Reaction of secondary phosphine selenides with the system Se/MOH (M = Li, Na, K, Rb, Cs): A novel three-component synthesis of diorganodiselenophosphinates

Article abstract of DOI:10.1016/j.jorganchem.2009.03.010

Secondary phosphine selenides, R₂P(Se)H (R = PhCH₂CH₂, PhCH(Me)CH₂, 4-t-BuC₆H₄CH₂CH₂, NaphthylCH₂CH₂, Ph), react with the system Se/MOH (M = Li,

Full text of DOI:10.1016/j.jorganchem.2009.03.010

Journal of Organometallic Chemistry 694 (2009) 4116–4120
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Reaction of secondary phosphine selenides with the system
Se/MOH (M = Li, Na, K, Rb, Cs): A novel three-component synthesis
of diorganodiselenophosphinates
*
Boris A. Trofimov , Alexander V. Artem’ev, Svetlana F. Malysheva, Nina K. Gusarova
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky St., Irkutsk 664033, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Secondary phosphine selenides, R2P(Se)H (R = PhCH2CH2, PhCH(Me)CH2, 4-t-BuC6H4CH2CH2, Naph-
thylCH2CH2, Ph), react with the system Se/MOH (M = Li, Na, K, Rb, Cs) in the system THF/EtOH at ambient
temperature unusually fast (20–30 s) to give cleanly and almost quantitatively (in 94–100% yield) earlier
unknown diorganodiselenophosphinates of alkali metals.
Received 28 January 2009
Received in revised form 25 February 2009
Accepted 6 March 2009
Available online 14 March 2009
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Secondary phosphine selenides
Elemental selenium
Alkali metal hydroxides
Diselenophosphinates
1. Introduction
The complex of lithium diphenyldiselenophosphinate with THF
and TMEDA, [Li(Se2PPh2) Á THF Á TMEDA], was prepared by the
Diselenophosphinates of alkali metals represent a scarcely stud-
ied, though a promising class of new elementoorganic compounds.
They are used as intermediates for the preparation of conducting
nanomaterials [1], single-source precursors (SSPs) in metal organic
chemical vapor deposition processes for design of semiconducting
thin films [2], extractants of rare earth and transuranic elements
[3], biologically active compounds possessing e.g., antimicrobial
properties [4] as well as reactive building blocks for organic and ele-
mentoorganic synthesis [5]. For example, the reactions of potas-
sium diphenyldiselenophosphinate with InCl3 [6a] and EuCl3 [6b]
led to the corresponding indium and europium diph-
enyldiselenophosphinates. The latter were further used for the syn-
thesis of nano-sized Eu selenide with remarkable magneto-optical
properties in the active wavelength shorter than 600 nm [6b].
Among diorganodiselenophosphinates of alkali metals, only
lithium, sodium and potassium diphenyldiselenophosphinates
are known.
reaction of Ph2PH with n-BuLi and Se in THF/TMEDA/toluene media
at (À78)–20° C [8].
The reaction of potassium diphenylphosphide with elemental
selenium in THF
– toluene solution furnished the complex
[K(Se2PPh2) Á THF]2 (no experimental details was reported) [6a].
Recently, the potassium diphenyldiselenophosphinate monohy-
drate, K(Se2PPh2) Á H2O, was prepared from potassium diphenyl-
phosphine and selenium (THF, À30° C, 6 h) in 74% yield [6b].
Thus, all the known syntheses of alkali metal dio-
rganodiselenophosphinates are multistep and laborious and re-
quire aggressive and poisonous phosphorus halogenides and
flammable unstable organometallic reactants. Moreover, these
methods have so far been limited only by preparation of Li, Na
and K diphenyldiselenophosphinates.
The goal of this work is to elaborate a novel general and simple
approach to the synthesis of alkali metal diorganodiseleno-
phosphinates.
