F. Blockhuys, A. V. Zibarev et al.
FULL PAPER
Table 8. Physical data of compounds: yield (in %), melting point (in °C) or boiling point (in °C/Torr), mass spectroscopic data and
elemental composition (in %).
Yield
m.p. or b.p. MS (M+, m/z)[a]
Elemental analysis: found (calculated)[b]
found
calculated
C
H or F
Cl
N
5
64
26
68
36
41
78
58
69
92–93
80–81
50–51
81–82
Ͻ20
65/3
72–73
89/3
345.9236
441.8129
489.8460
585.7377
429.8687
–
345.9227
441.8116
489.8467
585.7366
429.8685
–
41.22 (41.50)
33.26 (32.68)
29.77 (29.34)
24.67 (24.64)
–
2.23 (2.32)
2.34 (1.83)
30.87 (30.94)
25.99 (25.98)
–
30.36 (30.27)
29.27 (28.95)
–
20.46 (20.42)
16.15 (16.07)
13.90 (14.43)
12.01 (12.12)
–
–
8.04 (8.07)
6.02 (6.35)
6.02 (5.70)
4.42 (4.79)
–
–
–
–
6
7
8
9
10
11
12
–
525.7567
–
525.7579
–
27.53 (27.46)
24.24 (24.19)
13.48 (13.51)
–
[a] For 35Cl and 80Se. [b] For S, found (calculated): for 5, 27.65 (27.70); for 7, 19.60 (19.58).
(4.62 g, 25 mmol) in Et2O (60 mL). After 60 min at the same tem-
perature, finely ground sulfur (0.80 g, 25 mmol) was added. After
an additional 75 min, the reaction mixture was warmed up to 0 °C
and iodine (3.30 g, 13 mmol) was added, followed by a solution of
Na2S2O3·5H2O (3 g) in H2O (30 mL). The reaction mixture was
extracted with Et2O (4ϫ 15 mL), the extract was dried with
MgSO4, and the solvents evaporated. The residue was recrystallized
from hexane at –40 °C. 3,3-Dichloro-2,2Ј,4,4Ј,5,5Ј,6,6Ј-octafluoro-
diphenyl disulfide (9, Table 8) was obtained as pale-yellow crystals.
19F NMR: δ = 52.8, 36.0, 35.3, 2.6 ppm. (b) An excess of Cl2 was
passed through a solution of 9 (1.29 g, 3 mmol) in CCl4 (10 mL).
The solvent was distilled off, and the residue was distilled at re-
duced pressure. 3-Chloro-2,4,5,6-tetrafluorophenylsulfenyl chloride
(10, Table 8) was obtained as a dark-red oil. 19F NMR: δ = 56.8,
39.8, 38.7, 2.9 ppm. (c) Under argon, a solution of 10 (0.33 g,
1.3 mmol) in hexane (20 mL) was added, over a period of 1 h, to a
solution of (Me3SiN=)2S (0.14 g, 0.66 mmol) in hexane (14 mL).
The volume of the reaction mixture was reduced to 2 mL and
brought down to –20 °C. Compound 7 (Tables 6 and 8) was ob-
tained as orange–yellow crystals.
Crystallographic Analysis
Crystallographic data on the four new compounds 5–8 can be
found in Table 9. The XRD data were obtained on a Bruker Kappa
Apex II CCD (for 5 and 6), a Bruker-Nonius X8 Apex CCD (for
7) and a Bruker P4 (for 8) diffractometer. Absorption corrections
were applied by using the SADABS (for 5–7) and XPREP (for 8)
programs. The structure was solved by direct methods implemented
in the SHELXS-97 program[26] and refined by the full-matrix least-
squares method in an anisotropic approximation by using the
SHELXL-97 program.[26] The obtained crystal structures were ana-
lyzed for short contacts between nonbonded atoms with the PLA-
TON program.[20] CCDC-757826 (5), -757827 (7), -757828 (6) and -
757829 (8) contain the supplementary crystallographic data for this
paper; CCDC-604700 contains the data for compound 4. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. X-
ray powder diffraction data for compound 8 were obtained with a
DRON-3M automated diffractometer (R = 192 mm, Cu-Kα radia-
tion, Ni-filter, scintillation point detector with amplitude discrimi-
nation, and 2.5° Soller slits on the primary and reflected beams) at
room temperature over the 2θ range 3–50° with a step size of 0.02°
in 2θ and 12 s counting time per step. An equatorial divergence slit
of 2 mm and an axial divergence slit of 12 mm were used.
