Green synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst-and solvent-free addition of secondary phosphine chalcogenides to vinyl selenides

Article abstract of DOI:10.1080/17415993.2015.1066375

Secondary phosphine sulfides and phosphine selenides react with vinyl selenides under mild conditions (80-82°C, without catalyst and solvent) to form regioselectively functionalized anti-Markovnikov adducts in high yield.

Full text of DOI:10.1080/17415993.2015.1066375

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Green synthesis of tertiary
alkylselanylphosphine chalcogenides
via catalyst- and solvent-free addition
of secondary phosphine chalcogenides
to vinyl selenides
N.K. Gusarovaa, N.A. Chernyshevaa, S.V. Yas'koa & B.A. Trofimova
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of
the Russian Academy of Sciences, Irkutsk, Russian Federation
Published online: 24 Jul 2015.
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To cite this article: N.K. Gusarova, N.A. Chernysheva, S.V. Yas'ko & B.A. Trofimov (2015): Green
synthesis of tertiary alkylselanylphosphine chalcogenides via catalyst- and solvent-free addition
of secondary phosphine chalcogenides to vinyl selenides, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2015.1066375
To link to this article: http://dx.doi.org/10.1080/17415993.2015.1066375
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Journal of Sulfur Chemistry, 2015
http://dx.doi.org/10.1080/17415993.2015.1066375
Green synthesis of tertiary alkylselanylphosphine chalcogenides
via catalyst- and solvent-free addition of secondary phosphine
chalcogenides to vinyl selenides
N.K. Gusarova, N.A. Chernysheva, S.V. Yas’ko and B.A. Trofimov∗,
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Irkutsk,
Russian Federation
(Received 8 June 2015; accepted 23 June 2015)
Secondary phosphine sulfides and phosphine selenides react with vinyl selenides under mild conditions
(80–82°C, without catalyst and solvent) to form regioselectively functionalized anti-Markovnikov adducts
in high yield.
Keywords: secondary phosphine chalcogenides; vinyl selenides; addition reaction; synthesis; alkylse-
lanylethylphosphine chalcogenides
1. Introduction
Addition of phosphines and phosphine chalcogenides to the double carbon–carbon bond rep-
resents a convenient and atom-economic approach to the C–P bond formation and synthesis
of phosphines and phosphine chalcogenides including functionalized ones.[1–9] As a rule,
these reactions proceed in the presence of catalysts (bases,[2,10] radical initiators [1–3,5,11]
or metallocomplexes [4,6–8]) and in organic solvents.
In recent years, catalyst- and solvent-free reactions attract particular attention. This is espe-
cially important in view of modern requirements of green chemistry. For example, it has
been shown that secondary phosphines [12] and phosphine chalcogenides [13,14] react with
diverse alkenes under catalyst- and solvent-free conditions to afford anti-Markovnikov adducts.
Mechanism of these reactions still remains obscure.
To expand the synthetic scope of new environmentally benign methods for the prepa-
*Corresponding author. Email: boris_trofimov@irioch.irk.ru
© 2015 Taylor & Francis

2
N.K. Gusarova et al.
ration of functionalized phosphine chalcogenides and to gain a better understanding of the
catalyst- and solvent-free C–P bond formation from PH-addends and alkenes, we have studied
here the reaction of secondary phosphine sulfides and phosphine selenides with available alkyl
vinyl selenides, easily obtained from acetylene, elemental selenium and alkyl bromides.[15,16]
2. Results and discussion
Earlier we have reported that secondary phosphine sulfides and selenides add to alkyl vinyl
selenides under radical initiation (AIBN, 65–70°C or UV-irradiation) in dioxane to give tertiary
alkylselanylphosphine chalcogenides.[17]
We have found that the reaction can also be successfully accomplished without catalyst and
solvent. The process is realized upon heating (80–82°C) of equimolar amounts of the initial
secondary phosphine chalcogenides 1–4 and alkyl vinyl selenides 5, 6 to regioselectively afford
anti-Markovnikov adducts 7a–h in 82–95% yields (Table 1).
