Unexpected redox reaction of alkali metal diselenophosphinates with elemental iodine

Article abstract of DOI:10.1016/j.mencom.2012.01.006

Redox reaction between alkali metal diselenophosphinates R2P(Se)SeM (M = Na, K) and elemental iodine in a 2:1 molar ratio (1,4-dioxane, room temperature, 2 min) gives bis(diorganylselenophosphoryl)selenides [R₂P(Se)] ₂Se and bis(diorganylselenophosphoryl) triselenides [R ₂P(Se)]₂Se₃ in 87-90% total yields.

Full text of DOI:10.1016/j.mencom.2012.01.006

Mendeleev
Communications
Mendeleev Commun., 2012, 22, 18–20
Unexpected redox reaction of alkali metal
diselenophosphinates with elemental iodine
Alexander V. Artem’ev,a Svetlana F. Malysheva,a Boris G. Sukhov,a Nataliya A. Belogorlova,a
Yurii V. Gatilov,b Victor I. Mamatyukb and Nina K. Gusarova*a
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
664033 Irkutsk, Russian Federation. Fax: +7 3952 41 9346; e-mail: gusarova@irioch.irk.ru
b N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy
of Sciences, 630090 Novosibirsk, Russian Federation
DOI: 10.1016/j.mencom.2012.01.006
Redox reaction between alkali metal diselenophosphinates R2P(Se)SeM (M = Na, K) and elemental iodine in a 2:1 molar ratio
(1,4-dioxane, room temperature, 2 min) gives bis(diorganylselenophosphoryl)selenides [R2P(Se)]2Se and bis(diorganylselenophos-
phoryl)triselenides [R2P(Se)]2Se3 in 87–90% total yields.
Nowadays the chemistry of diselenophosphinates is intensively
studied1–3 due to the development of efficient methods for their
synthesis via novel three-component reactions between secondary
phosphines or secondary phosphine selenides, elemental selenium
and bases, such as alkali metal hydroxides4 or amino compounds.5–8
For example, alkali metal diselenophosphinates are useful as
precursors of remarkable nanocrystalline materials,2,9 ligands for
metal complexes10 and building blocks for organic synthesis.3(a),(e)
In the present work we report on redox reaction of alkali
metal diselenophosphinates with elemental iodine.
lysis.§ The crystalline structure of the co-crystal 8 is formed by
two pair of crystallographically independent molecules 4 and 6
(Figure 1). In selenides 4 and 6, coordination geometry around
the phosphorus atoms is a slightly distorted tetrahedron. The
Se=P–Se–P=Se fragment of monoselenide 4 has cis-trans (syn-
anti, sp-ap) conformation. One of close analogues of monoselenide
4, [Pr2iP(Se)]2Se,12 has the same conformation, while other analogue,
[Ph2P(Se)]2Se,12 is in gauche-trans (syn-anti, sc-ap) conforma-
The 1H, 13C, 31P and 77Se NMR spectra were recorded on a BrukerAV-400
†
Alkali metal dithiophosphinates, R2P(S)SM (R = Alk, Ar;
M = Na, K), are known to be readily oxidized by elemental iodine
to afford the homocoupling products, disulfides of R2P(S)SS(S)PR2
spectrometer (400.13, 101.61, 161.98 and 76.31 MHz, respectively) and
referenced to H3PO4 (31P NMR) and Me2Se (77Se NMR). FTIR spectra
were run on a Bruker Vertex 70 instrument. All steps of the experiment
were carried out in dry argon atmosphere. Absolute 1,4-dioxane was used
in the reaction as a solvent. Alkali metal diselenophosphinates 1–3 were
prepared according to a published method.4
t
ype.11 It might be anticipated that alkali metal diselenophosphinates,
R2P(Se)SeM would react with elemental iodine in a similar fashion
giving the corresponding diselenides, R2P(Se)SeSe(Se)PR2.
However, it has been found that this reaction between alkali
metal diselenophosphinates 1–3 and elemental iodine in a 2:1
molar ratio unexpectedly furnishes monoselenides [R2P(Se)]2Se
4, 5 and triselenides [R2P(Se)]2Se3 6, 7 in 87–90% total yields
(Scheme 1).†,‡ The reaction proceeds in 1,4-dioxane media at
room temperature unusually fast (2 min), the expected diselenides
[R2P(Se)]2Se2 being not formed (31P and 77Se NMR).
