Alkali metal thioselenophosphinates, M[SeSPR2]: One-pot multicomponent synthesis, DFT study, and synthetic application

Article abstract of DOI:10.1002/ejic.201200947

Diverse alkali metal thioselenophosphinates, M[SeSPR₂] (M = Li, Na, K, Rb, and Cs; R = alkyl, aryl, aralkyl, and hetaralkyl), have been synthesized in 78-94 % yields by means of a one-pot multicomponent reaction between secondary phosphanes, sulfur, selenium, and alkali metal hydroxides under mild conditions (room temperature, -50 °C, 0.5 h, EtOH). The molecular and electronic structure of the [SeSPPh₂]^- anion and its coordination behavior towards Li⁺, Na⁺, and K⁺ cations have been investigated at the B3LYP level of theory. The alkylation of the alkali metal thioselenophosphinates with various organic halides proceeds regiosecifically at the selenium center to form Se-organyl thioselenophosphinates, R₂P(S)SeR (R = Me, Et, Bn, allyl, propargyl), in 78-96 % yields. By the action of molecular iodine, the alkali metal thioselenophosphinates instantly (room temperature, ca. 1 s, 1,4-dioxane) undergo selective Se-Se oxidative coupling to afford the corresponding diselenides, R₂P(S)SeSe(S)PR₂, in 81-92 % yields. The alkali metal thioselenophosphinates are readily converted into the corresponding ammonium derivatives. Square-planar Ni^II complexes, Ni[SeSPR ₂]₂ (R = Ph, CH₂CH₂Ph), have been prepared in 68-81 % yield by the treatment of sodium thioselenophosphinates, Na[SeSPR₂], with NiBr₂ at room temperature (EtOH/CH ₂Cl₂, 10 min). Efficient one-pot multicomponent synthesis of Li, Na, K, Rb, and Cs thioselenophosphinates from secondary phosphanes, sulfur, selenium, and metal hydroxides has been developed. The molecular and electronic structure of the alkali metal thioselenophosphinates has been investigated by DFT (B3LYP) calculations. Their reactivity as well as synthetic usefulness has also been demonstrated. Copyright

Full text of DOI:10.1002/ejic.201200947

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DOI:10.1002/ejic.201200947
Alkali Metal Thioselenophosphinates, M[SeSPR2]: One-
Pot Multicomponent Synthesis, DFT Study, and Synthetic
Application
Alexander V. Artem’ev,[a] Nina K. Gusarova,[a]
Irina Yu. Bagryanskaya,[b] Evgeniya P. Doronina,[a]
Svetlana I. Verkhoturova,[a] Valery F. Sidorkin,[a] and
Boris A. Trofimov*[a]
Keywords: Sulfur / Selenium / Phosphanes / Multicomponent reactions / Solid-state structures
Diverse alkali metal thioselenophosphinates, M[SeSPR2] (M
= Li, Na, K, Rb, and Cs; R = alkyl, aryl, aralkyl, and hetaralk-
yl), have been synthesized in 78–94% yields by means of a
one-pot multicomponent reaction between secondary phos-
phanes, sulfur, selenium, and alkali metal hydroxides under
mild conditions (room temperature, –50 °C, 0.5 h, EtOH). The
molecular and electronic structure of the [SeSPPh2]– anion
and its coordination behavior towards Li+, Na+, and K+ cat-
ions have been investigated at the B3LYP level of theory. The
alkylation of the alkali metal thioselenophosphinates with
various organic halides proceeds regiosecifically at the sele-
nium center to form Se–organyl thioselenophosphinates,
R2P(S)SeRЈ (RЈ = Me, Et, Bn, allyl, propargyl), in 78–96%
yields. By the action of molecular iodine, the alkali metal
thioselenophosphinates instantly (room temperature, ca. 1 s,
1,4-dioxane) undergo selective Se–Se oxidative coupling to
afford the corresponding diselenides, R2P(S)SeSe(S)PR2, in
81–92% yields. The alkali metal thioselenophosphinates are
readily converted into the corresponding ammonium deriva-
tives. Square-planar NiII complexes, Ni[SeSPR2]2 (R = Ph,
CH2CH2Ph), have been prepared in 68–81% yield by the
treatment of sodium thioselenophosphinates, Na[SeSPR2],
with NiBr2 at room temperature (EtOH/CH2Cl2, 10 min).
In sharp contrast, the mixed alkali metal thioselenophos-
phinates, M[SeSPR2], have been virtually ignored, mainly
owing to the lack of expedient methods for their synthesis.
At the same time, such salts are of special interest because
the adjacent sulfur and selenium atoms should impart to
these compounds beneficial features of both dithiophos-
phinates and diselenophosphinates. Moreover, one might
expect that the thioselenophosphinates would possess new,
unpredictably useful proprieties.
In addition, alkali metal thioselenophosphinates are con-
venient starting compounds for the preparation of both S
and Se derivatives of thioselenophosphinic acids[13] as well
as numerous novel and useful metal complexes,[14] some of
which are already applied as single-source precursors for
the fabrication of desired nanomaterials. For instance, sil-
ver(I) thioselenophosphinate, [Ag(SeSPiPr2)]4, is employed
for the deposition of Ag2Se films by means of aerosol-as-
sisted and low-pressure chemical vapor deposition meth-
ods.[11f] More recently, O’Brien et al. have been reported the
use of lead(II) thioselenophosphinate, Pb[SeSPPh2]2, for the
preparation of PbSe micro- and nanocrystals.[15]
Introduction
The alkali metal dithiophosphinates, M[S2PR2], repre-
sent one of the most studied classes of chalcogeno-phos-
phorus organic compounds.[1] They are widely used as ex-
traction[2] and flotation[3] reagents, versatile ligands in coor-
dination chemistry,[4] and intermediates for the synthesis of
lubricant oil additives,[5] agrochemicals,[6] vulcanization ac-
celerators,[7] antitumor and antimicrobial agents,[8] as well
as single-source precursors (SSPs) of remarkable nanomat-
erials.[9] The selenium analogues, the diselenophosphinates,
M[Se2PR2], are less studied,[10] although in recent years
they have gained special attention on account of their appli-
cations as ligands for the design of SSPs to advanced nano-
materials[11] and building blocks for organic and inorganic
syntheses.[12]
[a] A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences,
1 Favorsky Str., 664033 Irkutsk, Russian Federation
Fax: +7-3952-419346
E-mail: boris_trofimov@irioch.irk.ru
Homepage: http://www.irkinstchem.ru
[b] N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch, Russian Academy of Sciences,
9 Lavrentiev Ave., 630090 Novosibirsk, Russian Federation
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200947.
