Reactivity of extended chalcogen-nitrogen π-systems: Compounds Ar-Se-N=S=N-Se-Ar

Article abstract of DOI:10.1016/j.mencom.2011.11.009

The reactions of Ar-Se-N=S=N-Se-Ar with SO₂Cl₂ (as well as with ArSeCl and p-TolICl₂) and H₂O gave Ar-SeCl₂-N=S=N-Se-Ar and [NH₄]⁺[ArSeSO ₃]^- (Se-Bunte salts), respectively, whose structures were confirmed by X-ray diffraction.

Full text of DOI:10.1016/j.mencom.2011.11.009

Mendeleev
Communications
Mendeleev Commun., 2011, 21, 320–322
Reactivity of extended chalcogen–nitrogen
p-systems: compounds Ar–Se–N=S=N–Se–Ar
Arkady G. Makarov,a Tatiana D. Grayfer,b Alexander Yu. Makarov,a
Irina Yu. Bagryanskaya,a Vladimir G. Vasilieva and Andrey V. Zibarev*a,c
a N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy
of Sciences, 630090 Novosibirsk, Russian Federation. Fax: +7 383 330 9752; e-mail: zibarev@nioch.nsc.ru
b Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russian Federation
c Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russian Federation
DOI: 10.1016/j.mencom.2011.11.009
The reactions of Ar–Se–N=S=N–Se–Ar with SO2Cl2 (as well as with ArSeCl and p-TolICl2) and H2O gave Ar–SeCl2–N=S=N–Se–Ar
and [NH4]+[ArSeSO3]– (Se-Bunte salts), respectively, whose structures were confirmed by X-ray diffraction.
Currently, the electronic and molecular structures of oligomeric
PhSeCl, or
SO2Cl2, or
p-TolICl2
Cl
Ph Se
Cl
analogues of polymeric sulfur nitride (SN)x (a molecular metal and
low-temperature superconductor),1 particularly Ar–X–N=S=N–
X–Ar (X = S, Se),2 receive much attention. The heteroatom reac-
tivity of these extended chalcogen–nitrogen p-systems, expected to
be high and varied, is less studied. For Ar–S–N=S=N–S–Ar, it is
only known that they react with ArSCl to give [ArSNSNSNS–
Ar]+Cl– salts.3
We found that, in contrast to S congeners, compounds Ph–
Se–N=S=N–Se–Ph 1 and PhSeCl afford Ph–SeCl2–N=S=N–
Se–Ph 2 and PhSeSePh (Scheme 1).† The structure of 2 was
elucidated by X-ray diffraction (XRD) as the E,Z configuration
(Figure 1).‡ The same product was also obtained with other
Ph Se N
S
1
N
N
Se Ph
N
S
N Se Ph
– PhSeSePh, or
– SO2, or
2
– p-TolI
Cl
Ph Se
Cl
S
N
Se Ph
Ph Se Cl
–[N2], –[S]
2
Scheme 1
3.376 Å
3.386 Å
†
The ESI mass spectra were obtained with a Bruker Daltonik micrOTOF-Q
3.283 Å
hybrid quadrupole time-of-flight mass-spectrometer equipped with an
electrospray ionization (ESI) source, for MeCN solutions with nitrogen as
drying gas. ESI-MS conditions: negative scan in the range m/z 100–3000;
Vcap = 4000 V; drying gas flow, 4 dm3 min–1 and temperature, 220°C;
nebylizer pressure, 1.0 bar. A small syringe pump was used for the intro-
duction of solutions samples directly to spray chamber of the mass-spec-
trometer, flow rate was 3 ml min–1. In all cases, isotopic distributions in
the experimental mass-spectra were in a good agreement with theoretical
simulations.
(a)
(b)
Thermal analysis in the range of 30–300°C was performed in a helium
atmosphere with a Hetzsch 409 PC/PG instrument equipped with a platinum
pan; the heating rate was 10°C min–1.
Figure 1 XRD (a) molecular and (b) crystal structures of compound 2.
Selected bond lengths (Å), bond and torsion angles (°): C–Se(E) 1.937(5),
Se–Cl 2.3124(17) and 2.5177(17), Se–N 1.814(5), N–S 1.570(5), S–N
1.526(5), N–Se(Z) 1.863(5), Se(Z)–C 1.915(6); C–Se(E)–N 96.7(2), C–Se–Cl
91.10(17) and 89.41(16), Cl–Se–Cl 176.70(6), N–Se–Cl 91.21(17) and
91.97(17), Se–N–S 118.5(3), N–S–N 108.2(3), S–N–Se(Z) 117.7(3), N–Se–C
94.0(2); C–C–Se(E)–N 169.0(4), C–C–Se–Cl 77.6(4) and –99.1(4), Cl–Se–
N–S 125.5(3) and –53.7(3), C–Se–N–S –143.3(3), Se–N–S–N –174.9(3),
N–S–N–Se(Z) –2.6(4), S–N–Se–C –171.2(3), N–Se–C–C –113.4(5).