The secondary phosphine oxides are found to be inactive in this reaction: no formation of the
tertiary phosphine oxide is observed after heating a mixture of bis(2-phenethyl)phosphine oxide
with vinyl selenide 5 at 80°C for 30 h.
Table 1. Synthesis of alkylselanylphosphine chalcogenides 7a–h under catalyst- and solvent-free conditions.a
NMR
Isolated
Entry Phosphine chalcogenide
1
Vinyl selenide
Time (h)
31
Product (7)
yield (%) yield (%)
98
96
89
5
a
1
2b
30
20
90
5
5
2
b
3
99
94
3
c
(Continued).

Journal of Sulfur Chemistry
3
Table 1. Continued
NMR
Isolated
Entry Phosphine chalcogenide
4b
Vinyl selenide
Time (h)
23
Product (7)
yield (%) yield (%)
94
86
5
4
d
5
30
23
30
98
92
99
90
82
95
6
6
6
1
e
f
6b
2
7
3
g
8b
29
30
92
98
88
93
6
5
4
h
b
9c
2
10d
30
30
98
98
92
92
5
5
2
b
b
11e
2
aStandard reaction condition: molar ratio phosphine chalcogenide/vinyl selenide = 1:1, 80–82°C, argon.
bThe reaction of secondary phosphine chalcogenides with vinyl selenides also gives Markovnikov adducts in trace amounts (1H and 31
NMR data).
P
cExperiment was carried out in the presence of hydroquinone (10 mol%).
dExperiment was carried out in the presence of TEMPO (5 mol%).
eExperiment was carried out in dark.

4
N.K. Gusarova et al.
Scheme 1. A tentative mechanism for the formation of alkylselanylphosphine chalcogenides.
It should be emphasized that the radical scavengers (hydroquinone or TEMPO) do not inhibit
the addition of phosphine selenide 2 to vinyl selenide 5 (Table 1, entries 9, 10). Moreover, in
the dark, this reaction proceeds with the same efficiency as in the light (Table 1, entries 2, 11).
Consequently, the radical chain mechanism is improbable for the studied reaction. It may be
assumed that in this case, the non-catalyzed addition of secondary phosphine chalcogenides to
vinyl selenides proceeds according to the molecular mechanism via four- or six-membered peri-
cyclic transition states A or B followed by concerted transfer electron pairs (or in a single electron
transfer mode) without preliminary formation of ions or radicals (Scheme 1). A driving force for
such a concerted cyclic electron transfer would be a partial positive charge on the tetracoordi-
nated phosphorus atom of phosphine chalcogenides, from one hand, and partial negative charge
on the beta-carbon of vinyl group, on the other hand.
As seen from Scheme 1, the reaction studied should be more readily realized for secondary
phosphine sulfides and phosphine selenides than for phosphine oxides.
3. Conclusion
The environmentally attractive synthesis of tertiary alkylselanylphosphine sulfides and selenides
has been elaborated via the regioselective addition of secondary phosphine chalcogenides to
alkyl vinyl selenides under catalyst- and solvent-free conditions.
The synthesized products are prospective ligands for the design of metal complex
catalysts,[18–23] precursors of pharmaceutically compounds [24,25] as well as they can be fur-
ther used for fabrication of nanosized metal selenide nanoparticles.[26–32] The described results
complement substantially the known non-catalyzed methods of the C–P bonds formation by the
reaction of PH-addends with alkenes.
4. Experimental
4.1. General
The C, H microanalyses were performed on a Flash EA 1112 HNS-O/MAS analyzer, while the
P and Se contents were determined by the combustion method. IR spectra were run on a Bruker
Vertex 70 instrument. The 1H, 13C, 31P and 77Se NMR spectra were recorded on a Bruker DPX
400 and Bruker AV-400 spectrometer (400.13, 100.61, 161.98 and 76.31 MHz, respectively).
Eighty-five percent of H3PO4/H2O was employed as the external standard for 31P NMR, HMDS
was used for 1H, 13C NMR and Me2Se was the external standard for 77Se NMR. Melting points
(uncorrected) were measured on a Kofler micro hot-stage apparatus.