Sodium diphenyldiselonophosphinate was synthesized as a
complex with THF and H2O, [Na(Se2PPh2) Á THF Á 5H2O], in small
yield [7a–f] from toxic and readily hydrolysable Ph2PCl and inac-
cessible NaxSey. Also, it was reported [7g] that the reaction be-
tween NaxSey and Ph2PCl was irreproducible and gave a mixture
of products.
To reach this goal we have studied for the first time the three-
component reaction of secondary phosphine selenides with ele-
mental selenium and alkali metal hydroxides.
2. Results and discussion
Our experiments have shown that bis(arylalkyl)phosphine sele-
nides 1–3, now available [9], react with the system Se/MOH
(M = Li, Na, K, Rb, Cs) in the system THF/EtOH at ambient temper-
* Corresponding author. Fax: +7 3952 419346.
E-mail address: boris_trofimov@irioch.irk.ru (B.A. Trofimov).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.03.010

B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 4116–4120
4117
R1
R1
R2
R2
Se
Se
Se
H
THF/EtOH
Se
+
P
+ MOH
P
M+
20-25 oC, 20-30 s
R2
R2
R1
R1
1-3
4a-g
R1
R2
Initial phosphine
selenide 1-3
MOH
Salt
4
a
b
c
d
e
Isolated
yield, %
96
97
~ 100
98
98
97
~100
1
1
1
1
1
2
3
H
H
H
H
H
H
H
H
H
H
LiOH
NaOH
KOH
RbOH
CsOH
RbOH
KOH
H
t-Bu
Me
H
f
g
Scheme 1. Synthesis of alkali metal diorganodiselenophosphinates 4a–g (hereinafter: argon atmosphere, equimolar ratio of the reactants).
ature unusually fast (20–30 s) to afford earlier unknown alkali me-
tal diorganodiselenophosphinates 4a–g in almost quantitative
yields (96–100%) (Scheme 1).
Se
Se
Se
H
THF/EtOH
P
+
KOH
P
K+
Se
+
20-25 oC, 30 s
The reaction proved to be of general character showing the
same efficiency, e.g., with such sterically encumbered secondary
phosphine selenide as bis[2-(2-naphthyl)ethyl]phosphine selenide
5 to form diselenophosphinate 4h in 94% yield (Scheme 2).
A novel secondary phosphine selenide 5 was specially synthe-
sized in this work from 2-vinylnaphthalene, red phosphorus and
elemental selenium according to the protocol [9] (Scheme 3).
The generality and efficacy of the approach elaborated was
additionally demonstrated by the synthesis of non-hydrated potas-
sium diphenyldiselenophosphinate 4i in 95% yield (Scheme 4).
Noteworthy, that diphenyldiselenophosphinate 4i was earlier
isolated only in the hydrated form, [K(Se2PPh2) Á H2O], in 74% yield
[6b].
The salts 4a–i synthesized are colorless solids soluble in water
(except for salt 4h) being stable upon storing at room temperature
under inert atmosphere in the dark.
The structures of the compounds 4a–i were proved by multinu-
clear 1H, 13C, 31P and 77Se NMR. The chemical equivalency of both
selenium atoms in the salts 4a–i was evidenced from the follow-
ings NMR features:
6
4i
Scheme 4. Synthesis of potassium diphenyldiselenophosphinate (4i).
2. In the 31P NMR spectra, a singlet with a one typical satellite pair
[8,10] was observed (1JSeP = 550–613 Hz).
1
3. The JSeP value (550–613 Hz) was intermediate between the
coupling constant values for P–Se and P@Se moieties (200–
600 and 800–1200 Hz, respectively), thus corresponding to
the 1.5 order of the phosphorus–selenium bonds [10].
Amazingly, alkali metal cation exerted no effect on both 31P and
77Se chemical shifts appeared, apparently due to a strong solvation
of ions by the molecules of D2O upon recording the NMR spectra.
At the same time, 31P and 77Se chemical shifts were noticeably sen-
sitive towards insignificant changes in organic moieties structure
(the corresponding shifts ranged from 21.61 to 26.92 ppm and
from À35.82 to À68.85 ppm for 31P and 77Se, respectively).