The IR spectra were measured in KBr pellets on a Bruker Vector 22
1
spectrometer; and the H and 19F NMR spectra, on Bruker AV-400 and
Bruker AV-300 spectrometers, respectively, at frequencies of 400.13 and
282.4 MHz, respectively; the standards were TMS and C6F6.
Interaction between Ph–Se–N=S=N–Se–Ph 1 and SO2Cl2, p-TolICl2
or PhSeCl. Compound Ph–SeCl2–N=S=N–Se–Ph 2:
(a) At 0°C and under argon, a solution of SO2Cl2 (120 mg, 0.8 mmol)
in 5 ml of toluene was added dropwise to a stirred solution of 12 (315 mg,
0.8 mmol) in a mixture of 10 ml of hexane and 5 ml of toluene. The
reaction mixture was stirred for additional 3 h at ambient temperature,
and the precipitate was filtered off, washed twice with both solvents and
dried in vacuo. Compound 2 was obtained in the form of yellow crystals
in a yield of 262 mg (74%).
(b)At 0°C and under argon, a solution of p-TolICl2 (251 mg, 0.9 mmol)
in 20 ml of toluene was added dropwise to a stirred solution of 1 (324 mg,
0.9 mmol) in a mixture of 20 ml of hexane and 2 ml of toluene. The
reaction mixture was stirred overnight at ambient temperature, and the
precipitate was filtered off, washed with hexane and dried in vacuo.
Compound 2 was obtained in a yield of 152 mg (38%).
(c) At –10°C and under argon, a solution of PhSeCl (300 mg, 1.6 mmol)
in a mixture of 10 ml of hexane and 1 ml of toluene was added dropwise
to a stirred solution of 1 (292 mg, 0.8 mmol) in a mixture of 20 ml of
hexane and 2 ml of toluene. The precipitate was filtered off and recrys-
tallized from toluene at low temperature. Compound 2 was obtained in a
yield of 71 mg (16%).
For 2: Tdecomp. 70°C. 1H NMR (toluene-d8) d: 7.47 (m, 2H), 6.89 (m,
3H). Found (%): Cl, 15.95; N, 6.40; S, 6.85. Calc. for C12H10Cl2N2SSe2
(%): Cl, 16.00; N, 6.32; S, 7.24. The single crystals suitable to XRD were
obtained by low-temperature crystallization from toluene.
Hydrolysis of Ar–Se–N=S=N–Se–Ar. Typical procedure. A solution of
0.1 mmol of Ar–Se–N=S=N–Se–Ar2 in 2 ml of hexane was placed in one
tube of an H-shaped Schlenk vessel, and 10 ml of water into another.
© 2011 Mendeleev Communications. All rights reserved.
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Mendeleev Commun., 2011, 21, 320–322
H2O
chlorinating agents such as SO2Cl2 and p-TolICl2.† The highest
isolated yield of 2, 74% was achieved with SO2Cl2.
Ar–Se–N=S=N–Se–Ar
Ar–Se–SO3 NH4
3–6
The Se(E) center of 2 possesses the geometry of a distorted
trigonal bipyramid with the chlorine atoms in axial positions,
which is typical of R2SeHal2 compounds.6 In the crystal, the Se–Cl
bonds have different lengths, and the Cl atom of the longer bond
(2.518 Å) is involved in three shortened intermolecular contacts
with one S and two Se atoms, whereas that of the shorter bond
(2.312 Å) does not reveal such contacts (Figure 1).
3 Ar = Ph
4 Ar = 3-ClC6H4
5 Ar = C6F5
6 Ar = 3-ClC6F4
Scheme 2
(a)
(b)
Compound 2 is thermally unstable and produces PhSeCl upon
heating in an individual state above 70°C or boiling its toluene
solution (Scheme 1).