Journal of Sulfur Chemistry
5
All steps of the experiment were carried out in argon atmosphere. Vinyl selenides 5, 6
were readily prepared from elemental selenium, acetylene and alkyl bromides according to
the published procedure.[15,16] Secondary phosphine chalcogenides 1–2 were synthesized
by oxidation of the corresponding phosphines with powdered sulfur or selenium. The initial
phosphine was prepared from red phosphorus and styrene as described in the literature.[33]
Diphenylphosphine sulfide and selenide 3–4 were prepared by oxidation of commercially
available diphenylphosphine (Aldrich) with elemental sulfur or selenium.
4.2. General procedure for the synthesis of tertiary alkylselanylphosphine chalcogenides
7a–h
A mixture of secondary phosphine chalcogenide 1–4 (1.0 mmol) and vinyl selenide 5–6 (1.0
mmol) was stirred at 80–82°C for 20–30 h (depends on reactants structure) under argon atmo-
sphere. The reaction was monitored by 31P NMR following the disappearance of the signal of
the starting phosphine chalcogenide (δP = 3–23 ppm) and simultaneous appearance of a new
signal at 33–49 ppm, corresponding to tertiary phosphine chalcogenide 7a–h. After complete
reaction, the crude product was purified by flash chromatography (neutral alumina, hexane/Et2O
1:1 mixture as eluent) to give compounds 7a–h in 82–95% yields (see Table 1).
4.2.1. 2-(Pentylselanyl)ethyl(diphenethyl)phosphine sulfide (7a)
1
Colorless oil; yield: 0.40 g (89%). H NMR (400.13 MHz, CDCl3): δ = 0.93 (m, 3 H, CH3),
1.36 (m, 4 H, CH2CH2CH3), 1.69 (m, 2 H, CH2C3H7), 2.19 (m, 6 H, CH2P), 2.60 (m, 2 H,
CH2C4H9), 2.77 (m, 2 H, PCH2CH2Se), 2.97 (m, 4 H, PhCH2), 7.21 (m, 4 H, Ho, Ph), 7.24
(m, 2 H, Hp, Ph), 7.32 (m, 4 H, Hm, Ph). 13C NMR (100.61 MHz, CDCl3): δ = 13.8 (CH3),
2
2
15.3 (d, JPC = 3.3 Hz, PCH2CH2Se), 22.0 (CH2CH3), 24.4 (CH2C4H9), 29.3 (d, JPC = 2.2
1
Hz, CH2Ph), 30.0 (CH2C3H7), 31.8 (CH2C2H5), 32.1 (d, JPC = 36.1 Hz, PCH2CH2Se), 32.4
1
(d, JPC = 40.9 Hz, CH2CH2Ph), 126.3 (Cp, Ph), 128.2 (Co, Ph), 128.6 (Cm, Ph), 140.1 (d,
3JPC = 13.6 Hz, Ci, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 48.98. 77Se NMR (76.31 MHz,
CDCl3): δ = 208.2 (d, JPSe = 8.6 Hz). IR (neat, cm−1): 3084, 3061, 3026, 3000 (ν = CH of
3
=
phenyl rings), 2955, 2925, 2867, 2856 (ν CH), 1602, 1584, 1496 (ν C C of phenyl rings), 1453,
1406 (δ CH2), 1379 (δ CH3), 1332, 1295, 1268, 1244, 1211, 1199, 1174, 1135, 1103, 1092, 1072,
1029, 1008, 948, 908, 893, 857, sh 771 (δ CH of phenyl rings), 752 (ν P–C), 698 (δ CH of phenyl
=
rings), sh 612, 598 (ν P S). Anal. Calcd for C23H33PSSe: C, 61.18; H, 7.37; P, 6.86; S, 7.10; Se,
