T.A. Shaikh et al. / Journal of Organometallic Chemistry 691 (2006) 1825–1833
1827
1277 (w), 1106 (w), 929 (w,sh), 827 (m), 664 (m), 445 (w).
Mass spectra (GC–MS): 294 (AsI(SCH2CH2S))+, 167
(As(SCH2CH2S))+.
1493 (s), 1440 (s), 1416 (w), 1385 (w), 1301 (w), 1236 (m),
1211 (w), 1185 (m), 1156 (w), 1073 (w), 949 (w), 860
(w), 828 (w), 766 (vs), 762 (s), 666 (s), 589 (m), 499 (m).
Mass spectra (GC–MS): 243 (As(SCH2)2(C6H4))+, 168
((SCH2)2(C6H4))+, 104 ((CH2)2(C6H4))+.
2.4. Preparation of 2-chloro-1,3,2-dithiarsenane (3)
1,3-Dithiopropane (2.75 g, 25.5 mmol) was dissolved in
25 mL of CCl4 and added dropwise to a solution of arsenic
trichloride (5.04 g, 27.1 mmol) in 25 mL CCl4 at room tem-
perature. The reaction was stirred for an hour and the solu-
tion cooled to ꢀ20 °C and kept at that temperature for 24 h
at which point a white crystalline precipitate formed. The
solution was filtered and the resulting solid dried com-
pletely, yielding 4.96 g of a crystalline solid in 90.0% yield.
2.7. Preparation of 1,2-bis-dithiarsolan-2-ylmercapto-ethane
(6)
2-Chloro-1,3,2-dithiarsolane (1.01 g, 5.00 mmol) was
dissolved in 20 mL of THF and an aqueous solution of
Na2CO3 (1.00 g, 9.43 mmol, in 60 mL H2O) was added to
form a white precipitate. The solution was stirred for
5 min and then filtered to isolate 0.379 g of a white precip-
itate in a yield of 53.4%. The precipitate was dissolved in a
50/50 solution of CHCl3/CH3OH and slowly evaporated to
1
Mp: 40.5–41.0 °C. H NMR (CDCl3) d: 3.50 (m, 2H), d
3.06 (m, 2H), d 2.27 (m, 2H). 13C NMR (CDCl3) d:
26.587 (s), 25.797 (s). IR (m, cmꢀ1, KBr): 3448 (m, br),
2904 (m), 2820 (w), 2360 (w), 1635 (w), 1416 (s), 1338 (w),
1296 (m), 1269 (m), 1245 (m), 1179 (w), 1115 (w), 995 (w),
899 (w), 855 (w), 803 (w), 739 (w), 618 (m), 411 (w). Mass
spectra (GC–MS): 216 (AsCl(SCH2CH2CH2S))+, 181
(As(SCH2CH2CH2S))+.
1
obtain X-ray quality crystals. Mp: 81.5–82.0 °C. H NMR
(CDCl3) d: 3.507 (m, 8H), d 3.106 (s, 4H). 13C NMR
(CDCl3) d: 42.722 (s), d 35.890 (s). IR (m, cmꢀ1, KBr):
3449 (b), 2947 (w), 2906 (s), 1594 (m), 1409 (s), 1275 (s),
1195 (s), 1110 (w), 991 (w), 929 (w), 831 (s), 720 (w), 679
(m), 645 (w), 451 (w). Mass spectra (GC–MS): 167
(AsSCH2CH2S)+.
2.5. Preparation of 2-iodo-1,3,2-dithiarsenane (4)
2.8. Preparation of tris-(pentafluorophenylthio)-arsen (7)
Sodium iodide (0.75 g, 5.00 mmol) in 10 mL acetone was
added to 2-chloro-1,3,2-dithiarsenane (1.08 g, 4.99 mmol)
dissolved in 20 mL of acetone at room temperature. Both
solutions were clear before addition. Upon addition, the
solution took on a bright orange tint and a white precipitate
formed. The white precipitate was filtered out and part of
the solvent was removed from the solution under vacuum.
