60
J. Beckmann et al. / Journal of Organometallic Chemistry 688 (2003) 56Á61
/
crystallization from chloroformÁ
white crystalline solid (16.8 g, 95%). m.p. 98Á
1H-NMR: d 1.58 (t, 4H), 1.82 (m, 4H), 3.26 (t, 4H),
7.26Á
7.63 (m, 20H; Ph). 13C{1H}-NMR: d 14.41
(1J(13CÁ117/119 420/439 Hz), 25.80 (2J(13Cm Á
Sn)ꢁ
117/119Sn)ꢁ27 Hz), 72.10 (3J(13Cp Á117/119
Sn)ꢁ63 Hz),
128.54, 129.56 (2J(13Cm Á117/119
Sn)ꢁ13 Hz), 135.73
(2J(13Co Á117/119 (1J(13Ci Á
Sn)ꢁ47 Hz), 137.14
117/119Sn)ꢁ531/554 Hz). 119Sn{1H}-NMR: d ꢂ
85.8.
/
hexane afforded 2 as a
(2J(13CÁ117/119
/
Sn)ꢁ
/
36 Hz), 71.06 (3J(13CÁ117/119
/
Sn)ꢁ
/
/
100 8C.
73 Hz). 119Sn{1H}-NMR: d 79.1. Anal. Calc. for
C14H34Cl2OSi2Sn2 (653.83): C, 25.7; H, 5.2; Found: C,
25.7; H, 5.6%.
/
/
/
/
/
/
/
3.5. Synthesis of {[(Me3SiCH2)(O)Sn(CH2)3]2O}n
/
/
(5)
/
/
/
/
/
A solution of KOH (0.24 g, 4.28 mmol) in water (50
ml) was added to a solution of 4 (0.70 g, 1.07 mmol) in
toluene (50 ml) and the mixture stirred at 100 8C for 1 d.
The white precipitate that formed was collected by
filtration. The collected precipitate was then stirred
with water (400 ml), filtered and further dried by heating
at 80 8C (0.01 mm Hg) for 2 d to give 5 as a white solid
(0.50 g, 86%). m.p.ꢀ300 8C (decomp.).
Anal. Calc. for C14H34O3Si2Sn2 (544.01): C, 30.9; H,
6.3; Found: C, 30.5; H, 6.2%.
Anal. Calc. for C30H32I2OSn2 (899.86): C, 40.0; H, 3.6;
Found: C, 40.1; H, 3.5%.
3.3. Synthesis of [(Me3SiCH2)Ph2Sn(CH2)3]2O (3)
A solution of 2 (10.4 g, 11.6 mmol) in THF (100 ml)
was added to a solution of Me3SiCH2MgCl [prepared
from magnesium (2.47 g, 102 mmol) and Me3SiCH2Cl
(3.12 g, 25.4 mmol) in THF (150 ml)] and the mixture
stirred at reflux for 2 d. The reaction was quenched by
the addition of saturated ammonium chloride at 25 8C.
The organic layer was separated, and the aqueous layer
/
3.6. Synthesis of
{{[(Me3SiCH2)(Cl)Sn(CH2)3]2O}O}4 (6)
was extracted with diethyl ether (3ꢃ100 ml). The
/
combined organic extracts were dried (Na2SO4) and
the solvent was removed in vacuo. The residue was
A solution of 4 (90.0 mg, 0.13 mmol) in toluene (2 ml)
was added to a suspension of 5 (70.0 mg, 0.13 mmol) in
toluene (2 ml) and stirred at 100 8C for 24 h. Removal of
the solvent in vacuo and crystallization from
purified by column chromatography (silica gel 60, 70Á
/
230 mesh) using hexane. Removal of the solvent in
vacuo yielded 3 as a colorless oil (7.57 g, 80%).
1H-NMR: d 0.18 (s, 18H, SiMe3), 0.89 (s, 4H, SiCH2),
chloroformÁ
crystals (170 mg, 92%). m.p. 268Á
1H-NMR: d 0.13 (s, 36H, Me3Si), 0.72Á
/
hexane (30:70) afforded 6 as a colorless
/
270 8C.
