206
U. Herzog et al. / Journal of Organometallic Chemistry 602 (2000) 193–207
the two isomers of (PhMeSiS)3 (see Section 3.5). Rep-
etition of this reaction with Ph2SiCl2 (1.01 g, 4 mmol)
instead of PhMeSiCl2 yielded a solid product which
consisted of 45% 8 as well as 30% (Ph2SiS)3 (lSi: 4.5
ppm, [9]) and 25% (Ph2SiS)2 (lSi: −3.5 ppm, [9]).
11, GC–MS: 298 [M+, 38], 283 [M−Me, 34], 239
[M−SiMe2H, 21], 223 [Si3S2Me5, 19], 165 [Si2S2Me3,
21], 73 [SiMe3, 100].
3.12. Synthesis of 1,2,2,4,4,5,6,6-octamethyl-1,2,4,5,6-
pentasila-3,7,8-trithiabicyclo-[3,2,1]-octane (12a)
3.9. Synthesis of 1,2,2,4,4,5,6,6,8,8-decamethyl-
1,2,4,5,6,8-hexasila-3,7-dithiabicyclo-[3,3,0]-octane (9)
SiClMe(SiClMe2)2 (0.266 g, 1 mmol) and SiCl2Meꢀ
SiClMe2 (0.208 g, 1 mmol) were dissolved in 25 ml
hexane and 0.83 ml (6 mmol) NEt3 were slowly
added while H2S was bubbled through the solution.
After filtration from the ammonium salt and evapora-
tion of the solvent 0.28 g of an oily residue remained
which consisted of 65% 12a besides 25% 10a and 10%
13a.
Through a solution of [SiMe(SiClMe2)2]2 (0.35 g,
0.76 mmol) in 25 ml hexane was bubbled H2S while
NEt3 (0.43 ml, 3.1 mmol) was added. After filtration
and evaporation of the solvent, a viscous oil re-
mained. Sublimation at 120°C/0.03 Torr yielded 0.2 g
(69%) pure 9 as a crystalline product, F 75°C.
9, GC–MS: 382 [M+, 73], 367 [M−Me, 38], 323
[M−SiMe2H, 32], 309 [M−SiMe3, 61], 277 [Si5SMe7,
13], 249 [Si4SMe7, 19], 131 [Si2Me5, 16], 73 [SiMe3,
100], 59 [SiMe2H, 15].
12a, GC–MS: 356 [M+, 26], 341 [M−Me, 21], 297
[M−SiMe2H, 13], 283 [M−SiMe3, 13], 191 [Si3SMe5,
18], 176 [Si3SMe4, 18], 116 [Si2Me4, 21], 73 [SiMe3,
100], 59 [SiMe2H, 11].
3.10. Synthesis of 1,1,2,2-tetrakis-(butylthiodimethyl-
silyl)-1,2-dimethyldisilane
3.13. Synthesis of 1,2,2,4,4,5,6,6,8,8-decamethyl-
1,2,4,5,6,8-hexasila-3,7,9-trithiabicyclo-[3,3,1]-nonane
(13a)
[SiMe(SiClMe2)2]2 (0.23 g, 0.5 mmol) was added to
a BuSLi solution made from BuSH (0.18 g, 2 mmol)
and BuLi (1.25 ml, 1.6 M, 2 mmol) in 10 ml dry
THF. After stirring for 2 h and filtration from pre-
cipitated LiCl the solvent was removed in vacuo
yielding [SiMe(SiMe2(SBu))2]2 (0.25 g, 0.37 mmol) as
a colorless oily residue. NMR, l/ppm: 29Si: 5.7
SiClMe(SiClMe2)2 (0.398 g, 1.5 mmol) was dis-
solved in 20 ml hexane and while H2S passed through
the solution NEt3 (0.63 ml, 4.5 mmol) was slowly
added. After filtration and removal of the solvent an
oily residue of 13a remained. 13a was also a by-
product in the synthesis of 11 and 12a.
1
1
(SiMe2, JSiC: 44.7, JSiSi: 64.6 Hz), −74.7 (SiMe);
13C: 2.21 (SiMe2), −8.5 (SiMe), 26.85 (SC
H2), 35.2
(SCH2CH2), 22.0 (SCH2CH2CH2), 13.7 (SꢀC
0.545 (SiMe2), 0.400 (SiMe), 2.53 (SCH2
(SCH2CH2), 1.42 (SCH2CH2CH2), 0.91 (SꢀCH3
13a, GC–MS: 414 [M+, 7], 399 [M−Me, 4], 249
[Si4SMe7, 19], 234 [Si4SMe6, 27], 191 [Si3SMe5, 11],
131 [Si2Me5, 21], 116 [Si2Me4, 17], 73 [SiMe3, 100], 59
[SiMe2H, 12].
6
1
6
6
6
H3); H:
), 1.59
).
6
6
6
6
3.14. Synthesis of 1,2,2,4,6,6,7,7-octamethyl-1,2,4,6,7-
pentasila-3,5,8-trithiabicyclo-[2,2,2]-octane (14)
3.11. Synthesis of tetrasilatrithianorbornanes (10a, 11)
1,2,2,4,5,5-Hexamethyl-1,2,4,5-tetrasila-3,6,7-trithia-
norbornane (10a) resulted from the reaction of a so-
lution of SiCl2MeꢀSiClMe2 (0.52 g, 2.5 mmol) in 20
ml hexane with H2S and 1.04 ml (7.5 ml) NEt3 after
filtration from the precipitated ammonium salt and
evaporation of the solvent in vacuo as viscous oil, Kp
80°C/0.03 Torr.
A solution of SiMe(SiClMe2)3 (0.34 g, 1.05 mmol)
and MeSiCl3 (0.157 g, 1.5 mmol) in 25 ml hexane
were reacted with NEt3 (0.87 ml, 6.3 mmol), while
H2S bubbled through the solution. After filtration
and evaporation of the solvent 0.3 g of a semisolid
residue of 14 remained.
14, GC–MS: 356 [M+, 31], 341 [M−Me, 20], 297
[M−SiMe2H, 12], 283 [Si4S3Me5, 11], 191 [Si3SMe5,
14], 176 [Si3SMe4, 13], 131 [Si2Me5, 17], 116 [Si2Me4,
16], 73 [SiMe3, 100], 59 [SiMe2H, 13].
10a, GC–MS: 298 [M+, 47], 283 [M−Me, 40], 239
[M−SiMe2H, 24], 223 [Si3S2Me5, 22], 165 [Si2S2Me3,
27], 73 [SiMe3, 100].
The treatment of a mixture of 0.266 g (1 mmol)
SiClMe(SiClMe2)2 and 0.150 g (1 mmol) MeSiCl3 dis-
solved in 20 ml hexane with H2S and 0.83 ml (6
mmol) NEt3 resulted after filtration and evaporation
of the solvent in 0.25 g of an oily residue of
1,2,2,4,6,6-hexamethyl-1,2,4,6-tetrasila-3,5,7-trithianor-
4. Supplementary material
Crystallographic data (excluding structure factors)
for the structures in this paper have been deposited
with the Cambridge Crystallographic Data Centre as
supplementary publication nos. 4c: CCDC 141105, 6:
bornane (11, 82%) besides 10% (MeSiS3/2 4
)
(lSi:
17.2%, [9]) and 8% 13a.