17.49. Found: C, 60.96; H, 7.12; P, 7.05; S, 7.21; Se, 17.64%.
4.2.2. 2-(Pentylselanyl)ethyl(diphenethyl)phosphine selenide (7b)
Light yellow oil; yield: 0.45 g (90%). 1H NMR (400.13 MHz, CDCl3): δ = 0.90 (m, 3 H, CH3),
1.35 (m, 4 H, CH2CH2CH3), 1.66 (m, 2 H, CH2C3H7), 2.27 (m, 6 H, CH2P), 2.58 (m, 2 H,
CH2C4H9), 2.74 (m, 2 H, PCH2CH2Se), 2.94 (m, 4 H, PhCH2), 7.20 (m, 4 H, Ho, Ph), 7.24
(m, 2 H, Hp, Ph), 7.30 (m, 4 H, Hm, Ph). 13C NMR (100.61 MHz, CDCl3): δ = 14.1 (CH3),
2
2
15.6 (d, JPC = 4.8 Hz, PCH2CH2Se), 22.3 (CH2CH3), 24.6 (CH2C4H9), 29.4 (d, JPC = 3.0
1
Hz, CH2Ph), 30.1 (CH2C3H7), 32.1 (CH2C2H5), 32.3 (d, JPC = 36.1 Hz, PCH2CH2Se), 32.5
1
(d, JPC = 40.2 Hz, CH2CH2Ph), 126.7 (Cp, Ph), 128.2 (Co, Ph), 128.8 (Cm, Ph), 140.2 (d,
3JPC = 13.6 Hz, Ci, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 38.04 (1JP
= 702.2 Hz).
=
Se
77Se NMR (76.31 MHz, CDCl3): δ = −386.6 (d, JP
= 704.7 Hz), 208.3 (d, JPSe = 9.5
1
3
=
Se
Hz). IR (neat, cm−1): 3084, 3061, 3026, 3001 (ν = CH of phenyl rings), 2955, 2925, 2867, 2856
=
(ν CH), 1603, 1584, 1496 (ν C C of phenyl rings), 1453, 1406 (δ CH2), 1378 (δ CH3), 1332,

6
N.K. Gusarova et al.
1295, 1268, 1244, 1214, 1200, 1173, 1135, 1105, 1071, 1030, 1007, 948, 909, 859, 844, 806,
=
752 (ν P–C), 699 (δ CH of phenyl rings), sh 573, 555 (ν P Se). Anal. Calcd for C23H33PSe2: C,
55.43; H, 6.67; P, 6.21; Se, 31.69. Found: C, 55.62; H, 6.74; P, 6.18; Se, 31.43%.
4.2.3. 2-(Pentylselanyl)ethyl(diphenyl)phosphine sulfide (7c)
Light yellow oil, yield: 0.37 g (94%). 1H NMR (400.13 MHz, CDCl3): δ = 0.87 (m, 3 H, CH3),
1.29 (m, 4 H, CH2CH2CH3), 1.59 (m, 2 H, CH2C3H7), 2.55 (m, 2 H, CH2C4H9), 2.74 (m,
4 H, SeCH2CH2P), 7.46 (m, 6 H, Ph), 7.81 (m, 4 H, Ph). 13C NMR (100.61 MHz, CDCl3):
δ = 13.7 (CH3), 14.5 (d, 2JPC = 3.3 Hz, PCH2CH2Se), 22.1 (CH2CH3), 24.3 (CH2C4H9), 29.9
1
2
(CH2C3H7), 31.8 (CH2C2H5), 34.3 (d, JPC = 49.0 Hz, CH2P), 128.5 (d, JPC = 11.8 Hz, Co,
Ph), 130.7 (d, 3JPC = 10.0 Hz, Cm, Ph), 131.4 (d, 4JPC = 3.0 Hz, Cp, Ph), 132.1 (d, 1JPC = 78.9
Hz, Ci, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 42.53. 77Se NMR (76.31 MHz, CDCl3):
3
δ = 205.9 (d, JPSe = 13.2 Hz). IR (neat, cm−1): 3074, 3053 (ν = CH of phenyl rings), 2955,
=
2926, 2867, 2855 (ν CH), 1586, 1574, 1480 (ν C C of phenyl rings), 1464, 1436, (δ CH2),
1379 (δ CH3), 1334, 1309, 1260, 1243, 1168, 1104, 1070, 1027, 1016, 998, 884, sh 770 (δ CH
=
of phenyl rings), 751 (ν P–C), 741, 724, 711, 692 (δ CH of phenyl rings), sh 620, 609 (ν P S).