A conventional approach to the synthesis of the alkali
metal thioselenophosphinates is conducted on the basis of
the reaction of monochlorophosphanes R2PCl with elemen-
tal sulfur or selenium to form R2P(X)Cl (X = S or Se) fol-
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lowed by treatment with NaSeH or NaSH, respectively, to mental sulfur and selenium, and alkali metal hydroxides,
give sodium salt, Na[SeSPR2] (R = Et, Ph) in 50–78% total which has in fact proven to be a novel general and efficient
yield[14d,16] (Scheme 1).
synthesis of alkali metal thioselenophosphinates. Further-
more, preliminary results on application of the synthesized
salts and their study by DFT calculations are also reported.
Results and Discussion
Synthesis of Alkali Metal Thioselenophosphinates
Our experiments have shown that secondary phosphanes
1a–f react with elemental sulfur (S8), elemental selenium,
and alkali metal hydroxides in a 1:0.125:1:1 molar ratio
(room temp., –50 °C, 0.5 h, EtOH) to selectively afford alk-
ali metal thioselenophosphinates 2a–l in 78–94% yields
(Table 1).
Scheme 1. A conventional syntheses of sodium thioselenophos-
phinates.
The preparation of sodium diethylthioselenophosphin-
ate, Na[SeSPEt2]·2H2O, in low yield (35%) by the reaction
of tetraethyldiphosphane disulfide, Et2P(S)P(S)Et2, with so-
dium selenide and elemental selenium (Scheme 2) has also
been reported.[16]
Table 1. One-pot synthesis of alkali metal thioselenophosphinates
2a–l.
Scheme 2. An alternative route to sodium thioselenophosphinate.
Murai et al. have published[13] the original approach to
alkali metal thioselenophosphinates, which involves several
synthetic steps that utilize phenyldichlorophosphane, Grig-
nard and organolithium reagents, elemental selenium, alkali
metal fluorides, 18-crown-6 ether, as well as 2-(trimethyl-
silyl)ethanethiol (Scheme 3). Notably, this method allows
one to obtain the K, Rb, and Cs thioselenophosphinates
only as complexes with 18-crown-6 ether.[13]
Scheme 3. Synthesis of alkali metal thioselenophosphinates.
Clearly, the above reactions suffer from unsatisfactory
atom economy. Therefore, it is highly desirable to invent a
more straightforward approach for the synthesis of alkali
metal thioselenophosphinates.
[a] All yields refer to isolated products.
As seen in Table 1, this multicomponent reaction has
proved to be a very general route for a wide array of Li, Na,
Recently,[17] we briefly disclosed the synthesis of alkylam- K, Rd, and Cs thioselenophosphinates. Indeed, a variety of
monium thioselenophosphinates from secondary phos- secondary phosphanes have been involved in this reaction,
phanes, sulfur, selenium, and amines.
in which alkyl, aralkyl, hetaralkyl, and aryl substituents ap-
The present work is aimed at unfolding this promising pear to be suitable.
approach further, and extending its scope in particular. To
It is worth noting that the multicomponent reaction pro-
that end, we have implemented for the first time the multi- ceeds with 100% atom economy except for the elimination
component reaction between secondary phosphanes, ele- of water. Moreover, a nontoxic “green” solvent[18] (95%
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aqueous ethanol) has been used in the synthesis. As men- been reported.[13,16,19] However, such esters are promising
tioned above, conventional syntheses of thioselenophos- precursors for creating advanced nanomaterials and agro-
phinates require toxic (especially dry) solvents (e.g., THF, chemicals from metal chalcogenides. To obtain the new rep-
1,4-dioxane, or benzene).[13,16]
resentatives of thioselenophosphinic esters, salts 2a,c–e,j,k
The synthesized thioselenophosphinates 2a–l are micro- were introduced into the reaction with various organic hal-
crystalline powders, stable in air for several days. These ides. Experiments have shown, that in all the cases, alkyl-
compounds are highly soluble in water and in polar organic ation takes place chemoselectively at the selenium center of
solvents (e.g., DMSO, EtOH, CHCl3, 1,4-dioxane). Unfor- the ambident [SeSPR2]– anion with the formation of the
tunately, attempts to obtain single crystals of alkali metal corresponding Se-esters 3a–f in 78–96% yield (Table 2).
salts 2a–l were unsuccessful.
This result is in good agreement with the data of Murai et
The structures of compounds 2a–l have been proved by al.[13b] on the reaction of tetraalkylammonium salts,
multinuclear NMR (1H, 13C, 31P, and 77Se) and IR spec- [Bu4N][SeSPPh2] and [Me4N][SeSP(tBu)Ph], with MeI or
troscopy. The 31P NMR spectra of thioselenophosphinates allyl bromide.
2a–l show a sharp singlet in the range of δ = 43.98–
Table 2. Chemoselective reaction of thioselenophosphinates with
73.84 ppm, flanked by one typical pair of 77Se satellites
organic halides.