The IR spectra and elemental analysis of all the compounds iso-
lated correspond to their structures. So, the IR spectra of the dise-
lenophosphinates 4a–i, showed strong absorption bans at 540–570
1. In the 77Se NMR spectra, a one dublet (1JSeP = 550–613 Hz) was
present.
Se
Se
THF/EtOH
20-25 oC, 30 s
K+
Se
+
P
+
KOH
P
H
Se
5
4h
Scheme 2. Synthesis of potassium bis[2-(2-naphthyl)ethyl]diselenophosphinate (4h).
KOH/H2O
PhMe
Se
PH3/H2
5
Pred
P
H
KOH/DMSO
Scheme 3. Synthesis of bis[2-(2-naphthyl)ethyl]phosphine selenide (5).

4118
B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 4116–4120
oxidation of commercially available diphenylphosphine (Aldrich,
2008) with grey selenium. Bis[2-(2-naphthyl)ethyl]phosphine sel-
enide 5 was synthesized here for the first time.
Se
Se
H
OH
Se
P
P
P
Se
P
-H2O
Se
Se
A
B
4.1. Synthesis and characteristics of bis[2-(2-
naphthyl)ethyl]phosphine selenide (5) (Scheme 3)
Scheme 5. The deprotonation of secondary phosphine selenides first step of the
synthesis of salts (4).
A suspension containing KOH (20 g), H2O (3 mL) and DMSO
(50 mL) was blown with argon and saturated with phosphine–
hydrogen mixture, generated in a separate flask by addition of
50% aqueous solution of KOH (100 g) to a mixture of red phospho-
rus (20 g) in 40 mL of toluene at 70–75 °C. To the suspension ob-
tained, 2-vinylnaphthalene (4.5 g, 29.18 mmol) stabilized with
hydroquinone (0.02 g) in 20 mL of DMSO was added dropwise over
1 h 30 min at 60–65 °C (while bubbling phosphine at a rate of 68–
70 bubbles/min), and phosphine was passed for additional 15 min
under the same conditions. Next, the phosphine feeding was
stopped, the system was blown with argon and was stirred addi-
tionally for 30 min. The reaction mixture was cooled to room tem-
perature, H2O was added (100 mL) and the solution obtained was
extracted with toluene (100 mL Â 1); the extract was washed with
H2O (30 mL Â 2), filtered over K2CO3, the toluene was removed to
give 4.35 g (87%) of bis[2-(2-naphthyl)ethyl]phosphine. To the lat-
ter, toluene (50 mL) and elemental selenium (1.00 g, 12.70 mmol)
was added. The suspension obtained was stirred at 20–25 °C over
0.5 h, toluene was removed in vacuum to give 5.19 g (97%) phos-
phine selenide (5). Yellowish-brown oil. Anal. Calc. for C24H23PSe:
C, 68.41; H, 5.50; P, 7.35; Se, 18.74. Found: C, 68.35; H, 5.61; P,
7.40; Se, 18.86%. IR (film, cmÀ1): 3051, 3021, 2925, 2858, 2334,
1952, 1804, 1631, 1599, 1508, 1445, 1367, 1271, 1124, 1018,
996, 950, 892, 858, 819, 796, 746, 476. 1H NMR (400.13 MHz,
CDCl3): d 2.28–2.35 (m, 2H, CH2P), 2.38–2.49 (m, 2H, CH2P),
H
SeH
MOH
-H2O
Se
4a-i
P
P
Se
Se
Scheme 6. The oxidation of secondary phosphine selenides by elemental selenium
as a possible initial step of the synthesis of salts 4.
and 470–490 cmÀ1 which can be ascribed to the asymmetric (mas
and symmetric ( s) stretching vibrations of the PSe2 groups.
)
m
The first step of the reaction was assumed to be the deprotona-
tion of the molecule of secondary phosphine selenides by the
hydroxide-anion to generate the anion A which further cleaved
the Se–Se bond of the elemental selenium, finely delivering dise-
lenophosphinate-aniones B (Scheme 5).