Anal. Calcd for C19H25PSSe: C, 57.71; H, 6.37; P, 7.83; S, 8.11; Se, 19.97. Found: C, 57.91; H,
6.15; P, 7.80; S, 8.38; Se, 19.75%.
4.2.4. 2-(Pentylselanyl)ethyl(diphenyl)phosphine selenide (7d)
Light yellow oil, yield: 0.38 g (86%). 1H NMR (400.13 MHz, CDCl3): δ = 0.89 (m, 3 H, CH3),
1.31 (m, 4 H, CH2CH2CH3), 1.62 (m, 2 H, CH2C3H7), 2.58 (m, 2 H, CH2C4H9), 2.74 (m,
2 H, SeCH2CH2P), 2.91 (m, 2 H, CH2P), 7.49 (m, 6 H, Ph), 7.84 (m, 4 H, Ph). 13C NMR
(100.61 MHz, CDCl3): δ = 13.7 (CH3), 15.1 (d, 2JPC = 2.2 Hz, PCH2CH2Se), 22.1 (CH2CH3),
1
24.3 (CH2C4H9), 30.1 (CH2C3H7), 31.8 (CH2C2H5), 34.0 (d, JPC = 42.0 Hz, CH2P), 128.5
2
1
3
(d, JPC = 12.2 Hz, Co, Ph), 130.8 (d, JPC = 71.1 Hz, Ci, Ph), 131.2 (d, JPC = 10.3 Hz,
Cm, Ph), 131.3 (d, JPC = 3.0 Hz, Cp, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 34.19
4
(1JP
= 729.1 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = −346.5 (d, JP
= 728.5 Hz),
1
=
=
Se
Se
206.4 (d, 3JPSe = 10.0 Hz). IR (neat, cm−1): 3073, 3053, 3006 (ν =CH of phenyl rings), 2955,
=
2926, 2869, 2855 (ν CH); 1587, 1573, 1481 (ν C C of phenyl rings), 1464, 1436, 1402 (δ CH2),
1378 (δ CH3), 1333, 1309, 1266, 1243, 1188, 1167, 1130, 1100, 1070, 1027, 998, 924, 883,
=
847, 747, 720, 708, 691 (δ CH of phenyl rings), 643, sh 548, 531 (ν P Se). Anal. Calcd for
C19H25PSe2: C, 51.60; H, 5.70; P, 7.00; Se, 35.70. Found: C, 51.30; H, 5.98; P, 6.79; Se, 35.94%.
4.2.5. 2-(Hexylselanyl)ethyl(diphenethyl)phosphine sulfide (7e)
1
Colorless oil, yield: 0.42 g (90%). H NMR (400.13 MHz, CDCl3): δ = 0.89 (m, 3 H, CH3),
1.30 (m, 4 H, CH2CH2CH3), 1.38 (m, 2 H, CH2C3H7), 1.65 (m, 2 H, CH2C4H9), 2.17 (m, 6 H,
CH2P), 2.58 (m, 2 H, CH2C5H11), 2.74 (m, 2 H, PCH2CH2Se), 2.95 (m, 4 H, PhCH2), 7.20 (m, 4
H, Ho, Ph), 7.24 (m, 2 H, Hp, Ph), 7.30 (m, 4 H, Hm, Ph). 13C NMR (100.61 MHz, CDCl3):
2
δ = 14.0 (CH3), 14.8 (d, JPC = 4.5 Hz, PCH2CH2Se), 22.5 (CH2CH3), 24.8 (CH2C5H11),
2
28.5 (d, JPC = 2.5 Hz, CH2Ph), 29.4 (CH2C3H7), 30.4 (CH2C4H9), 31.2 (CH2C2H5), 32.7
(d, 1JPC = 43.3 Hz, PCH2CH2Se), 33.0 (d, 1JPC = 47.3 Hz, CH2CH2Ph), 126.6 (Cp, Ph), 128.2
3
(Co, Ph), 128.7 (Cm, Ph), 140.3 (d, JPC = 13.6 Hz, Ci, Ph). 31P NMR (161.98 MHz, CDCl3):
3
δ = 49.11. 77Se NMR (76.31 MHz, CDCl3): δ = 207.7 (d, JPSe = 9.6 Hz). IR (neat, cm−1):
3085, 3062, 3026, 3001 (ν =CH of phenyl rings), 2955, 2926, 2867, 2853 (ν CH), 1603, 1583,
=
1496 (ν C C of phenyl rings), 1465, 1454, 1410 (δ CH2), 1378 (δ CH3), 1366, 1286, 1268,

Journal of Sulfur Chemistry
7
1254, 1214, 1175, 1121, 1082, 1048, 1030, 1011, 949, 909, 888, 874, sh 781, 767 (δ CH of
=
phenyl rings), 752 (ν P–C), 699 (δ CH of phenyl rings), sh 612, 598 (ν P S). Anal. Calcd for
C24H35PSSe: C, 61.92; H, 7.58; P, 6.65; S, 6.89; Se, 16.96. Found: C, 61.85; H, 7.63; P, 6.81; S,
7.01; Se, 16.68%.