(1JP,Se = 550–645 Hz). The 77Se NMR spectra display a
doublet (1JP,Se = 550–645 Hz) in the range of δ = –86 to
4 ppm. The values of 31P,77Se coupling constants are be-
tween the coupling constant values for phosphorus–
selenium single (200–600 Hz) and double bonds (800–
1200 Hz), thus corresponding to a phosphorus–selenium
1
bond order of approximately 1.5. The H and 13C NMR
spectra of 2a–l reveal the presence of corresponding organic
groups at the phosphorus atoms. In the solid-state IR spec-
tra of 2a–l, strong bands at 560–630 cm–1 correspond to
stretching vibrations of the P–S bonds. Stretching vi-
brations of the P–Se bond are observed in the region of
450–525 cm–1.
The tentative pathway of thioselenophosphinate forma-
tion in this multicomponent reaction includes the following
steps: (i) oxidation of phosphanes 1 with elemental sulfur
to give secondary phosphane sulfides A; (ii) deprotonation
of the latter by the metal hydroxides, MOH, to generate
the P, S -ambident thiophosphinite B; and (iii) oxidation of
anions B with elemental selenium to afford thiselenophos-
phinate 2 (Scheme 4).
[a] All yields refer to isolated products.
Scheme 4. The possible mechanism of the multicomponent reaction
between secondary phosphanes, sulfur, selenium, and alkali metal
hydroxides.
The synthesis of thioselenophosphinic bis-ester 3g in
high yield (93%) by the treatment of salt 2j with 1,3-
bis(chloromethyl)benzene at a 2:1 molar ratio under the
same conditions has additionally demonstrated the general-
ity of this reaction (Scheme 5).
Reactivity of Alkali Metal Thioselenophosphinates
Moreover, the thioselenophosphinic Se-esters 3a–f can
be successfully synthesized with the same yield in a one-
pot procedure by means of the multicomponent reaction
between secondary phosphanes 1a,b,f, sulfur, selenium,
MOH, and R2-Hal (Hal = halide) (Scheme 6).
To elucidate the reactivity of alkali metal thioseleno-
phosphinates and to demonstrate their applicability to the
synthesis of more complex chalcogeno-phosphorus organic
compounds, we have investigated some reactions that in-
volve thioselenophosphinates 2a–e,j,k, namely, (i) alkylation
with organic halides, (ii) oxidation by molecular iodine, and
(iii) counterion exchange.
The structure of thioselenophosphinic esters 3a–g clearly
follows from their 31P and 77Se NMR spectra. In particular,
the 31P NMR spectrum of 3a–g shows a sharp singlet at δ
= 53–87 ppm flanked by one set of 77Se satellites (1JP,Se
=
Synthesis of Thioselenophosphinic Se-Esters
344–365 Hz), whereas the 77Se NMR spectrum contains a
The data on the thioselenophosphinic esters are very lim- doublet at δ = 239–362 ppm with a characteristic one-bond
ited: only about ten examples of these compounds have 31P,77Se coupling of 344–365 Hz. The presence of the P=S
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Table 3. Chemoselective reaction of thioselenophosphinates with
elemental iodine.
Entry
Salt
R1
M
Product
Yield[a] [%]
1
2
3
4
2a
2b
2e
2k
Cy
Na
Li
Cs
K
4a
4b
4b
4c
85
82
92
81
(CH2)2Ph
(CH2)2Ph
Ph
Scheme 5. Synthesis of thioselenophosphinic bis-esters 3g.
[a] All yields refer to isolated products.
distributed over the
S
atom (Figure 1). Therefore,
[R2PSeS]· radicals should act as Se-centered ones. Indeed,
the experimentally observable products are diselenides 3a–
c. Moreover, calculations [B3LYP/6-31+G(d,p)] of three al-
ternative products of dimerization of [Me2PSeS]· radicals
[i.e., (Me2P=S)2Se, Me2P(Se)S–Se(S)PMe2, and (Me2-
P=Se)2S] have confirmed that the diselenide is more stable
than the disulfide and thioselenide by 17.8 and
7.9 kcalmol–1, respectively.
Scheme 6. One-pot synthesis of thioselenophosphinic esters 3a–f.
bond in esters 3a–g is supported by the appearance of a
strong band in the region 612–646 cm–1 in the IR spectra.
DFT calculations of the two model isomers, Ph2P(S)-
SeMe and Ph2P(Se)SMe, have confirmed that the Se-esters
are more stable than the S-esters; the difference in Gibbs
free energies calculated at the B3LYP/6-31+G(d,p) level is
4.5 kcalmol–1.
Synthesis of Bis(diorganothiophosphanyl)diselenides
The oxidative dimerization of thioselenophosphinate
anions by the action of the appropriate oxidant is a promis-
ing route to the corresponding disufides, diselenides, or
mixed species (i.e., thioselenides). These compounds are
supposed to be prospective intermediates for the direct syn-
thesis of thioselenophosphinic diesters by means of the ad-
dition to alkenes and alkynes.
Figure 1. Electron-density plot for the singly occupied molecular
orbital (SOMO) of [Me2PSeS]· free radical calculated at the UB3-
LYP/6-31+G(d,p) level.
We have found that the treatment of thioselenophosphin-
ates 2a,b,e,k with elemental iodine in a 2:1 molar ratio gives
It should be emphasized that compounds 4a–c are repre-
diselenides 4a–c chemoselectively in 81–92% yields sentatives of a rare family of bis(diorganothiophosphanyl)-
(Table 3). The reaction instantly proceeds in 1,4-dioxane at diselenides, (R2P=S)2Se2. Currently, only two representa-
room temperature to avoid the formation of the expected tives of these diselenides have been prepared, namely,
[20]
disulfides, (R2P=Se)2S2, or thioselenides, R2P(Se)S–Se(S)- [Ph(tBu)P=S]2Se2 and (Et2P=S)2Se2.[16,21]
PR2 (31P NMR spectroscopy).
Diselenides 4a,b are air- and moisture-stable red-orange
To understand the chemo- and regioselectivity of the oxi- crystals, which are highly soluble in most organic solvents.
dative coupling of thioselenophosphinate anions, DFT These compounds have been characterized in solution and
computations were performed. We suggest that such a cou- the solid state by multinuclear NMR spectra and X-ray
pling is triggered by the one-electron oxidation of [R2PSeS]– crystallography.