The easy deprotonation of secondary phosphine selenides
should be due to their known enhanced PH-acidity.
An alternative for the first step might also be the oxidation of
secondary phosphine selenides by the elemental selenium to form
diselenophosphinic acids which were instantly neutralized by the
alkali metal hydroxides (Scheme 6). The latter can function as a
catalyst or a third component in the three-molecule collision
(nucleophilic assistance).
1
2.99–3.28 (m, 4H, CH2Naphthyl), 6.00 (d, 1H, PH, JHP = 433.8 Hz),
7.13–7.82 (m, 14 H, Naphthyl). 13C NMR (100.69 MHz, CDCl3): d
3. Conclusions
2
1
29.86 (d, JCP = 2.9 Hz, CH2Naphthyl), 30.62 (d, JCP = 43.5 Hz,
CH2P), 125.79–133.55 (Naphthyl), 136.88 and 136.98 (d,
3JCP = 12.0 Hz, C2, Naphthyl). 31P NMR (161.98 MHz, CDCl3): d
2.27 (1JSeP = 710.6 Hz). 77Se NMR (76.31 MHz, CDCl3): d À414.07
An unusually rapid three-component reaction between second-
ary phosphine selenides, elemental selenium and alkali metal
hydroxides to cleanly afford the corresponding salts of diseleno-
phosphinic acids in almost quantitative yields (94–100%) has been
discovered. The generality and preparative efficacy of the method
developed have been demonstrated by the synthesis of earlier un-
known series of Li, Na, K, Rb, Cs salts of disilenophosphinic acids
bearing aralkyl- and aryl substituents as well as condensed aro-
matic moieties (2-naphthylethyl). The salts synthesized are prom-
ising intermediates to produce conducting nanomaterials and SSPs
in metal organic vapor deposition to manufacture semiconducting
thin films as well as building blocks for the design of diverse phos-
phorus–selenium organic compounds. Also, the alkali metal dise-
lenophosphinates, easily synthesized from available starting
materials, have a potential as indispensable source of other metal
diselenophosphinates (particularly, heavy, rare earth and transi-
tion metals) through the exchange reaction with various metal
derivatives.
1
(d, JSeP = 710.7 Hz).
4.2. Synthesis and characteristics of lithium and sodium salts 4a,b:
typical procedure (Scheme 1)
To a solution of secondary phosphine selenide 1 (0.200 g,
0.623 mmol) in THF (2 mL), amorphous grey selenium (0.049 g,
0.623 mmol) was added at room temperature under Ar. To the sus-
pension, upon stirring, MOH (M = Li, Na, 0.623 mmol) in EtOH
(6 mL) was added: selenium was dissolved instantly (ꢀ20–30 s)
to give a colorless transparent solution. The solvents were removed
under reduced pressure and the residue (colorless viscous oil with
increments of solid particles) was dissolved in Et2O (2 mL). After a
evaporation of the solvent in vacuum (1 mm Hg, room tempera-
ture), the salts 4a,b were obtained as crystals.
4. Experimental
4.2.1. Lithium salt of bis(2-phenethyl)phosphinodiselenoic acid (4a)
Colorless solid. Yield: 0.243 g (96%), m.p. 99° C. Anal. Calc. for
C16H18PSe2Li: 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%. IR (KBr, cmÀ1): 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. 1H NMR (400.13 MHz, D2O): d 2.11–2.17 (m,
4H, CH2P), 2.60–2.67 (m, 4H, CH2Ph), 6.96–7.01 (m, 10H, Ph). 13C
The 1H, 13C, 31P and 77Se NMR spectra were recorded on a Bru-
ker DPX 400 and Bruker AV-400 spectrometer (400.13, 100.61,
161.98 and 76.31 MHz, respectively) in D2O, CDCl3 or DMSO-d6
solutions and referenced to HMDS (1H NMR, 13C NMR), H3PO4
(
31P NMR) and Me2Se (77Se NMR). IR spectra were run on a Bruker
IFS 25 instrument. All steps of the experiment were carried out in
inert atmosphere (argon). Solvents were distilled prior to use.