4.2.6. 2-(Hexylselanyl)ethyl(diphenethyl)phosphine selenide (7f)
Light yellow oil, yield: 0.42 g (82%). 1H NMR (400.13 MHz, CDCl3): δ = 0.88 (m, 3 H, CH3),
1.29 (m, 4 H, CH2CH2CH3), 1.37 (m, 2 H, CH2C3H7), 1.65 (m, 2 H, CH2C4H9), 2.26 (m, 6 H,
CH2P), 2.58 (m, CH2C5H11), 2.73 (m, 2 H, PCH2CH2Se), 2.94 (m, 4 H, PhCH2), 7.21 (m, 4
H, Ho, Ph), 7.24 (m, 2 H, Hp, Ph), 7.30 (m, 4 H, Hm, Ph). 13C NMR (100.61 MHz, CDCl3):
2
δ = 14.3 (CH3), 15.6 (d, JPC = 4.1 Hz, PCH2CH2Se), 22.6 (CH2CH3), 24.7 (CH2C5H11),
2
29.4 (d, JPC = 2.2 Hz, CH2Ph), 29.6 (CH2C3H7), 30.5 (CH2C4H9), 31.5 (CH2C2H5), 32.2
1
1
(d, JPC = 36.5 Hz, PCH2CH2Se), 32.4 (d, JPC = 40.9 Hz, CH2CH2Ph), 126.8 (Cp, Ph),
128.4 (Co, Ph), 128.8 (Cm, Ph), 140.2 (d, JPC = 13.6 Hz, Ci, Ph). 31P NMR (161.98 MHz,
3
CDCl3): δ = 37.62 (1JP
= 706.7 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = −346.3 (d,
=
Se
1JP
= 722.7 Hz), 206.0 (d, JPSe = 9.4 Hz). IR (neat, cm−1): 3085, 3061, 3026, 3001
3
=
Se
=
(ν =CH of phenyl rings), 2954, 2925, 2854, (ν CH), 1603, 1583, 1496 (ν C C of phenyl rings),
1454, 1405 (δ CH2), 1378 (δ CH3), 1271, 1253, 1232, 1213, 1192, 1175, 1133, 1072, 1030, 1007,
948, 903, 873, 844, 751 (ν P-C), 699 (δ CH of phenyl rings), sh 573, 556 (ν P Se). Anal. Calcd
=
for C24H35PSe2: C, 56.25; H, 6.88; P, 6.04; Se, 30.82. Found: C, 56.33; H, 6.91; P, 5.78; Se,
30.98%.