1,5-Bis(3-chloro-2,4,5,6-tetrafluorophenyl)-2,4-diaza-1,5-diselena-3-
thia-2,3-pentadiene (8): (a) Under argon and at –60 °C, 17.3 mL of
a 2.5 hexane solution of BuLi (43 mmol) was added, over a
period of 15 min, to a solution of 1-chloro-2,3,4,6-tetrafluoroben-
zene (7.97 g, 43 mmol) in Et2O (100 mL). After an additional
60 min at the same temperature, finely ground selenium (3.41 g,
43 mmol) was added. The reaction mixture was kept at –60 °C for
60 min, warmed up to 0 °C and iodine (5.59 g, 22 mmol) was
added. After 30 min at ambient temperature, the reaction mixture
was treated with a solution of Na2S2O3·5H2O (3 g) in H2O (30 mL)
and extracted with Et2O (4ϫ 15 mL). The extract was dried with
MgSO4 and evaporated, and the residue was recrystallized from
hexane. 3,3Ј-Dichloro-2,2Ј,4,4Ј,5,5Ј,6,6Ј-octafluorodiphenyl dis-
elenide (11, Table 8) was obtained as yellow crystals. NMR: δ13C
= 154.4, 150.0, 149.7, 137.3, 107.4, 103.0 ppm; δ19F = 58.9, 42.2,
34.3, 2.5 ppm; δ77Se = 376 ppm. (b) An excess of Cl2 was passed
through a solution of 11 (5.0 g, 10 mmol) in CCl4 (15 mL). The
solvent was distilled off, and the residue was distilled at reduced
pressure. 3-Chloro-2,4,5,6-tetrafluorophenylselenenyl chloride (12,
Table 8) was obtained as a dark-red oil. NMR: δ13C: = 154.2,
151.3, 149.7, 137.5, 107.8, 104.5 ppm; δ19F = 62.0, 45.2, 38.0,
3.2 ppm; δ77Se = 808 ppm. (c) Under argon and at –30 °C, a solu-
tion of 12 (0.45 g, 1.5 mmol) in hexane (30 mL) was added, over a
period of 70 min, to a solution of (Me3SiN=)2S (0.15 g, 0.75 mmol)
in hexane (10 mL). The reaction mixture was warmed up to 20 °C,
and the solvent was distilled off. The residue was recrystallized
from hexane at –20 °C. Compound 8 (Tables 6 and 8) was obtained
as orange–yellow crystals.
Quantum Chemical Calculations
DFT calculations were performed using the Gaussian 03 suite of
programs[27] applying standard gradient techniques at the B3LYP
level of theory by using the 6-311+G* basis set on all atoms; the
basis set was used as it is implemented in the program. Force-field
calculations were used to ascertain whether the resulting structures
were energy minima. The energies are not ZPE-corrected. All sub-
sequent calculations of molecular properties were performed at the
B3LYP/6-311+G* geometries. Chemical shielding factors were cal-
culated at all atomic positions at the DFT/B3LYP/6-311+G* level
of theory by using the GIAO method implemented in Gaussian 03.
The chemical shift for the selenium atom was obtained by sub-
tracting the chemical shielding value of this atom from that calcu-
lated for dimethylselenide, which is 1623.1500 ppm at the B3LYP/
6-311+G* level of theory, based on the corresponding geometry
(C2v symmetry, anti,anti-conformer). Bond orders (or rather over-
lap populations; see ref. 15) were calculated according to the Hirsh-
feld scheme. QTAIM bond and ring properties were calculated by
using the AIMPAC suite of programs.[28]
Supporting Information (see footnote on the first page of this arti-
cle): X-ray powder diffractogram of compound 8 (Figure S1), vari-
able-temperature and variable-solvent 77Se and 19F NMR spectra
of compounds 4, 7 and 8 (Figures S2–S6) and packing diagrams of
compounds 4–8 (Figure S7) are available.
4808
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Eur. J. Inorg. Chem. 2010, 4801–4810