Secondary phosphine selenides 1–3 were prepared from sty-
renes, red phosphorus and elemental selenium as described in
the literature [9]. Diphenylphosphine selenide 6 was prepared by
1
NMR (100.69 MHz, D2O): d 29.78 (CH2Ph), 42.08 (d, JCP = 35.4 Hz,
CH2P), 125.58 (p-C), 127.77 (o-C), 128.03 (m-C), 140.77 (d,
3JCP = 16.0 Hz, i-C). 31P NMR (161.98 MHz, D2O): d 26.66 (+d satel-

B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 4116–4120
4119
1
lite, JSeP = 555.9 Hz). 77Se NMR (76.31 MHz, D2O): d À66.75 (d,
1396, 1315, 1265, 1206, 1193, 1180, 1159, 1144, 1123, 1066, 1027,
1008, 955, 929, 913, 862, 834, 753, 737, 712, 696, 571, 561, 519,
495, 483, 417. 1H NMR (400.13 MHz, D2O): d 2.42–2.46 (m, 4H,
CH2P), 2.92–2.94 (m, 4H, CH2Ph), 7.22–7.31 (m, 10H, Ph). 13C
1JSeP = 555.9 Hz).
4.2.2. Sodium salt of bis(2-phenethyl)phosphinodiselenoic acid (4b)
Colorless solid. Yield: 0.255 g (97%), m.p. 182° C. Anal. Calc. for
C16H18PSe2Na: 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%. IR (KBr, cmÀ1): 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. 1H NMR (400.13 MHz, D2O): d
2.19–2.26 (m, 4H, CH2P), 2.69–2.76 (m, 4H, CH2Ph), 6.94–7.08
(m, 10H, Ph). 13C NMR (100.69 MHz, D2O): d 30.68 (CH2Ph),
1
NMR (100.69 MHz, D2O): d 30.61 (CH2Ph), 42.94 (d, JCP = 35.6 Hz,
CH2P), 126.47 (p-C), 128.65 (o-C), 128.92 (m-C), 141.70 (d,
3JCP = 15.8 Hz, i-C). 31P NMR (161.98 MHz, D2O): d 26.92 (+d satel-
1
lite, JSeP = 555.2 Hz). 77Se NMR (76.31 MHz, D2O): d À68.85 (d,
1JSeP = 555.0 Hz).
4.3.4. Rubidium salt of bis(2-phenylpropyl)phosphinodiselenoic acid
(4f)
Colorless solid. Yield: 0.310 g (97%), m.p. 180–182° C. Anal. Calc.
for C18H22PSe2Rb: C, 42.17; H, 4.32; P, 6.04; Se, 30.80. Found: C,
42.31; H, 4.34; P, 6.10; Se, 30.66%. IR (KBr, cmÀ1): 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. 1H NMR
1
42.91 (d, JCP = 35.9 Hz, CH2P), 126.28 (p-C), 128.52 (o-C), 128.73
(m-C), 141.43 (d, JCP = 16.1 Hz, i-C). 31P NMR (161.98 MHz, D2O):
3
d 26.83 (+d satellite, JSeP = 559.1 Hz). 77Se NMR (76.31 MHz,
1
1
D2O): d = À61.07 (d, JSeP = 559.2 Hz).
