; P, 7.26; S, 7.52; Se, 18.52. Found: C, 56.25;
H, 7.14; N, 3.40; P, 7.19; S, 7.44; Se, 18.50.
4.3.14. Triethylammonium diphenylthioselenophosphinate (2n)
White powder; yield: 0.34 g (85%); m.p. 201–205 ◦C. IR (KBr, ν, cm−1): 3064, 3043, 2972, 2938,
2806, 2788, 2745, 2652, 2512, 2480, 1639, 1468, 1455, 1437, 1387, 1306, 1285, 1172, 1159, 1089,
1067, 1054, 1028, 1011, 997, 980, 896, 837, 804, 788, 770, 757, 698, 631, 603, 525, 481, 420. 1H
NMR (400.13 MHz, CDCl3): δ = 1.29 (t, 3JHH = 7.4 Hz, 9 H, Me), 3.21–3.27 (m, 6 H, CH2N),
7.25–7.31 and 8.10–8.15 (m, 10 H, Ph), 10.06 (s, 1 H, HN). 13C NMR (100.61 Hz, CDCl3): δ = 8.3
2
4
(Me), 45.7 (CH2N), 127.3 (d, JCP = 12.5 Hz, i-CPh), 129.1 (d, JCP = 2.7 Hz, p-CPh), 130.6
3
1
(d, JCP = 11.4 Hz, M-CPh), 142.7 (d, JCP = 70.9 Hz, i-CPh). 31P NMR (161.98 Hz, CDCl3):
δ = 44.43 (s, 1JPSe = 606 Hz). 77Se NMR (76.31 Hz, CDCl3): δ = 1.9 (d, 1JPSe = 606 Hz). Anal.
Calcd for C18H26NPSSe: C, 54.26; H, 6.58; N, 3.52; P, 7.77; S, 8.05; Se, 19.82. Found: C, 54.35;
H, 6.61; N, 3.69; P, 7.60; S, 7.91; Se, 19.90.
4.4. Synthesis of zwitterionic thioselenophosphinate 2o
The powdered gray selenium (0.079 g, 1.0 mmol) was added to a solution of secondary phosphine
sulfide 1e (1.0 mmol) in dioxane (10 ml) at room temperature. The suspension was stirred at
90–95 ◦C until dissolution of selenium (∼1 h) to give a transparent solution. The solvents were
removed under reduced pressure and the residue was washed with ether (2 × 10 ml) and dried in
vacuo (1Torr, 45 ◦C) to afford the zwitterionic thioselenophosphinate 2o.

610 A.V. Artem’ev et al.
4.4.1. 2-(2-methylpyrid-5-yl)ethyl[2-(2-methylpyrid-inium-5-yl)ethyl]thio- selenophosphinate
(2o)
White powder, yield: 0.32 g (84%); m.p. 201–205 ◦C with decomp. IR (KBr, ν, cm−1): 3444,
3096, 3029, 3006, 2919, 2855, 1639, 1601, 1568, 1491, 1445, 1402, 1334, 1300, 1247, 1213,
1197, 1147, 1029, 1017, 969, 952, 930, 910, 865, 836, 789, 764, 755, 739, 729, 714, 646, 616,
562, 542, 489, 411. 1H NMR (400.13 MHz, DMSO-d6): δ = 2.35–2.41 (m, 4 H, CH2P), 2.41 (s, 6
H, MePy), 3.10–3.19 (m, 4 H, CH2Py), 7.11 (d, 2 H, Py), 7.61 (d, 2 H, Py), 8.54 (br. s, 3 H, Py, HN).
1
13C NMR (100.61 MHz, DMSO-d6): δ = 24.1(MePy), 27.9 (CH2Py), 43.4 (d, JCP = 41.5 Hz,
CH2P), 123.1 (C3Py), 135.1 (d, 3JCP = 17.0 Hz, C5Py), 137.3 (C4Py), 149.1 (C6Py), 155.4 (C2Py).
31P NMR (161.98 Hz, DMSO-d6): δ = 49.01 (s, 1JPSe = 577 Hz). 77Se NMR (76.31 Hz, DMSO-
d6): δ = −76 (d, 1JPSe = 577 Hz). Anal. Calcd for C16H21N2PSSe: C, 50.13; H, 5.52; N, 7.31; P,
8.08; S, 8.36; Se, 20.60. Found: C, 50.17; H, 5.66; N, 7.35; P, 7.95; S, 8.42; Se, 20.48.
Acknowledgement
This work was supported by the Russian Foundation for Basic Research (grant no. 11-03-92003-HHC_a) and the President
of the Russian Federation [programs for the support of leading scientific schools (grant NSh-3230.2010.3) and young
Russian scientists (grant MK-629-2010.3)].
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