In both hydrocarbon and fluorocarbon series, the hydrolysis
of Ar–Se–N=S=N–Se–Ar in a hexane solution by water vapor at
ambient temperature led to ammonium Se-arylselenosulfates
[NH4]+[ArSeSO3]– 3–6 (Scheme 2),† whose structures were con-
firmed by XRD (Figure 2).‡ In the IR spectra of the salts, bands
at 1243–1234 and 1037–2025 cm–1 can be assigned to the
stretching modes of the SO3 moiety, and those at 628–617 and
520–519 cm–1, to the deformation modes.7
Figure 2 XRD structures of salts (a) 5 and (b) 6 (disorder of the Cl atom
over two positions‡ is omitted). Selected bond lengths (Å) and bond angles (°):
5: C–Se 1.913(9), Se–S 2.270(2), S–O 1.441(6), 1.458(6) and 1.464(6);
C–Se–S 94.5(3), Se–S–O 102.6(3), 104.1(3) and 106.4(3), O–S–O 113.7(4),
114.1(4) and 114.5(4); 6: C–Se 1.901(5), Se–S 2.2634(11), S–O 1.443(3),
1.453(3) and 1.455(3); C–Se–S 94.73(16), Se–S–O 102.31(14), 104.21(14)
and 107.18(14), O–S–O 113.4(2), 113.8(2) and 114.6(2).
and for R = Ar only a few derivatives are described.9 To the
best of our knowledge, any polyfluorinated selenosulfate salts
[Cat]+[RSeSO3]– were unknown.
S-Organylthiosulfates or Bunte salts, [Cat]+[RSSO3]– (R = Alk,
Ar), have found numerous applications in fundamental and applied
chemistry.8 Their Se-organyl congeners are much less studied,
As compared with Se congeners, Ar–S–N=S=N–S–Ar deriv-
atives2 revealed enhanced stability toward water vapor under
employed conditions† and were quantitatively recovered after
eight weeks of exposing to the vapor. However, note that a few
[NH4]+[ArSSO3]– salts together with Ar–S–N=S=N–S–Ar deriv-
atives were isolated earlier as minor by-products after the aqueous
acid decomposition of reaction mixtures produced by (SN)4 and
ArMgHal, the main products were ArSSAr.10 Taking into account
that the hydrolysis conditions were very different, we believe that
the discussed [NH4]+[ArSSO3]– salts10 came from the hydrolysis
of Ar–S–N=S=N–S–Ar during the workup of reaction mixtures.
For comparison, salt 5 was also prepared from C6F5SeBr and
aqueous (NH4)2SO3† by a modified approach,9(c) and its properties
were identical to those of the salt obtained from the hydrolysis.
The salts [NH4]+[ArSeSO3]– are thermally unstable. For
example, according to thermal analysis data, salt 5 decomposes
After 4 weeks at ambient temperature, crystals of [NH4]+[ArSeSO3]–
appeared in the first tube were separated from solvent and dried in vacuo.
[NH4]+[C6H5SeSO3]– 3 was obtained in the form of small white scales
not suitable to XRD, yield 75%, Tdecomp. 120°C. MS, m/z: 236.901 (calc.
for [C6H5O3SSe]–: 236.913). IR (n/cm–1): 3431 (s), 3177 (s), 3065 (s),
2928 (m), 2855 (m), 1630 (w), 1574 (w), 1476 (m), 1435 (s), 1304 (w),
1196 (vs), 1184 (vs), 1173 (vs), 1065 (w), 1028 (vs), 1016 (vs), 999 (m),
748 (s), 694 (m), 631 (vs), 528 (m), 469 (w). Found (%): C, 27.94;
H, 3.53; N, 5.57; S, 12.57. Calc. for C6H9NO3SSe (%): C, 28.35; H, 3.57;
N, 5.51; S, 12.62.
[NH4]+[3-ClC6H4SeSO3]– 4 was obtained in the form of white powder,
yield 20%, Tdecomp. 140°C. IR (n/cm–1): 3441 (m), 3179 (s), 3082 (s),
2912 (m), 1636 (w), 1566 (m), 1458 (m), 1398 (s), 1221 (vs), 1184 (vs),
1159 (s), 1105 (w), 1082 (w), 1065 (w), 1026 (vs), 993 (m), 891 (w),
795 (s), 756 (m), 685 (m), 638 (vs), 542 (w), 521 (m), 430 (w). Found (%):
C, 24.94; H, 2.80; Cl, 12.25; N, 5.32; S, 11.34. Calc. for C6H8ClNO3SSe
(%): C, 24.97; H, 2.79; Cl, 12.28; N, 4.85; S, 11.11.
‡
X-ray diffraction data.