2
4.3. Synthesis and characteristics of potassium, rubidium and caesium
(400.13 MHz, D2O): d 1.32 and 1.39 (d, JHH = 6.7 Hz, Me), 2.17–
salts 4c–i: typical procedure (Schemes 1, 2 and 4)
2.32 (m, 2H, CH2P), 2.39–2.52 (m, 2H, CH2P), 3.35–3.48 (m, 2H,
CHPh), 7.15–7.28 (m, 10H, Ph). 13C NMR (100.69 MHz, D2O): d
3
3
To a solution of secondary phosphine selenide (2, 3, 5 or 6)
(0.623 mmol) in THF (4 mL), amorphous grey selenium (0.049 g,
0.623 mmol) was added at room temperature under Ar. To the sus-
pension, upon stirring, MOH Á nH2O (n = 0.5 for K, n = 1 for Rb and
Cs; 0.623 mmol) in EtOH (3 mL) was added: selenium was dis-
solved instantly (ꢀ20–30 s) to give a colorless transparent solu-
tion. The solvents were removed under reduced pressure and the
residue (colorless solid) was washed with Et2O (2 mL), dried in vac-
uum (1 mm Hg, room temperature) to give the salts 4c–i.
23.49 and 23.84 (d, JCP = 9.7 and JCP = 9.2 Hz, Me), 36.96 and
1
1
37.05 (CHPh), 49.04 and 49.31 (d, JCP = 32.6 and JCP = 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, JCP = 11.3 and JCP = 11.9 Hz, i-C). 31P NMR
3
3
(161.98 MHz, D2O): d 24.88 and 26.01 (two singlets in ratio 3:1),
1
1
(+d satellite, JSeP = 556.9 Hz and JSeP = 550.0 Hz). 77Se NMR
1
(76.31 MHz, D2O):
d
À62.44 (d, JSeP = 564.5 Hz), À26.13 (d,
1JSeP = 556.9 Hz), À6.28 (d, JSeP = 550.0 Hz).
1
4.3.5. Potassium salt of bis[(4-tertbutyl)phenethyl]phosphino-
diselenoic acid (4g)
4.3.1. Potassium salt of bis(2-phenethyl)phosphinodiselenoic acid (4c)
Colorless solid. Yield: 0.273 g (ꢀ100%), m.p. 209 °C. Anal. Calc.
for C16H18PSe2K: 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, cmÀ1): 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. 1H NMR
(400.13 MHz, D2O): d 2.13–2.19 (m, 4H, CH2P), 2.61–2.68 (m, 4H,
CH2Ph), 6.80–6.88 (m, 10H, Ph). 13C NMR (100.69 MHz, D2O):
Colorless solid. Yield: 0.343 g (ꢀ100%) m.p. 186° C. Anal. Calc.
for C24H34PSe2K: 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%. IR (KBr, cmÀ1): 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. 1H NMR (400.13 MHz,
D2O): d 1.26 (s, 6H, Me), 2.37–2.53 (m, 4H, CH2P), 2.86–3.04 (m,
4H, CH2C6H4), 7.13–7.35 (m, 8H, C6H4). 13C NMR (100.69 MHz,
D2O): d 30.66 (CH2C6H4), 31.44 (Me), 32.38 (d, CH2P, 1JCP = 41.7 Hz),
34.39 (CMe), 125.45 (C2, C6H4), 128.32 (C3, C6H4), 138.04 (d, C1,
1
30.92 (CH2Ph), 42.99 (d, JCP = 35.4 Hz, CH2P), 126.27 (p-C),
3
3
128.45 (o-C), 128.71 (m-C), 141.32 (d, JCP = 15.9 Hz, i-C). 31P
C6H4, JCP = 15.7 Hz), 148.95 (C4, C6H4). 31P NMR (161.98 MHz,
1
NMR (161.98 MHz, D2O): d 26.45 (+d satellite, JSeP = 557.4 Hz).
D2O):
d
25.42 (+d satellite, 1JSeP = 558.8 Hz). 77Se NMR
1
1
77Se NMR (76.31 MHz, D2O): d À63.09 (d, JSeP = 557.4 Hz).
(76.31 MHz, D2O): d À65.45 (d, JSeP = 558.6 Hz).
