Extending Distannoxane Double Ladders
product was recrystallized from toluene/hexane/CH2Cl2
mixture (35 mL, 8 mL, 5 mL) to give 6′ as a colorless solid
(520 mg, 78% yield, mp 225-235 °C). IR (Nujol): νOH 3652
cm-1. Anal. Calcd for C80H169Cl7O5Si16Sn8: C 33.42, H 5.84;
Cl, 8.68. Found: C 33.40, H 6.01; Cl 8.25.
Organometallics, Vol. 21, No. 4, 2002 651
Ta ble 1. Cr ysta llogr a p h ic Da ta for 6 a n d
a
11‚Tolu en e
6
11‚toluene
formula
fw
C80H168Cl8O4Si16Sn8 C79H144Cl8O4Si8Sn8
2876.7
2615.8
Syn t h esis of 1,3-Bis[(2-t r ip h en ylst a n n yl)et h yl]b en -
zen e, 7. A solution of Ph3SnH (15.39 g, 43.85 mmol) and AIBN
(0.36 g, 2.19 mmol) in benzene (50 mL) was added dropwise
to a magnetically stirred solution of 1,3-divinylbenzene
(2.85 g, 21.92 mmol) in benzene (50 mL) at reflux. The
resulting reaction mixture was stirred at reflux for 2 h. After
removing the benzene in vacuo the crude product was crystal-
lized from dichloromethane/hexane to give 7 as a colorless solid
(15.1 g, 83% yield, mp 143-146 °C). 1H NMR (299.98 MHz,
cryst size, mm
cryst syst
space group
a, Å
b, Å
c, Å
0.10 × 0.10 × 0.18
monoclinic
Pc
22.913(1)
12.680(1)
22.019(1)
101.592(1)
6266.9(5)
2
1.524
2880
19.28
24 166
0.10 × 0.10 × 0.15
monoclinic
P21/n
19.091(1)
13.155(1)
24.413(1)
104.945(1)
5923.7(5)
2
1.466
2596
19.55
34 550
â, deg
V, Å3
Z
D
calcd, g cm-3
2
CDCl3): δ 1.98 [t, 4H, J (117/119Sn-1H) ) 52, SnCH2], 3.14 [t,
F(000)
4H, 3J (117/119Sn-1H) ) 54, CH2], 7.09 (s, 1H, C6H4), 7.18 (d,
2H, C6H4), 7.34 (t, 1H, C6H4), 7.45-7.80 (m, 30H, SnPh3). 13C-
{1H} NMR (75.44 MHz, CDCl3): δ 13.0 [1J (117/119Sn-13C) ) 367/
384, SnCH2], 32.4 [2J (117/119Sn-13C) ) 19, CH2], 125.5 (C6H4),
127.6 (C6H4), 128.4 [3J (117/119Sn-13C) ) 47, Cm], 128.6 (C6H4),
128.8 [4J (117/119Sn-13C) ) 11, Cp], 137.0 [2J (117/119Sn-13C) ) 35,
Co], 138.7 [1J (117/119Sn-13C) ) 466/488, Ci], 144.9 [3J (117/119Sn-
µ, cm-1
no. of data colld
θmax, deg
25.7
25.7
10 509
10 031
no. of unique data 18 138
no. of unique data 6261
with I g 3.0σ(I)
R
Rw
0.090
0.105
0.063
0.034
13C) ) 57, C6H4]. 119Sn{1H} NMR (111.85 MHz, CDCl3):
δ
-100.1 [1J (13C-119Sn) ) 386, 1J (13C-119Sn) ) 488]. Anal. Calcd
4H, 2J (117/119Sn-1H) ) 54, SnCH2], 3.11 [t, 4H, 3J (117/119Sn-
1H) ) 112, CH2], 7.14 (d, 2H, C6H4), 7.16 (s, 1H, C6H4), 7.31 (t,
1H, C6H4). 13C{1H} NMR (75.44 MHz, CDCl3): δ 1.0 [1J (29Si-
for C46H42Sn2: C 66.39, H 5.09. Found: C 66.15, H 4.72.