Reaction between alkali metal diselenophosphinates 1, 2 and elemental
iodine. To a solution of alkali metal diselenophosphinate 1, 2 (1.0 mmol)
in 1,4-dioxane (6 ml), a solution of elemental iodine (0.127 g, 0.5 mmol)
in 1,4-dioxane (10 ml) was added dropwise with stirring at room tempera-
ture over a period of 2 min. The resulting reaction mixture was diluted
with water (20 ml) and extracted with toluene (2×20 ml). The extract was
dried over K2CO3 and concentrated in vacuo to one tenth of its volume.
Upon addition of hexane (10 ml) and storage at 5–8°C overnight, co-crystal
8 precipitated as orange-red solid, which was washed with hexane (5 ml)
and dried in vacuo (1 Torr) to give crystals suitable for X-ray analysis.
Co-crystal 8 {co-crystal of bis[di(2-phenethyl)selenophosphoryl]selenide
4 and bis[di(2-phenethyl)selenophosphoryl]triselenide 6}: orange-red
crystals, yield 0.36 g (90%), mp 117–118 °C (hexane–toluene). IR (KBr,
n/cm–1): 3060, 3020, 2919, 2888, 2854, 1951, 1878, 1806, 1644, 1590,
1491, 1444, 1387, 1330, 1270, 1210, 1131, 1020, 1005, 939, 906, 825,
According to 31P NMR data, monoselenides 4, 5 and triselenides
6, 7 were formed in an equimolar ratio.
The structure of the compounds synthesized unambiguously
follows from 31P, 77Se, 13C and 1H NMR spectra. Monoselenide 4
and triselenide 6 were isolated as molecular (1:1) co-crystals 8,†
the structure of which was determined by X-ray diffraction ana-
1
745, 670, 570, 507, 458. H NMR (400.13 MHz, CDCl3) d: 2.78–2.91
Se
P
Se
P
R
(m, 16H, CH2P), 3.23–3.33 (m, 16H, CH2Ph), 7.37–7.48 (m, 40H, Ph).
13C NMR (100.62 MHz, CDCl3) d: 29.43, 29.56 and 29.74 (CH2Ph),
R
R
R
1
Se
37.95, 37.97 and 38.10 (d, CH2P, JPC 30.1, 30.0 and 32.0 Hz), 126.56
and 126.61 (p-CPh), 128.29 and 128.64 (o,m-CPh), 139.25, 139.35 and 139.37
(d, i-CPh, 3JPC 10.35, 10.83 and 10.73 Hz). 31P NMR (161.98 MHz, CDCl3)
d: 50.15 (s + satellites, 1P, triselenide, 1JPSe 384 Hz, 1JPSe 740 Hz), 51.94
(br.s, 1P, triselenide), 55.64 (s + satellites, 2P, monoselenide, 1JPSe 382 Hz,
1JPSe 726 Hz, 1JPSe 766 Hz, 2JPP 19.5 Hz). 77Se NMR (76.31 MHz, CDCl3)
d: –195 (d, 2Se, P=Se of triselenide, 1JPSe 740 Hz), –142 (d, 2Se, P=Se
4, 5
R
R
Se
Se
dioxane
+
I2
M
+
P
Se
P
Se
P
23–25 °C,
2 min
Se
R
R
R
1–3
Se
Se
R
6, 7
1
of monoselenide, JPSe 741 Hz), 283 (t, 1Se, P–Se–P of monoselenide,
1 R = Ph(CH2)2, M = Na
2 R = Ph(CH2)2, M = K
1
4, 6 R = Ph(CH2)2
1JPSe 382 Hz), 364 (d, 2Se, P–Se of triselenide, JPSe 420 Hz), 415 (d,
2
3 R = 2-Fur(CH2)2, M = Na
Scheme 1
© 2012 Mendeleev Communications. All rights reserved.
5, 7 R = 2-Fur(CH2)2
1Se, P–Se–Se–Se–P of triselenide, JPSe 115 Hz). Found (%): C, 48.20;
H, 4.56; P, 7.81; Se, 39.46. Calc. for C64H72P4Se8 (%): C, 48.14; H, 4.54;
P, 7.76; Se, 39.56.
– 18 –

Mendeleev Commun., 2012, 22, 18–20
(a)
(b)
Se(9)
C(81)
P(6)
C(65)
Se(4)
Se(12)
Se(1)
Se(5)
C(9)
Se(2)
C(25)
Se(4)
Se(1)
Se(11)
P(1)
C(1)
Se(1)
P(5)
Se(13)
Se(4)
C(89)
C(17)
P(2)
Se(9)
C(73)
Se(3)
Figure 2 Intermolecular contacts between selenium atoms of triselenide
molecules in the lattice of co-crystal 8. Hydrogen atoms are omitted for clarity.