The solution was then allowed to crystallize and 0.24 g of
dark red orange crystals formed at ꢀ20 °C in a 15.6% yield.
Mp: 45–46 °C.1H NMR (CDCl3, ppm) d: 3.24 (t, 4H), d:
2.29 (p, 2H). 13C NMR (CDCl3, ppm) d: 31.14 (s),
26.95(s). IR (m, cmꢀ1, KBr): 3448 (m, br), 2896 (m), 2832
(m), 2364 (w), 1627 (m), 1412 (s), 1364 (w), 1293 (w), 1265
(m), 1179 (w), 892 (w), 851 (w), 802 (w), 775 (w), 616 (w).
Mass spectra (GC–MS): 308 (AsI(SCH2CH2CH2S))+, 181
(As(SCH2CH2CH2S))+.
Arsenic trifluoride (1.00 ml, 20.02 mmol) was dissolved
in 5 mL of CCl4 and pentafluorothiophenol (5.40 mL,
40.50 mmol) was dissolved in 20 mL of CCl4. Upon slow
addition of the two solutions, a white precipitate formed.
The reaction was left stirring for 24 h under a N2 atmo-
sphere. The solvent was then removed and the precipitate
was dissolved in a mixture of CH2Cl2, toluene, acetonitrile
and trifluorotoluene in a 1:1:3:3 ratio. The solvent mixture
was evaporated slowly to produce 9.068 g of X-ray quality
crystals in a yield of 99.96%. Mp: 76–77 °C. 19F NMR
(CDCl3, ppm) d ꢀ135.29 (m)(C–F meta), d ꢀ153.35
(m)(C–F para), d ꢀ164.27 (m)(C–F ortho). IR(m, cmꢀ1
,
KBr): 1637 (m), 1488 (s), 1401 (w), 1377 (w), 1291 (w),
1093 (vs), 1019 (w), 980 (vs), 859 (vs), 723 (w), 634 (w),
417 (w). Mass spectra (GC–MS): 473 (As(SC6F5)2)+, 274
(As(SC6F5))+.
2.6. Preparation of 3-chloro-4H,7H-5,6-benz-1,3,2-
dithiarsepine (5)
2.9. X-ray crystallographic analysis
1,2-bis-Mercaptomethylbenzene (1.00 g, 5.87 mmol) was
dissolved in 20 mL of CCl4 and added dropwise to arsenic
trichloride (1.20 g, 6.62 mmol) in 20 mL CCl4 at room tem-
perature. The reaction was stirred overnight and cooled to
ꢀ20 °C and kept at that temperature for a week. Clear
star-like crystals formed in the solution. The solvent was
then removed yielding 1.57 g of a crystalline solid in a yield
of 96.2%. Mp: 117–119 °C. 1H NMR (CDCl3, ppm): d 7.17
(phenyl, m, 4H), d 5.11 (CH2, d, 2H), d 3.934 (CH2, d, 2H).
13C NMR (CDCl3, ppm): d 139.31, d 130.51, d 129.60
(–phenyl–), d 33.20 (–CH2–). IR (m, cmꢀ1, KBr): 3448
(wb), 3055 (w), 3026 (w), 2964 (w), 2933 (w), 1643 (w),
X-ray diffraction data were collected at 90 K on a Non-
ius Kappa CCD diffractometer unit using Mo Ka radiation
from colorless regular shaped crystals mounted in Par-
atone-N oil on glass fibers. Initial cell parameters were
obtained using DENZO [10] from 1° frames and were refined
via a least-square scheme using all data-collection frames
(SCALEPACK) [10]. The structures were solved by direct
methods (SHELXL-97) [11] and completed by difference Fou-
rier methods (SHELXL-97) [11]. Refinement was performed
against F2 by weighted full-matrix least-square. Hydrogen
atoms were placed at calculated positions using suitable
riding models with isotropic displacement parameters