¯
Diselenide 4a crystallizes in the triclinic P1 space group,
anions with iodine to afford the corresponding free radicals,
[R2PSeS]·, which are the key precursors of the reaction whereas diselenide 4b crystallizes in the monoclinic C2/c
products. Apparently, the structure of the latter strongly de- space group with a solvating benzene molecule per unit.
pends on localization of the unpaired electron in intermedi- Their crystallographic data are listed in Table 4. The struc-
ate [R2PSeS]· radicals. Our calculation [UB3LYP/6- ture of 4a is formed by two crystallographically indepen-
311+G(d,p)] of the model [Me2PSeS]· free radical shows dent (Cy2P=S)2Se2 molecules, one of which is shown in Fig-
that approximately 60% of the spin density is localized on ure 2. The molecular structure of diselenide 4b is presented
the Se atom, and approximately 40% of the spin density is on Figure 3. As expected, the P atoms in diselenides 4a,b
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Table 4. Data collection and refinement parameters for 2m, 4a,b, and 5a,b.
2m
4a
4b
5a
5b
Empirical formula
C32H44N2P2S2Se2
740.67
P1
C48H88P4S4Se4
1233.14
P1
C38H42P2S2Se2
782.70
C2/c
35.555(10)
6.0157(14)
37.465(10)
90.00
113.280(17)
90.00
7361(3)
8
1.413
2.235
200
C24H20NiP2S2Se2
651.09
C2/c
10.5564(3)
15.1155(5)
16.2080(4)
90.00
106.413(1)
90.00
2480.85(12)
4
1.743
4.025
200
C32H36NiP2S2Se2
763.30
P1
Formula mass [gmol–1]
¯
¯
¯
Space group
a [Å]
b [Å]
c [Å]
α [°]
9.6873(7)
13.8550(11)
15.1765(12)
114.657(2)
99.788(3)
91.719(2)
1812.7(2)
4
12.3414(14)
12.8348(13)
20.750(2)
75.470(4)
73.031(4)
68.788(4)
2891.6(5)
4
9.2442(5)
10.2796(6)
10.2934(6)
102.506(2)
108.251(2)
109.609(2)
816.55(8)
1
β [°]
γ [°]
V [Å3]
Z
Dcalcd. [gcm–3
μ [mm–1]
T [K]
]
1.357
2.266
200
1.416
2.823
240
1.552
3.070
200
Reflections collected
Independent reflections
R1, wR2 [IϾ2σ(I)]
R1, wR2 (all data)
Goodness of fit
48935
93610
22800
26271
27110
7175 (Rint = 0.0532) 12584 (Rint = 0.0447) 7805 (Rint = 0.0372) 4212 (Rint = 0.0441) 4854 (Rint = 0.0392)
0.0471, 0.1289
0.0699, 0.1463
1.093
0.0261, 0.0699
0.0393, 0.0924
1.182
0.0595, 0.1599
0.0906, 0.1845
1.065
0.0287, 0.0712
0.0416, 0.0761
1.078
0.0311, 0.0859
0.0446, 0.0913
1.127
Largest diff. peak and hole [eÅ–3] 1.18 and 0.59
0.53 and –0.61
1.99 and –1.07
0.42 and –0.36
0.46 and –0.34
adopt a slightly distorted tetrahedral geometry. The P–S
bond lengths in 4a,b lie in the range of 1.943–1.960 Å,
which is comparable to 1.940(2) Å in [Ph(tBu)P=S]2Se2.[20]
The average Se–Se distances (2.335 Å) fall close to the val-
ues found in similar diselenido compounds.[20–22] The P–Se
bond lengths range 2.252–2.309 Å, which are comparable
to those observed in compounds that bear the PV–Se single
bonds.[20–23] Both molecules of 4a have similar structural
motifs and display sin–anti configuration of the S–P–Se–
Se–P–S unit with Se–Se–P–S torsion angles of 22.03(4) and
175.34(3)° for one molecule and –18.98(4) and –170.98(3)°
for the other molecule. In contrast, the S–P–Se–Se–P–S
chain in diselenide 4b adopts an anti–anti configuration
with Se–Se–P–S torsion angles of –167.65(9) and
177.87(8)°. The P–Se–Se–P torsion angles in the both dis-
elenides have an anti configuration with values of
–129.17(2) and 130.36(3)° for 4a and 146.36(7)° for 4b.
Figure 3. Perspective view of diselenide 4b (30% thermal ellipsoid)
with benzene solvate molecule omitted for clarity. Selected bond
lengths [Å] and angles [°]: Se1–Se2 2.3867(11), Se1–P1 2.2524(18),
Se2–P2 2.2569(17), P1–S1 1.956(2), P2–S2 1.946(2), P1–Se1–Se2
98.70(5), P2–Se2–Se1 102.36(5), S1–P1–Se1 105.76(8), S2–P2–Se2
106.65(8).
Synthesis of Alkylammonium Thioselenophosphinates
In the example of the conversion of K[SeSPPh2] (2k) to
Et2NH2[SeSPPh2] (2m), it has been shown that alkali metal
thioselenophosphinates can be successfully used for prepa-
ration of the corresponding alkylammonium salts. Thus,
acidification of salt 2k with a solution of HCl in methanol
(room temp., 5 min, MeOH) followed by treatment with di-
ethylamine furnishes the corresponding ammonium salt 2m
in 89% isolated yield (Scheme 7).
Figure 2. Perspective view of diselenide 4a (30% thermal ellipsoid).
Selected bond lengths [Å] and angles [°]: Se–Se 2.3346(4); P–Se
2.2544(7)–2.3092(7); P–S 1.9430(9)–1.9599(9); S–P–Se 104.49(3)–
116.37(4); P–Se–Se 99.761(19)–102.80(2).