Selected bond lengths (Å): Se(1)···Se(1) 3.455(2), Se(4)···Se(9) 3.509(1).
Figure 1 X-ray structures of (a) monoselenide 4 (one of two independent
molecules) and (b) triselenide 6 (one of two independent molecules) in the
co-crystal 8. Range of selected bond lengths (Å): P=Se 2.071(4)–2.108(3),
P–Se 2.237(3)–2.291(3), P–C 1.79(1)–1.90(1), Se–Se 2.336(2)–2.344(2).
the Se(1)···Se(1) and Se(4)···Se(9) distances of 3.455(2) and
3.509(1) Å, respectively, which is less than the sum of the van
der Waals radii (3.80 Å).15
tion. The Se=P–Se–Se–Se–P=Se fragment of both independent
molecules of triselenide 6 can be ascribed to trans-gauche-gauche-
trans (anti-syn-syn-anti, ap-sc-sc-ap) conformation. Close con-
geners of triselenide 6, [Et2P(Se)]2Se313 and [(EtO)2P(Se)]2Se3,14
have the same conformation. The values of the P–Se and P=Se
bond lengths in the molecules of monoselenide and triselenide
are similar to literature ones.12–14
Furthermore, the 31P NMR spectra of triselenides 6, 7 comprise
two singlets at 49.31–51.49 ppm which are accompanied by
sets of 77Se satellites. The presence of the several signals in the
31P NMR spectra of the triselenides can be explained by inter-
molecular interactions between molecules of triselenides in solu-
tion. The results of investigation of this phenomenon will be
published elsewhere.
Note that Se–Se intermolecular contacts exist between mole-
cules of triselenide in co-crystal 8 (Figure 2) as is evident from
To our knowledge, molecular co-crystal 8 is first example of
co-crystals of these rare and unstudied mono- and triselenides.
Currently, only few representatives of monoselenides and tri-
selenides were prepared (all in the form of monomolecular
crystals).12–14,16–18
‡
Reaction between sodium diselenophosphinate 3 and elemental iodine.
To a solution of sodium bis[2-(2-furyl)ethyl]diselenophosphinate 3 (0.402 g,
1.0 mmol) in 1,4-dioxane (6 ml), a solution of elemental iodine (0.127 g,
0.5 mmol) in 1,4-dioxane (10 ml) was added dropwise with stirring at room
temperature over a period of 2 min. The resulting reaction mixture was
diluted with water (20 ml) and extracted with toluene (2×20 ml). The
extract was dried over K2CO3, the toluene was removed in vacuo, and the
residue was reprecipitated from 1,4-dioxane (4 ml) to hexane (18 ml), dried
in vacuo (1 Torr) to give mixture of selenides 5 and 7 in a 1:1 molar ratio
(31P NMR data).
The mechanism of the discovered redox reaction still needs to
beelucidated.Atthemoment, formationofmono-andtriselenides
via sequence of the following processes seems to be most probable
(Scheme 2). Single electron oxidation of diselenophosphinate
1–3 by iodine generates diselenophosphinate radical A (stage 1)
which is recombined giving intermediate diselenide B (stage 2).
Disproportionation of the latter affords monoselenide 4, 5 and
triselenide 6, 7 (stage 3) as the reaction products. The mechanism
proposed is in compliance with experimental data indicating that
mono- and triselenides are formed in equimolar amounts.
In summary, the unexpected pathway of the redox reaction
between alkali metal diselenophosphinates and elemental iodine
has been discovered. The reaction proceeds under mild condi-
tions (room temperature, 2 min) to give bis(diorganylseleno-
phosphoryl)selenides and bis(diorganylselenophosphoryl)tri-
selenides in high total yields. The results obtained significantly
contribute to basic chemistry of selenophosphorus compounds
(including their solid state chemistry).