[NH4]+[C6F5SeSO3]– 5 was obtained in the form of white needles
suitable to XRD, yield 15%, Tdecomp. 160°C. MS, m/z: 326.863 (calc. for
[C6F5O3SSe]–, 326.866). IR (n/cm–1): 3223 (s), 3102 (m), 2929 (w),
2879 (w), 2855 (w), 1634 (m), 1514 (s), 1486 (vs), 1428 (s), 1237 (s),
1195 (s), 1107 (m), 1088 (s), 1027 (vs), 974 (s), 825 (m), 628 (s), 520
(w). Found (%): C, 20.78; H, 1.24; F, 27.91; N, 4.29; S, 9.65. Calc. for
C6H4F5NO3SSe (%): C, 20.94; H, 1.17; F, 27.60; N, 4.07; S, 9.32.
[NH4]+[3-ClC6F4SeSO3]– 6 was obtained in the form of transparent
colorless needles suitable to XRD, yield 28%, Tdecomp. 160°C. MS, m/z:
342.828 (calc. for [C6ClF4O3SSe]–, 342.836). 1H NMR, d: 5.93. 19F NMR,
d: 60.2 (d, J 9.5 Hz), 43.6 (dd, J 25.1 and 6.1 Hz), 31.3 (dd, J 20.1 and
6.4 Hz), 1.3 (ddd, J 25.0, 20.2 ad 9.3 Hz). IR (n/cm–1): 3202 (s), 3096 (m),
3060 (m), 2877 (w), 2840 (w), 1615 (m), 1487 (vs), 1447 (vs), 1424 (s),
1234 (vs), 1198 (vs), 1079 (s), 1025 (vs), 909 (s), 761 (m), 719 (w), 627
(vs), 519 (w). Found (%): C, 19.98; H, 1.12; N, 3.84; Cl, 9.90; F, 20.76;
S, 8.85. Calc. for C6H4ClF4NO3SSe (%): C, 19.99; H, 1.12; N, 3.88;
Cl, 9.83; F, 21.08; S, 8.89.
Synthesis of salt 5. At 0°C, a solution of (NH4)2SO3·H2O (445 mg,
3.3 mmol) in 5 ml of water was added to a stirred solution of C6F5SeBr4
(978 mg, 3 mmol) in 10 ml of CHCl3. After 15 min, the reaction system
was filtered, and the white solid was washed with CHCl3 (3×10 ml) on
the filter and extracted with acetone (3×10 ml). The acetone solution was
evaporated to dryness, and the residue was combined with that from
evaporation of water part of the filtrate under reduced pressure. The
combined crude product was extracted with MeCN (3×5 ml), the extract
was filtered, and the mixture of 15 ml of toluene and 15 ml of hexane was
added to the filtrate. The precipitate was filtered off, washed subsequently
with toluene and hexane and dried in vacuo. Salt 5 was obtained in the
form of shiny white crystals, 395 mg (40%).
For 2: C12H10Cl2N2SSe2, M = 443.11, orthorhombic, space group Pbca,
a = 8.4475(6), b = 8.5870(7) and c = 41.614(4) Å, V = 3018.6(4) Å3, Z = 8,
dcalc = 1.950 g cm–3, m = 5.378 mm–1, F(000) = 1712, crystal dimensions
0.01×0.07×0.30 mm, 20101 reflections collected with 1.0 < q < 28.8°,
2806 [I > 2s(I)] used in structural analysis, R1 = 0.0574, wR2 = 0.1135,
S = 1.15.
For 5: C6H4F5NO3SSe, M = 344.13, monoclinic, space group P21/c,
a = 4.8854(3), b = 31.846(2) and c = 6.6899(4) Å, b = 102.402(4)°, V =
= 1016.53(11)Å3, Z = 4, dcalc = 2.249 g cm–3, m = 3.970 mm–1, F(000) = 664,
crystal dimensions 0.20×0.20×0.20 mm, 4623 reflections collected with
2.6 < q < 27.5°, 2123 [I > 2s(I)] used in structural analysis, R1 = 0.0722,
wR2 = 0.1840, S = 1.03.
For 6: C6H4ClF4NO3SSe, M = 360.58, monoclinic, space group P21/c,
a = 4.9135(2), b = 33.2112(14) and c = 6.7559(3) Å, b = 100.372(2)°, V =
= 1084.44(8)Å3, Z = 4, dcalc = 2.209 g cm–3, m = 3.952 mm–1, F(000) = 696,
crystal dimensions 0.10×0.10×0.90 mm, 19894 reflections collected with
1.2 < q < 30.1°, 2919 [I > 2s(I)] reflections used in structural analysis,
R1 = 0.0584, wR2 = 0.1205, S = 1.02. The Cl atom is disordered over
the positions 3 and 5 of the ring with the occupation ratio 0.52:0.48. The
disorder leads to enlarged thermal ellipsoids because of which the F atoms
(when in one of these positions) can be refined only isotropically.