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Scheme 7. Synthesis of N,N-diethylammonium thioselenophos-
phinate 2m.
According to X-ray analysis, thioselenophosphinate 2m
¯
crystallizes in the triclinic space group P1. The selected
crystallographic data for 2m are presented in Table 4. The
structure of 2m is formed by two sets of crystallographically
independent [SeSPPh2]– and [Et2NH2]+ ions. The geometry
of the phosphorus atom in the [SeSPPh2]– anion is a dis-
torted tetrahedron (Figure 4). The S and Se atoms in both
independent anions are disordered over two positions with
Se/S:SЈ/SeЈ occupancy ratios of 0.66:0.34 and 0.74:0.26. It
is worth noting that such disordering of chalcogen atoms is
quite typical for salts of thioselenophosphinic acids.[13,15,17]
Figure 5. Fragment of the 1D infinite chains in the crystal of com-
pound 2m.
Synthesis of NiII Thioselenophosphinate Complexes
Currently, the investigation of reactions of thioseleno-
phosphinates 2a–l with heavy-metal ions is underway, and
some preliminary results on the preparation and characteri-
zation of Ni[SeSePR2]2 complexes are reported herein. It
should be emphasized that there are no structurally charac-
terized examples of nickel thioselenophosphinates. How-
ever, examples of dithiophosphinato,[2a] diselenophosphin-
ato,[11c,11e] and diselenophosphonato[25] NiII complexes are
known.
We have found that reaction of sodium salt 2c or 2k with
NiBr2 in a 2:1 molar ratio proceeds under mild conditions
(room temp., EtOH/CH2Cl2, 10 min) to give NiII thio-
selenophosphinates 5a,b in high yields (Scheme 8).
Figure 4. Perspective view of the [Ph2PSeS]– anion (shows one of
two independent anions) in salt 2m (30% thermal ellipsoid). The S
and Se atoms are disordered over two positions.
One-dimensional infinite chains of molecules 2m along
the a axis are formed in the crystal through intermolecular
hydrogen bond N–H···S with parameters detailed in Table 5
and Figure 5. Notably, the normal S···H and Se···H con-
tacts are 2.92 and 3.10 Å.[24] In addition to the hydrogen
bond, the C–H···π interaction of the hydrogen atoms of the
C4–H, C7–H, and C24–H bonds with phenyl rings are ob-
served; the atom-to-plane distances are 2.91, 2.89, and
2.92 Å.
Scheme 8. Synthesis of NiII thioselenophosphinates.
Complexes 5a,b were isolated as dark green crystals,
which are soluble in dichloromethane and chloroform. The
molecular structures of NiII thioselenophosphinates have
been established by single-crystal X-ray diffraction (Fig-
ures 6 and 7). The selected crystallographic data are given
in Table 4. The selenium and sulfur atoms in the NiII thio-
selenophosphinates are disordered over two positions in
an Se/S:SeЈ/SЈ ratio of 0.662:0.338(1) (for 5a) and
0.565:0.435(1) (for 5b) with the retention of the cis arrange-
ment of selenium atoms. In each complex, the nickel atom
is located on the crystallographic inversion center and is
coordinated by four chalcogen atoms of thioselenophos-
phinate ligands in a square-planar geometry. Therefore,
both [SeSPR2] groups act as S,Se-bidentate ligands. For 5a,
the Ni(SePS)2 metallobicycle formed is nonplanar: the
maximum and minimum deviations from the mean plane
constituted by P1, S1, Se1, and Ni1 are 0.200 and 0.102 Å,
Table 5. Hydrogen-bonding parameters [Å and ] for compound 2m
(Ch = S, Se).
N–H···Ch
N–H [Å] H···Ch [Å] N···Ch [Å] N–H···Ch angle [°]
N1–H···S1
N1–H···Se1
N1–H···S2
N2–H···S1
N2–H···Se2
N2–H···S2
0.92
0.92
0.92
0.92
0.92
0.92
2.73
2.87
2.37
2.48
2.73
2.66
3.476(7)
3.633(4)
3.289(5)
3.383(7)
3.539(4)
3.341(5)
139
141
172
167
147
131
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respectively. Meanwhile, the corresponding values for 5b are DFT Study of Alkali Metal Thioselenophosphinates
0.029 and 0.005 Å [i.e., the Ni(SePS)2 unit in this com-
Before this work, data on the structural chemistry of alk-
pound is almost planar]. As expected, the P atoms in 5a,b
ali metal thioselenophosphinates were scarce, if any. In par-
adopt a slightly distorted tetrahedral geometry. The C–P
ticular, X-ray investigations and quantum-chemical models
bond lengths lie in the range 1.801–1.817 Å, which are com-
of these compounds have not been reported. Therefore, mo-
parable to the corresponding values in similar NiII complex-
lecular and electronic structures as well as coordinating
es.[11c,11e]
capability of [SeSPR2]– anions toward alkali metal cations
remain unexplored.
To address this challenge, we have performed DFT in-
vestigations of Li, Na, and K diphenylthioselenophosphin-
ates, M[SeSPPh2] and M2[SeSPPh2]2, at the B3LYP [6-
31+G(d,p), 6-311++G(d,p), and 6-311++G(3df,3pd)] level
of theory in the Gaussian 09 package.[26]
Our calculations have revealed that the phosphorus atom
in the [SeSPPh2]– anion adopts a distorted tetrahedral envi-
ronment (see the bond-angle values in Figure 8). The P–Se
and P–S bond lengths are intermediate between the corre-
sponding single and double bonds. Indeed, in the optimized
geometry [B3LYP/6-31+G(d,p)] of Se–methyl thioseleno-
phosphinate, Ph2P(S)SeMe, P=S and P–Se distances are
Figure 6. Perspective view of complex 5a (30% thermal ellipsoid).