Mixture of bis{di[2-(2-furyl)ethyl]selenophosphoryl}selenide 5 and
bis{di[2-(2-furyl)ethyl]selenophosphoryl}triselenide 7: orange-red oil,
yield 0.33 g (87%). IR (film, n/cm–1): 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. 1H NMR (400.13 MHz,
C6D6) d: 2.56–2.69 and 2.71–2.84 (m, 16H, CH2P), 2.93–3.25 (m, 16H,
CH2Fur), 6.10–7.33 (m, 24H, Fur). 13C NMR (100.62 MHz, C6D6) d:
22.54 (CH2Fur), 32.80 (d, CH2P, 1JPC 35.4 Hz), 106.42 (3-CFur), 110.45
(4-CFur), 141.35 (5-CFur), 152.90 (d, 2-CFur,
3JPC 18.6 Hz). 31P NMR
(161.98 MHz, C6D6) d: 49.31 (s + satellites, 1P, triselenide, 1JPSe 380 Hz,
1JPSe 740 Hz), 50.88 (br.s, 1P, triselenide), 54.95 (s + satellites, 2P, mono-
selenide, 1JPSe 376 Hz, 1JPSe 734 Hz, 1JPSe 770 Hz, 2JPP 19.7 Hz). 77Se NMR
(76.31 MHz, C6D6) d: –193 (d, 2Se, P=Se of triselenide, 1JPSe 740 Hz),
–147 (d, 2Se, P=Se of monoselenide, 1JPSe 752 Hz), 280 (t, 1Se, P–Se–P of
monoselenide, 1JPSe 376 Hz), 357 (d, 2Se, P–Se of triselenide, 1JPSe 424 Hz),
419 (d, 1Se, P–Se–Se–Se–P of triselenide, 2JPSe 120 Hz). Found (%): C,
38.10; H, 3.68; P, 8.11; Se, 41.57. Calc. for C48H56O8P4Se8 (%): C, 38.02;
H, 3.72; P, 8.17; Se, 41.65.
R
R
Se
Se
R
R
Se
Se
stage 1
+
0.5 I2
P
+
MI
M
P
1–3
A
§
X-ray diffraction analysis of co-crystal 8 was performed on a Bruker
SMART KAPPA APEX-II CCD diffractometer at 150 K [MoKa radiation,
l(MoKa) = 0.71073 Å, j,w-scans]. The structure was solved by direct
methods and refined by a full matrix least-squares anisotropic procedure
using SHELXTL97 programs.19 The parameters of the hydrogen atoms
were given geometrically.
Co-crystals 8 (C64H72P4Se8, M = 1596.83) are monoclinic, space group
P21/n, a = 26.733(1), b = 10.6037(5) and c = 48.118(2)Å, b = 103.736(2)°,
V = 13250(1) Å3, Z = 8, dcalc = 1.601 g cm–3, m(MoKa) = 4.546 mm–1,
89949 reflections were measured, from which 24246 were independent
(Rint = 0.0561), R1 = 0.0829 for 16480 reflections with I > 2s(I), wR2 =
= 0.2185, S = 1.155.
Se
P
Se
R
R
Se
Se
stage 2
P
P
R
R
R
Se Se
R
A
B
Se
Se
P
P
R
R
Se
R
R
Se
Se
4, 5
stage 3
P
P
+
R
R
R
R
Se Se
Se
Se
P
Se
P
B
R
R
R
Se
Se
CCDC 822761 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.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2012.
R
6, 7
Scheme 2
– 19 –

Mendeleev Commun., 2012, 22, 18–20
6 A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva and B. A. Trofimov,
This work was supported by the Russian Foundation for Basic
Research (grant no. 11-03-92003-HHC_a) and the RF President
programs for the support of leading scientific schools (grant
NSh-3230.2010.3) and young Russian scientists (grant MK-629-
2010.3).
Izv. Akad. Nauk, Ser. Khim., 2010, 1626 (Russ. Chem. Bull., Int. Ed.,
2010, 59, 1671).
7 (a) B. A. Trofimov, A. V. Artem’ev, N. K. Gusarova, S. F. Malysheva,
S. V. Fedorov, O. N. Kazheva, G. G. Alexandrov and O. A. Dyachenko,
Synthesis, 2009, 3332; (b)A.V.Artem’ev, N. K. Gusarova, S. F. Malysheva,
P. B. Kraikivskii, N. A. Belogorlova and B. A. Trofimov, Synthesis, 2010,
3724.
Online Supplementary Materials
Supplementary data (31P NMR spectra of reaction mixtures)
associated with this article can be found in the online version at
doi:10.1016/j.mencom.2012.01.006.
8 N. K. Gusarova,A.V.Artem’ev, S. F. Malysheva, S.V. Fedorov, O. N. Kazheva
,
G. G.Alexandrov, O.A. Dyachenko and B.A. Trofimov, Tetrahedron Lett.,
2010, 51, 1840.
9 T. Kawai, Y. Hasegawa and T. Adachi, US Patent WO 2007/102271,
2007 (Chem. Abstr., 2007, 147, 368034).
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– 20 –