The data were collected on a Bruker Kappa Apex-II diffractometer
using MoKa radiation (l = 71.073 pm) at 150 K. The structures were
solved by direct methods using the SHELXL-97 program,5 all non-hydro-
gen atoms were refined unisotropically unless otherwise indicated.
CCDC 835104–835106 contain 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, 2011.
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Mendeleev Commun., 2011, 21, 320–322
3 (a) C. M. Aherne, A. J. Banister, I. Lavender, S. E. Lawrence and J. M.
above 160°C with the quantitative formation of C6F5SeSeC6F5,
whose identity was confirmed by 19F NMR spectroscopy. The
salts are also unstable in solution at ambient temperature. For
instance, an initially colorless solution of 6 in MeCN became
yellow and released a precipitate of NH4HSO4 (IR) after 20 h
at ambient temperature; 19F NMR spectroscopy revealed that
the solution contained a 3:7 mixture of 6 and corresponding
ArSeSeAr.
Rawson, Polyhedron, 1996, 15, 1877; (b) J. A. K. Howard, I. Lavender,
J. M. Rawson and E. A. Swain, Main Group Chem., 1996, 1, 317; (c) J. J.
Mayerle, J. Kuyper and J. B. Street, Inorg. Chem., 1978, 17, 2610.
4 T. M. Klapötke, B. Krumm and K. Polborn, Eur. J. Inorg. Chem., 1999,
1359.
5 G. M. Sheldrick, Acta Crystallogr., Sect. A, 2008, 64, 112.
6 S. M. Godfrey, C. A. McAuliffe, R. G. Pritchard and S. Sarwar, J. Chem.
Soc., Dalton Trans., 1997, 1031.
7 J. S. Church and D. J. Evans, Spectrochim. Acta, Part A, 2008, 69, 256.
8 (a) H. Distler, Angew. Chem., Int. Ed. Engl., 1967, 6, 544; (b) S. Schneller,
Int. J. Sulfur Chem., 1972, 7, 155; (c) Comprehensive Organic Chemistry,
eds. D. H. R. Barton and W. D. Ollis, Pergamon Press, Oxford, 1979,
vol. 3; (d) Comprehensive Organic Functional Group Transformations,
eds. A. R. Katritzky, S. V. Ley, O. Meth-Kohn and C. W. Rees, Elsevier,
Oxford, 1995; (e) Comprehensive Organic Functional Group Transforma-
tions II, eds. A. R. Katritzky and R. J. K. Taylor, Elsevier, Amsterdam,
2005.
This work was supported by the Russian Foundation for Basic
Research (project no. 09-03-00361). A.G.M. is grateful to the
Russian Science Support Foundation for a 2010 Postgraduate
Scholarship.
References
1 A. J. Banister and I. B. Gorrell, Adv. Mater., 1998, 10, 1415.
2 (a) A. G. Makarov, I. Yu. Bagryanskaya, Yu. V. Gatilov, N. V. Kuratieva,
A. Yu. Makarov, M. M. Shakirov, A. V. Alexeyev, K. Tersago, C. Van
Alsenoy, F. Blockhuys and A.V. Zibarev, Eur. J. Inorg. Chem., 2010, 4801;
(b) K. Tersago, I. Yu. Bagryanskaya, Yu. V. Gatilov, S. A. Gromilov, A. Yu.
Makarov, M. Mandado, C. Van Alsenoy, A.V. Zibarev and F. Blockhuys,
Eur. J. Inorg. Chem., 2007, 1958; (c) K. Tersago, M. Mandado, C. Van
Alsenoy, I. Yu. Bagryanskaya, M. K. Kovalev, A. Yu. Makarov, Yu. V.
Gatilov, M. M. Shakirov, A. V. Zibarev and F. Blockhuys, Chem. Eur. J.,
2005, 11, 4544.
9 (a) Organic Selenium Compounds: Their Chemistry and Biology, eds.
D. L. Klayman and W. H. H. Günther, Wiley, New York, 1973; (b) T.
Austad, Acta Chem. Scand., Ser. A, 1976, 30, 479; (c) N. Patarasakulchai
and P. T. Southwell-Kelly, Phosphorus Sulfur, 1985, 22, 277.
10 S. Mataka, K. Takahashi, H. Yamamoto and M. Tashiro, J. Chem. Soc.,
Perkin Trans. 1, 1980, 2417.
Received: 20th July 2011; Com. 11/3769
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