4.3.2. Rubidium salt of bis(2-phenethyl)phosphinodiselenoic acid (4d)
Colorless solid. Yield: 0.296 g (98%), m.p. 202° C. Anal. Calc. for
C16H18PSe2Rb: 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%. IR (KBr, cmÀ1): 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. 1H NMR (400.13 MHz, D2O): d 2.21–2.28 (m, 4H, CH2P), 2.71–
2.78 (m, 4H, CH2Ph), 6.99–7.08 (m, 10H, Ph). 13C NMR
4.3.6. Potassium salt of bis[2-(2-naphthyl)ethyl]phosphinodiselenoic
acid (4h)
Yellowish solid. Yield: 0.316 g (94%), m.p. 192–194° C. Anal.
Calc. for C24H22PSe2K: 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%. IR (KBr, cmÀ1): 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. 1H NMR (400.13 MHz, DMSO-d6): d 2.35–2.42 (m,
4H, CH2P), 3.11–3.18 (m, 4H, CH2Naphthyl) 7.34–7.83 (m, 14H,
Naphthyl). 13C NMR (100.69 MHz, DMSO-d6): d 31.43 (CH2Naph-
1
(100.69 MHz, D2O): d 30.27 (CH2Ph), 42.52 (d, JCP = 35.8 Hz,
CH2P), 125.92 (p-C), 128.15 (o-C), 128.37 (m-C), 141.06 (d,
3JCP = 16.2 Hz, i-C). 31P NMR (161.98 MHz, D2O): d 26.63 (+d satel-
thyl), 45.33 (d, JCP = 36.6 Hz, CH2P), 125.60–133.79 (Naphthyl),
1
1
3
lite, JSeP = 559.0 Hz). 77Se NMR (76.31 MHz, D2O): d À61.58 (d,
140.79. (d, JCP = 15.8 Hz, C2, Naphthyl). 31P NMR (161.98 MHz,
1JSeP = 559.0 Hz).
DMSO-d6):
d
23.76 (+d satellite, JSeP = 612.8 Hz). 77Se NMR
1
1
(76.31 MHz, DMSO-d6): d À35.82 (d, JSeP = 612.8 Hz).
4.3.3. Caesium salt of bis(2-phenethyl)phosphinodiselenoic acid (4e)
Colorless solid. Yield: 0.325 g (98%), m.p. 187° C. Anal. Calc. for
C16H18PSe2Cs: 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%. IR (KBr, cmÀ1): 3097, 3080, 3059, 3021,
2997, 2946, 2926, 2898, 2855, 1654, 1597, 1579, 1493, 1453, 1441,
4.3.7. Potassium salt of diphenylphosphinodiselenoic acid (4i)
Colorless solid. Yield: 0.226 g (95%) m.p. 134° C. Anal. Calc. for
C12H10PSe2K: 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%. IR (KBr, cmÀ1): 3052, 2079,

4120
B.A. Trofimov et al. / Journal of Organometallic Chemistry 694 (2009) 4116–4120
[5] T. Kimura, T. Murai, J. Org. Chem. 70 (2005) 952.
[6] (a) R.P. Davies, C.V. Francis, A.P.S. Jurd, M.G. Martinelli, A.J.P. White, D.J.
Williams, Inorg. Chem. 43 (2004) 4802;
(b) Y. Hasegawa, T. Adachi, A. Tanaka, M. Afzaal, P. O’Brien, T. Doi, Y. Hinatsu,
K. Fujita, K. Tanaka, T. Kawai, J. Am. Chem. Soc. 130 (2008) 5710.
[7] (a) W. Kuchen, J. Metten, A. Judat, Chem. Ber. 97 (1964) 2306;
(b) W. Kuchen, B. Knop, Angew. Chem., Int. Ed. 4 (1965) 244;
(c) W. Kuchen, H. Hertel, Angew. Chem., Int. Ed. 8 (1969) 89;
(d) A. Muëller, V.V.K. Rao, P. Christophliemk, J. Inorg. Nucl. Chem. 104 (1971)
1905;
1819, 1628, 1471, 1429, 1395, 1335, 1299, 1171, 1122, 1086, 1060,
1027, 995, 748, 694, 587, 540, 478. 1H NMR (400.13 MHz, D2O): d
7.82–7.87 (m, 10H, Ph). 13C NMR (100.69 MHz, D2O): d 128.19
and 128.31 (o-C), 130.62 (m-C), 130.74 (p-C), 140.07 (d,
1JCP = 65.9 Hz, i-C). 31P NMR (161.98 MHz, D2O): d 21.61 (+d satel-
1
lite, JSeP = 582.8 Hz).