1.971 and 2.277 Å; whereas in the isomeric ester, Ph2P(Se)-
The S and Se atoms are disordered over two positions with Se/S:SЈ/
SMe, P–S and P=Se bonds lengths are 2.116 and 2.146 Å,
SeЈ occupancy ratio of 0.662:0.338(1).
respectively (Figure S2 in the Supporting Information).
Figure 8. B3LYP/6-31+G(d,p) optimized geometry of [SeSPPh2]–
anion and view of its HOMO.
The influence of the basis-set size on the geometrical pa-
rameters of the [SeSPPh2]– anion is insignificant. For in-
stance, the differences in bond lengths and bond angles are
less than 0.02 Å and 1.1°, respectively (see Table S1 in the
Supporting Information). Therefore, the further DFT study
was carried out at the B3LYP/6-31+G(d,p) level of theory.
Atomic charges have been calculated using natural bond-
Figure 7. Perspective view of complex 5b (30% thermal ellipsoid).
The S and Se atoms are disordered over two positions with Se/S:SЈ/
SeЈ occupancy ratio of 0.565:0.435(1).
The solid-state IR spectra of NiII thioselenophosphinates ing orbital (NBO) analysis[27] for the HF/6-31+G(d,p) wave
show bands at 563, 537 (for 5a) and 589, 568, 552 cm–1 (for function. As expected, the negative charge of the
5b), which are assigned to the P–S stretching vibration. The [SeSPPh2]– anion is distributed between sulfur and selenium
P–Se bond-stretching vibrations occur at 503, 475, 420 (for atoms. The absolute charge value on the sulfur atom
5a) and 501, 468, 458, 430 cm–1 (for 5b).
(–0.750) is a little bit larger than on the selenium atom
To investigate the cis/trans isomerism of NiII thioseleno- (–0.709). On the contrary, according to data from Murai et
phosphinates, DFT gas-phase calculations [B3LYP/6- al.,[13b] the Mulliken charges [HF/6-31+G(d)] on the chalco-
311++G(df,p)] of model isomers of Ni(SeSPMe2)2 have gen atoms in the simplest [SeSPH2]– anions are –0.670 for
been performed. The trans-Ni(SeSPMe2)2 turned out to be S and –0.831 for Se. Note that the NBO charges in the
more stable than the cis isomer by 0.2 kcalmol–1 (Figure S1 [SeSPH2]– anion additionally calculated by us show that the
in the Supporting Information).
S atom is more negative (–0.802) than the Se atom (–0.767).
The synthesized NiII complexes are highly prospective The inconsistency between NBO and Mulliken charges is
SSPs to nickel chalcogenide and/or phosphide nanopar- due to the known problems of atom-charge evaluation.[28]
ticles that possess many remarkable properties.
Nevertheless, literature data indicate that the NBO analysis
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is preferable to the Mulliken calculations.[28,29] Shapes of
The absolute values of the formation energies, ΔEc, of
the HOMO in [SeSPPh2]– (Figure 8) and [SeSPH2]–[13b] M[SeSPPh2] complexes in the gas phase (with zero-point
anions are in good compliance, which testifies to a greater vibrational energy contributions) are over 110 kcalmol–1
localization of the HOMO on the Se atom. According to (Figure 9). Notably, Li[SeSPPh2] is the most stable, whereas
the hard and soft (Lewis) acids and bases (HSAB) K[SeSPPh2] is the least stable.
theory,[30] the results obtained demonstrate that the Se atom
It is worth noting that the interaction of alkali metal cat-
in the thioselenophosphinate anion is a relatively softer nu- ions with the thioselenophosphinate anion might result in
cleophilic site than the S atom towards electrophiles. In- the formation of not only monomers M[SeSPPh2], but also
deed, protonation and acylation of thioselenophosphinates dimers M2[SeSPPh2]2. This is supported by the examples
proceed on the sulfur atom (charge control), whereas alkyl- of Li2(SeSPPh2)2 and K2(SeSPPh2)2 (Figure 10), which also
ation occurs on the selenium atom (orbital control), which correspond to minima on the PES. The structure of the di-
corresponds to the literature[13b] and our data (see above).
mers M2[SeSPPh2]2 depends substantially on the cation M+
On the potential energy surface (PES) of interaction of size. Indeed, if for K2(SeSPPh2)2 the coordination contacts
the [SeSPPh2]– anion with Li+, Na+, and K+ cations, the KSe (KЈSeЈ) and KSeЈ (KЈSe) are observed (Figure 10), in
minima are found to correspond to M[SeSPPh2] complexes the case of Li2(SeSPPh2)2 only LiSe and LiЈSeЈ appear
(Figure 9). The alkali metal cation in the structure of (LiSeЈ and LiЈSe distances are more than 4.1 Å). Upon go-
M[SeSPPh2] interacts simultaneously with S and Se atoms ing from M[SeSPPh2] to M2[SeSPPh2]2 the P–S and P–Se
of the [SeSPPh2]– anion, thus forming the almost planar bond lengths remain almost unchanged, whereas the SPSe
four-membered MSPSe cycle. When increasing the size of angle value decreases by approximately 3°. The most signifi-
the metal cation, the SPSe bite angle increases from 112.8 cant differences are observed for the M–S and M–Se bond
to 118.0°, whereas the M–S and M–Se bond lengths de- lengths: they are substantially higher in dimers
crease. At the same time, the P–S and P–Se bond lengths M2[SeSPPh2]2 than in M[SeSPPh2] (see Figures 9 and 10).
change insignificantly (Figure 9).
Figure 9. B3LYP/6-31+G(d,p)-optimized geometries of M[SeSPPh2] complexes in the gas phase and corresponding complexation energies,
ΔEc = E(M[SeSPPh2]) – {E([SeSPPh2]–) + E(M+)}.
Figure 10. B3LYP/6-31+G(d,p)-optimized geometries of M2[SeSPPh2]2 complexes in the gas phase and corresponding dimerization ener-
gies, Ed = E(M2[SeSPPh2]2) – 2E(M[SeSPPh2]).