Syn th esis
of
1,3-Bis{[2-(tr im eth ylsilylm eth yl)d i-
3
13C) ) 52, J (117/119Sn-13C) ) 26, SiMe3], 11.7 [1J (29Si-13C) )
p h en ylsta n n yl]eth yl}ben zen e, 8. To a magnetically stirred
solution (0 °C) of 7 (10.00 g, 12.01 mmol) in CHCl3 (100 mL)
was added I2 (6.10 g, 24.02 mmol) in small portions over 30
min. The reaction mixture was stirred for 2 h, the solvent
removed in vacuo, and the resulting yellow oil kept for 3 h at
130 °C and 10-3 Torr to remove all volatile byproducts. The
oily residue (11.19 g, 12.01 mmol) was dissolved in THF (100
mL) and added dropwise at room temperature during 1 h to a
Grignard solution prepared from chloromethyltrimethylsilane
(4.42 g, 36.05 mmol) and Mg (1.75 g, 72.10 mmol) in THF (100
mL). The reaction mixture was refluxed overnight and the
THF removed in vacuo. To the resulting colorless solid was
added Et2O and the suspension hydrolyzed with saturated
NH4Cl solution. The organic layer was washed twice with
water and dried over Na2SO4. After filtration the organic
solvent was evaporated in vacuo and the resulting yellow oil
kept for several hours at 130 °C and 10-3 Torr to remove all
volatile byproducts to give 8.57 g of crude product that could
be used without further purification. 1H NMR (299.98 MHz,
CDCl3): δ 0.25 (s, 18H, SiMe3), 0.45 [s, 4H, 2J (117/119Sn-1H) )
72/75, SiCH2], 1.87 [t, 4H, 2J (117/119Sn-1H) ) 45, SnCH2], 3.13
[t, 4H, 3J (117/119Sn-1H) ) 51, CH2], 7.22 (d, 2H, C6H4), 7.26 (s,
1H, C6H4), 7.41 (t, 1H, C6H4), 7.50-7.85 (m, 20H, SnPh2).
13C{1H} NMR (75.44 MHz, CDCl3): δ -5.5 [1J (117/119Sn-13C)
) 244/255, SiCH2], 1.6 [3J (117/119Sn-13C) ) 16, SiMe3], 13.7
[1J (117/119Sn-13C) ) 350/366, SnCH2], 32.5 [2J (117/119Sn-13C) )
17, CH2], 125.3 (C6H4), 127.5 (C6H4), 128.2 [3J (117/119Sn-13C)
) 47, Cm], 128.4 (C6H4), 128.5 (Cp), 136.6 [2J (117/119Sn-13C)
) 35, Co], 140.5 [1J (117/119Sn-13C) ) 440/462, Ci], 145.1
[3J (117/119Sn-13C) ) 57, C6H4]. 119Sn{1H} NMR (111.85 MHz,
CDCl3): δ -59.0 [1J (13C-119Sn) ) 463, 1J (13C-119Sn) ) 368,
1J (13C-119Sn) ) 254].
43, 1J (117/119Sn-13C) ) 284/297, SiCH2], 29.4 [1J (117/119Sn-13C)
) 450/471, SnCH2], 30.5 [2J (117/119Sn-13C) ) 30, CH2], 126.5
(C6H4), 127.9 (C6H4), 129.7 (C6H4), 143.1 [3J (117/119Sn-13C) )
76, C6H4]. 119Sn{1H} NMR (111.85 MHz, CDCl3): δ 130.6. Anal.
Calcd for C18H34Cl4Si2Sn2: C 31.52, H 5.00. Found: C 31.15,
H 5.05.
Syn th esis of th e Or ga n otin Oxid e 10. To a magnetically
stirred solution (0 °C) of NaOH (1 g, 25 mmol) in 15 mL of
H2O was added dropwise a solution of C (1.0 g, 1.46 mmol) in
20 mL of MeOH. The reaction mixture was stirred for 24 h
and the resulting white precipitate filtered off, washed with
water, and dried at 60 °C and 10-3 Torr to give 10 as a colorless
solid (840 mg, 100% yield, mp 290 °C dec). Anal. Calcd for
C
18H34O2Si2Sn2: C 37.53, H 5.95. Found: C 37.60, H 6.28.