References
(e) A. Muëller, V.V.K. Rao, P. Christophliemk, J. Inorg. Nucl. Chem. 34 (1972)
345;
(f) A. Muëller, V.V.K. Rao, P. Christophliemk, J. Inorg. Nucl. Chem. 36 (1974)
472;
(g) M.J. Pilkington, A.M.Z. Slawin, D.J. Williams, J.D. Woollins, Polyhedron 10
(1991) 2641.
[1] (a) S.P. Gubin, N.A. Kataeva, G.B. Khomutov, Russ. Chem. Bull. 54 (2005) 827;
(b) C.Q. Nguyen, A. Adeogun, M. Afzaal, M.A. Malik, P. O’Brien, Chem. Commun.
(2006) 2182;
(c) C.Q. Nguyen, M. Afzaal, M.A. Malik, M. Helliwell, J. Raftery, P. O’Brien, J.
Organomet. Chem. 692 (2007) 2669.
[8] (a) R.P. Davies, M.G. Martinelli, Inorg. Chem. 41 (2002) 348.
[9] (a) B.A. Trofimov, L. Brandsma, S.N. Arbuzova, S.F. Malysheva, N.K. Gusarova,
Tetrahedron Lett. 35 (1994) 7647;
[2] (a) G.C. Bwembya, X. Song, M. Bochmann, Chem. Vap. Deposit. 1 (1995) 78;
(b) X. Song, M. Bochmann, J. Chem. Soc., Dalton Trans. (1997) 2689;
(c) M.A. Malik, N. Revaprasadu, P. O’Brien, Chem. Mater. 13 (2001) 913;
(d) S.L. Cumberland, K.M. Hanif, A. Javier, G.A. Khitrov, G.F. Strouse, S.M.
Woessner, C.S. Yun, Chem. Mater. 14 (2002) 1576;
(e) Y.-J. Hsu, C.-M. Hung, Y.-F. Lin, B.-J. Liaw, T.S. Lobana, S.-Y. Lu, C.W. Liu,
Chem. Mater. 18 (2006) 3323;
(f) T.S. Lobana, Ju.-C. Wang, C.W. Liu, Coordin. Chem. Rev. 251 (2007) 91.
[3] (a) W.A. Rickelton, R.J. Boyl, Separ. Sci. Technol. 23 (1988) 1227;
(b) D.S. Flett, J. Organomet. Chem. 690 (2005) 2426.
(b) B.G. Sukhov, N.K. Gusarova, N.I. Ivanova, M.V. Bogdanova, O.N. Kazheva,
G.G. Alexandrov, O.A. D’yachenko, L.M. Sinegovskaya, S.F. Malysheva, B.A.
Trofimov, J. Struct. Chem. 46 (2005) 1066;
(c) N.K. Gusarova, S.F. Malysheva, V.A. Kuimov, N.A. Belogorlova, V.L.
Mikhailenko, B.A. Trofimov, Mendeleev Commun. 18 (2008) 260.
[10] (a) H. Duddeck, Prog. Nucl. Magn. Reson. Spectrosc. 27 (1995) 1;
(b) H. Duddeck, in: D.M. Grant, R.K. Harris (Eds.), Encyclopedia of Nuclear
Magnetic Resonance, Wiley, New York, 1996. p. 4623.
[4] (a) M.D. Mashkovskii, M. Drugs, Medicina (1998) (in Russian);
(b) G.A. Abdulina, A.M. Gazaliev, G.G. Baikenova, S.D. Fazylov, S.Zh.
Kudaibergenova, Khim. Farm. Zh. 3 (2002) 11.