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Figure 11. B3LYP/6-31+G(d,p)-optimized geometries of M[SeSPPh2] complexes in a water solution and the corresponding complexation
energies.
As expected,[31] in the highly polar solution [ε = 78.35; other structural units. For example, if Li(Se2PPh2)·(THF)·
conductor-like polarizable continuum model (C-PCM)],[32] (TMEDA) (TMEDA = tetramethylethylenediamine) is a
the interaction of cationic and anionic units of M[SeSPPh2] monomer,[33] K2(Se2PPh2)2·(THF)2 isolated from the mix-
and M2[SeSPPh2]2 salts is insignificant (see ΔEc values in ture of THF/toluene represents a dimer,[34] and [Na2-
Figure 11, and Ed in Figure 12). In this case, the structural (Se2PPh2)·THF·5H2O] obtained under more polar condi-
parameters of the anionic part of M[SeSPPh2] and tions (THF/EtOH) is a polymer.[35]
M2[SeSPPh2]2 are close to those of the free [SeSPPh2]–
A detailed investigation of the structure of thioseleno-
anion (see, for example, the data in Figures 8 and 11). phosphinate salts with alkali metals (depending on proper-
Moreover, according to the positive values of complexation ties of medium and cations) is a very laborious task and
free energy for Li[SeSPPh2] and K2[SeSPPh2]2 under the lies far beyond the scope of this study.
standard conditions in the highly polar solution (ε = 78.35;
C-PCM model), these complexes are dissociated (see ΔGc
in Figure 11 and ΔGd in Figure 12). Meanwhile, Na-
[SeSPPh2] and K[SeSPPh2] complexes are in equilibrium
with their ions.
Conclusion
In summary, a novel, general, and high-yield method for
the synthesis of diverse Li, Na, K, Rb, and Cs thioseleno-
phosphinates has been developed by exploiting the one-pot
multicomponent reaction between secondary phosphanes,
sulfur, selenium, and metal hydroxides. The reaction pro-
ceeds under mild conditions to provide the new or pre-
viously unavailable alkali metal thioselenophosphinates that
bear alkyl, aralkyl, hetaralkyl, and aryl substituents. The
structure of the [SeSPPh2]– anion and its coordination to-
ward Li+, Na+, and K+ cations have been studied theoretic-
ally by DFT (B3LYP) calculations. The reactivity as well as
the synthetic usefulness of the prepared thioselenophosphi-
nates has been demonstrated by reactions with organic hal-
ides, iodine, and the cation exchange, which leads to the
earlier unknown or unavailable thioselenophosphinic deriv-
atives. The sodium thioselenophosphinates have been used
as precursors of NiII–thioselenophosphinato square-planar
complexes. According to X-ray analysis of the latter, the
Figure 12. B3LYP/6-31+G(d,p)-optimized geometry of the [SeSPR2] ligands coordinate to the NiII ion in a S,Se-biden-
K2[SeSPPh2]2 complex in a water solution and the corresponding
dimerization energy.
tate fashion to form Ni(PSeS)2 metallobicycles. The results
obtained significantly contribute to the fundamental chem-
istry of thio- and selenophosphorus compounds.
If one were to take into account the effect of not only
polar but also donor–acceptor properties of the solvent, the
interaction of alkali metal cations with thioselenophosphin-
Experimental Section
ate anoins might lead to the formation (depending on the
size of M+) of solvent-separated pairs, M+[SeSPPh2]– com-
Materials and Methods: All manipulations were performed under
plexes, M2[SeSPPh2]2 dimers, Mn[SeSPPh2]n polymers, and an argon atmosphere. Melting points (uncorrected) were measured
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with a Stuart SMP3 apparatus. The microanalyses were performed
with a Flash EA 1112 CHNS elemental analyzer. FTIR spectra
were performed with a Bruker Vertex 70 FT-IR spectrometer. The
1H, 13C, 31P, and 77Se NMR spectra were recorded with a Bruker
AV-400 spectrometer (400.13, 100.61, 161.98, and 76.31 MHz,
respectively) at ambient temperature using the solvent as reference,
except for the 31P and 77Se NMR spectroscopy, in which the chemi-
cal shifts are relative to H3PO4 (85% in D2O) and Me2Se, respec-
tively.
dried under vacuum (1 Torr, 40–45 °C) to afford the target Se-esters
of thioselenophosphinic acids 3a–f.
Oxidative Coupling of Thioselenophosphinate 2a,b,e,k by the Action
of Iodine: Table 3. A solution of elemental iodine (254 mg, 1 mmol)
in 1,4-dioxane (10 mL) was added dropwise at room temp. to a
stirring solution of thioselenophosphinate 2a,b,e,k (2 mmol) in 1,4-
dioxane (10 mL). A white precipitate (alkali metal iodide) formed
immediately. The resulting mixture was then diluted with water
(30 mL) and extracted with benzene (2ϫ20 mL). The extract was
dried with Na2SO4 and concentrated to one-tenth of its volume.
Upon addition of hexane (15 mL) to the resulting solution and
exposure at 5–8 °C overnight, diselenide 4a–c was precipitated as a
microcrystalline solid. The latter was washed with cooled hexane
(5 mL) and dried under vacuum (1 Torr). Single crystals of 4a,b
suitable for an X-ray analysis were obtained by cooling of their
benzene/hexane solutions up to 3–5 °C over several days.
Ethanol (5% water content) and benzene were employed as re-
ceived. Diethyl ether and 1,4-dioxane were distilled from metallic
Na and Na/benzophenone, respectively, before use. Dicyclohex-
ylphosphane (1a) and diphenylphosphane (1f) were purchased from
Aldrich, whereas secondary phosphanes 1b–e were prepared in a
single step from red phosphorus and styrene,[36a] α-methylstyr-
ene,[36a] 4-methoxystyrene,[36b] or 2-vinylfuran[36a] according to lit-
erature methods. Organic halides were distilled prior to use. All
other chemicals were obtained commercially and used without fur-
ther purification.