Syn th esis of th e Tetr a m er ic Tetr a or ga n od ista n n ox-
a n e 11. 9 (595 mg, 0.868 mmol) and 10 (500 mg, 0.868 mmol)
were combined, toluene (20 mL) was added, and reaction
mixture was stirred for 24 h at reflux to give a clear solution.
The solution was concentrated to 2 mL to give 11 as color-
less crystals (790 mg, 72% yield, mp 278-279 °C). 1H NMR
(299.98 MHz, CDCl3): δ 0.23 (s, 18H, SiMe3), 0.23 (s, 18H,
SiMe3), 0.98 [s, 4H, 2J (117/119Sn-1H) ) 123, SiCH2], 1.02 [s, 4H,
2J (117/119Sn-1H) ) 123, SiCH2], 1.93 [m, 4H, SnCH2], 2.23 [m,
4H, SnCH2], 2.89 [t, 4H, CH2], 3.23 [t, 4H, CH2], 6.10 (s, 1H,
C6H4), 6.98 (d, 2H, C6H4), 7.01 (s, 1H, C6H4), 7.18-7.26 (m,
4H, C6H4). 13C{1H} NMR (75.44 MHz, CDCl3): δ 1.4 [1J (29Si-
13C) ) 52, 3J (117/119Sn-13C) ) 32, SiMe3], 2.0 [1J (29Si-13C) )
52, 3J (117/119Sn-13C) ) 30, SiMe3], 18.4 [1J (29Si-13C) ) 43,
1J (117/119Sn-13C) ) 402/420, SiCH2], 19.5 [1J (29Si-13C) ) 43,
1J (117/119Sn-13C) ) 377/394, SiCH2], 30.9 [2J (117/119Sn-13C) )
33, CH2], 31.1 [2J (117/119Sn-13C) ) 33, CH2], 32.3 [1J (117/119Sn-
13C) ) 569/595, SnCH2], 34.9 [1J (117/119Sn-13C) ) 612/640,
SnCH2], 124.8 (C6H4), 125.4 (C6H4), 126.9 (C6H4), 127.6
(C6H4), 128.8 (C6H4), 129.7 (C6H4), 143.2 [3J (117/119Sn-13C) )
76, C6H4], 143.5 [3J (117/119Sn-13C) ) 76, C6H4]. 119Sn{1H} NMR
(111.85 MHz, CDCl3): δ -79.1 [2J (119Sn-117/119Sn) ) 72],
-141.5 [2J (119Sn-117/119Sn) ) 72]. Anal. Calcd for C72H136Cl8O4-
Si8Sn8: C 34.26, H 5.43. Found: C 34.25, H 5.55.
Syn th esis
of
1,3-Bis{[2-(tr im eth ylsilylm eth yl)d i-
ch lor osta n n yl]eth yl}ben zen e, 9. To a magnetically stirred
solution (0 °C) of 8 (8.57 g, 10.05 mmol) in acetone (100 mL)
was added dropwise a solution of HgCl2 (10.92 g, 40.20 mmol)
in acetone (100 mL) over 30 min. The reaction mixture was
stirred overnight and the resulting precipitate (PhHgCl)
filtered off. After removing the acetone in vacuo Et2O (100 mL)
was added and the suspension stirred for 10 min. The PhHgCl
was removed by filtration and the organic solvent evaporated
in vacuo to give the crude product, which was recrystallized
from hexane to give 9 as a colorless solid (3.7 g, 54% yield, mp
64-67 °C). 1H NMR (299.98 MHz, CDCl3): δ 0.12 (s, 18H,
X-r a y Cr ysta llogr a p h y. Data were collected for colorless
crystals of 6 and 11‚toluene at 173 K employing graphite-
monochromatized Mo KR radiation, λ ) 0.7107 Å, on a Nonius
KappaCCD diffractometer. Corrections were made for Lorentz
and polarization effects26 and for absorption using an empirical
procedure (SORTAV). Crystal data are given in Table 1.
2
SiMe3), 0.55 [s, 4H, J (117/119Sn-1H) ) 87/91, SiCH2], 2.08 [t,