4.2.7. 2-(Hexylselanyl)ethyl(diphenyl)phosphine sulfide (7g)
Light yellow oil, yield: 0.39 g (95%). 1H NMR (400.13 MHz, CDCl3): δ = 0.86 (m, 3 H, CH3),
1.27 (m, 6 H, CH2CH2CH2CH3), 1.58 (m, 2 H, CH2C4H9), 2.55 (m, 2 H, CH2C5H11), 2.75 (m,
4 H, SeCH2CH2P), 7.46 (m, 6 H, Ph), 7.80 (m, 4 H, Ph). 13C NMR (100.61 MHz, CDCl3):
2
δ = 14.0 (CH3), 14.7 (d, JPC = 3.0 Hz, PCH2CH2Se), 22.5 (CH2CH3), 24.6 (CH2C5H11),
1
29.6 (CH2C3H7), 30.1 (CH2C4H9), 31.2 (CH2C2H5), 34.5 (d, JPC = 49.0 Hz, CH2P), 128.7
2
3
4
(d, JPC = 12.2 Hz, Co, Ph), 130.9 (d, JPC = 10.3 Hz, Cm, Ph), 131.6 (d, JPC = 3.0 Hz, Cp,
Ph), 132.4 (d, 1JPC = 79.2 Hz, Ci, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 42.93. 77Se NMR
(76.31 MHz, CDCl3): δ = 205.8 (d, 3JPSe = 12.5 Hz). IR (neat, cm−1): 3074, 3054, 3021, 3005
=
(ν =CH of phenyl rings), 2955, 2926, 2867, 2854 (ν CH), 1606, 1586, 1574, 1480 (ν C C of
phenyl rings), 1465, 1436, 1404 (δ CH2), 1378 (δ CH3), 1332, 1309, 1279, 1254, 1234, 1187,
1168, 1104, 1070, 1027, 1013, 998, 886, 849, sh 771 (δ CH of phenyl rings), 750 (ν P–C), 741,
=
723, 711, 692 (δ CH of phenyl rings), 642, sh 620, 609 (ν P S). Anal. Calcd for C20H27PSSe: C,
58.67; H, 6.65; P, 7.57; S, 7.83; Se, 19.29. Found: C, 58.75; H, 6.55; P, 7.62; S, 8.01; Se, 19.05%.
4.2.8. 2-(Hexylselanyl)ethyl(diphenyl)phosphine selenide (7h)
1
Light yellow oil, yield: 0.40 g (88%). H NMR (400.13 MHz, CDCl3): δ = 0.86 (m, 3 H,
CH3), 1.27 (m, 6 H, CH2CH2CH2CH3), 1.61 (m, 2 H, CH2C4H9), 2.56 (m, 2 H, CH2C5H11),
2.71 (m, 2 H, SeCH2CH2P), 2.90 (m, 2 H, CH2P), 7.45 (m, 6 H, Ph), 7.81 (m, 4 H, Ph).
13C NMR (100.61 MHz, CDCl3): δ = 14.0 (CH3), 15.4 (d, 2JPC = 2.2 Hz, PCH2CH2Se), 22.4
(CH2CH3), 24.5 (CH2C5H11), 29.4 (CH2C3H7), 30.3 (CH2C4H9), 31.1 (CH2C2H5), 34.3 (d,
1JPC = 42.0 Hz, CH2P), 128.6 (d, 2JPC = 12.2 Hz, Co, Ph), 131.5 (d, 3JPC = 10.3 Hz, Cm, Ph),
4
131.6 (d, JPC = 3.0 Hz, Cp, Ph), 132.1 (Ci, Ph). 31P NMR (161.98 MHz, CDCl3): δ = 33.37
1
(1JP
= 727.4 Hz). 77Se NMR (76.31 MHz, CDCl3): δ = −353.2 (d, JP
= 727.6 Hz),
=
=
Se
Se

8
N.K. Gusarova et al.
202.1 (d, 3JPSe = 10.2 Hz). IR (neat, cm−1): 3074, 3053, 3006 (ν =CH of phenyl rings), 2955,
=
2925, 2867, 2854 (ν CH), 1614, 1588, 1573, 1481 (ν C C of phenyl rings), 1465, 1436, 1404
(δ CH2), 1378 (δ CH3), 1334, 1309, 1278, 1251, 1234, 1188, 1168, 1131, 1100, 1070, 1027, 998,
961, 929, 885, 847, 741, 728, 707, 691 (δ CH of phenyl rings), 641, sh 548, 531 (ν P Se). Anal.
=
Calcd for C20H27PSe2: C, 52.64; H, 5.96; P, 6.79; Se, 34.61. Found: C, 52.39; H, 6.03; P, 6.73;
Se, 34.81%.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work has been carried out under financial support of leading scientific schools by the President of the Russian
Federation [Grant NSh-156.2014.3].
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