Synthesis of Diethylammonium Salt 2m: Scheme 7. A solution of
hydrochloric acid (1 m, 1 mL, ca. 1 mmol) in methanol was added
at room temp. to a solution of the potassium thioselenophosphin-
ate 2k (335 mg, 1 mmol) in MeOH (6 mL). The mixture was stirred
for 5 min at the same temperature, and diethylamine (73 mg,
1 mmol) was added. The KCl precipitate was removed by filtration,
and solvent was evaporated from the filtrate. The residue obtained
was washed with dry Et2O (2ϫ5 mL) and dried under vacuum
(1 Torr) to give thioselenophosphinate 2m in 89% yield. Single
crystals of 2m were grown by slow evaporation of its ethanol solu-
tion at 3–5 °C.
Safety Note: Selenium and its derivatives are toxic! These materials
should be handled with great care.
Typical Procedure for Synthesis of Alkali Metal Thioselenophos-
phinates 2a–l: See Table 1. Powdered S8 (32 mg, 0.125 mmol) was
added to a solution of freshly distilled secondary phosphane 1a–f
(1 mmol) in EtOH (7 mL), and the mixture was stirred at room
temp. until the dissolution of sulfur residue (ca. 20 min). Amorph-
ous gray selenium (79 mg, 1.00 mmol) and
a solution of
MOH·nH2O (n = 0 for Li and Na; n = 0.5 for K; n = 1 for Rb and
Cs; 1.0 mmol) in EtOH (8 mL) were consecutively added to the
transparent solution thus obtained. The resulting mixture was
stirred at 40–50 °C until the dissolution of the selenium powder
(ca. 10 min). The solvent was removed under reduced pressure, then
the residue was washed with dry Et2O (2ϫ10 mL) and dried under
vacuum (1 Torr, 40–45 °C) to afford thioselenophosphinates 2a–l.
Synthesis of NiII Thioselenophosphinates: See Scheme 8. A solution
of thioselenophosphinate ligand 2c or 2k (1 mmol) in EtOH (5 mL)
was added to a suspension of NiBr2 (109 mg, 0.5 mmol) in CH2Cl2
(20 mL). The mixture was stirred for 10 min at room temp. and
diluted with H2O (30 mL). The organic layer was additionally
washed with H2O (2ϫ10 mL), dried with Na2SO4, and evaporated
under vacuum. The solid was dissolved in CH2Cl2 (10 mL) and
layered with hexane (15 mL) to afford complexes 5a,b as dark-
green crystals.
Alkylation of Alkali Metal Thioselenophosphinates 2a,c–e,j,k with
Organic Halides: See Table 2. A corresponding organic halide
(1.1 mmol) [for the preparation of bis-ester 3g, 1,3-bis(chlorome-
thyl)benzene (0.5 mmol) was used (Scheme 5)] was added at room
temp. to a solution of thioselenophosphinate 2a,c–e,j,k (1 mmol) in
EtOH (8 mL). The mixture was stirred for 10 min at 40–43 °C. The
solvent and the excess amount of organic halide were removed un-
der reduced pressure, and dry Et2O (10 mL) was added to the resi-
due. The precipitated white powder (alkali metal halide) was re-
moved by filtration, and Et2O was evaporated from the filtrate.
The residue obtained was dried under vacuum (1 Torr, 40–45 °C)
to afford the corresponding Se-esters of thioselenophosphinic acids
3a–g.
X-ray Diffraction Analysis: X-ray crystallography studies of the
crystals were carried out with a Bruker Kappa Apex II CCD dif-
fractometer using φ,ω scans of narrow (0.5°) frames with Mo-Kα
radiation (λ = 0.71073 Å) and a graphite monochromator. The
structure was solved by direct methods and refined by full-matrix
least-squares methods against all F2 in an anisotropic approxi-
mation using the SHELX-97 programs set.[37] In the case of 4b and
2m, the C atoms of the benzene molecule and the minor SЈ and SeЈ
atoms were refined isotropically with geometrical restrictions. The
positions of the hydrogen atoms were calculated with the riding
model. Absorption corrections were applied using the empirical
multiscan method with the SADABS program.[38]
One-Pot Synthesis of Se-Esters of Thioselenophosphinic Acids 3a–f:
See Scheme 6. Powdered S8 (32 mg, 0.125 mmol) was added to a
solution of freshly distilled secondary phosphane 1a,b,f (1 mmol)
in EtOH (7 mL), and the mixture was stirred at room temp. until
the dissolution of sulfur residue (ca. 20 min). Amorphous gray
selenium (78.9 mg, 1.00 mmol) and a solution of NaOH (40 mg,
1 mmol) in EtOH (8 mL) were consecutively added to the trans-
parent solution thus obtained. The resulting mixture was stirred at
40–50 °C until the dissolution of the selenium powder (ca. 10 min),
and corresponding organic halide (1 mmol) was added. The mix-
ture was stirred for 10 min at 40–43 °C. The solvent and the excess
amount of organic halide were removed under reduced pressure,
and dry Et2O (10 mL) was added to the residue. The precipitated
white powder (alkali metal halide) was removed by filtration, and
Et2O was evaporated from the filtrate. The residue obtained was
The obtained crystal structures were analyzed for short contacts
between nonbonded atoms using PLATON[39] and MERCURY
programs.[40]
CCDC-894978 (for 2m), -894980 (for 4a), -894979 (for 4b), -901601
(for 5a), and -901600 (for 5b) contain the supplementary crystallo-
graphic 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.
Supporting Information (see footnote on the first page of this arti-
cle): X-ray crystallographic data for 2m, 4a, 4b, 5a, and 5b as well
as analytical data for the synthesized compounds.
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Acknowledgments
The authors wish to acknowledge financial support from the Rus-
sian Foundation for Basic Research (grant number 11-03-00334-a)
and the President of the Russian Federation (program for the sup-
port of leading scientific schools, grant number NSh-1550.2012.3).
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