1.29 (s, 4H), 1.85 (s, 4H, SnCH2), 3.30 (s, 4H), 7.27 (m,
/1.28 (m, 16H,
1
20H). 13C{1H}-NMR: d ꢂ
/
9.97 (s, J(13CÁ117/119
/
Sn)ꢁ
/
SiCH2), 1.59Á
/
1.89 (m, 16H), 2.13Á
/
2.29 (m, 16H), 3.47Á
/
3
245/257 Hz; SiCH2), ꢂ
Hz, Si)ꢁ51
1J(13CÁ29
(1J(13CÁ117/119
Sn)ꢁ363/380
(2J(13CÁ117/119 19 Hz), 69.32 (3J(13CÁ117/119
Sn)ꢁ
72 Hz), 123.71, 123.97, 132.15 (2J(13Co Á117/119
Hz), 136.22 Sn)ꢁ440/461
(1J(13Ci Á117/119
119Sn{1H}-NMR: d ꢂ56.5 (1J(119SnÁ13
C)ꢁ463 Hz).
/
2.92 (s, J(13CÁ117/119
Hz; Me3Si),
Hz),
/
Sn)ꢁ16
/
3.62 (m, 16H). 119Sn{1H}-NMR: refer to text and Fig. 2.
Anal. Calc. for C56H136Cl8O8Si8Sn8 (2395.68): C, 28.1;
H, 5.7; Found: C, 28.2; H, 5.5%.
/
/
3.22
22.11
/
/
/
/
/
Sn)ꢁ
Sn)ꢁ39
Hz).
/
/
/
/
/
4. Crystallography
/
/
/
Anal. Calc. for C38H54OSi2Sn2 (820.49): C, 55.6; H, 6.6;
Found: C, 55.4; H, 6.7%.
Slow evaporation of a chloroformÁ
solution of 6 gave crystals suitable for X-ray analysis.
Data were collected for a colorless crystal of 6, 0.12ꢃ
0.21ꢃ0.34, at 183 K employing graphite monochroma-
tized MoÁ
AXS SMART CCD diffractometer.
Crystal data for 6: C56H136Cl8O8Si8Sn8, Mꢁ
monoclinic, space group C2/c, aꢁ38.014(1), bꢁ
105.805(9)8, Vꢁ
1.592 g cmꢂ3, mꢁ2.312 mmꢂ1
4736, 14484 unique data, 11203 data with
2.0s(I), Rꢁ0.079, Rw (all data)ꢁ0.207, rꢁ2.34
/
hexane (30:70)
/
3.4. Synthesis of [(Me3SiCH2)Cl2Sn(CH2)3]2O (4)
/
˚
Ka radiation, lꢁ0.71069 A, on a Bruker
/
/
To a solution of 3 (6.00 g, 7.31 mmol) in chloroform
(100 ml) was added excess concentrated HCl (200 ml,
32%). The reaction mixture was stirred and maintained
at 70 8C for 1 d. The organic layer was separated and the
/2395.49,
/
/
˚
12.438(3), cꢁ
/
21.972(5) A, bꢁ
9996(4) A , Dx ꢁ
F(000)ꢁ
I ]
/
/
3
˚
aqueous layer extracted with chloroform (3ꢃ
/100 ml).
/
/
,
The combined organic extracts were dried (CaCl2) and
the solvent removed in vacuo to afford 4 as a brown oil
(3.35 g, 70%) of sufficient purity for further use.
1H-NMR: d 0.15 (s, 18H, Me3Si), 0.83 (s, 4H,
/
/
/
/
/
ꢂ3
˚
e A
(near Sn).
The structure was solved by heavy-atom methods [6]
and refined by a full-matrix least-squares procedure
based on F2 [6b]. Non-hydrogen atoms were refined
anisotropically, hydrogen atoms were included in the
model in the riding model approximation and a weight-
SiCH2), 1.69 (t, 4H), 2.08Á
/
2.10 (m, 4H), 3.57 (t, 4H).
13C{1H}-NMR: d 1.02 (s, 3J(13CÁ117/119
/
Sn)ꢁ
12.39
SiCH2),
Hz),
/
28 Hz,
(s,
1J(13CÁ29
1J(13CÁ117/119
(1J(13CÁ117/119
/
Si)ꢁ
/
52
Hz;
327/342
Me3Si),
Hz;
/
Sn)ꢁ
/
23.36
24.03
/
Sn)ꢁ
/
503/526
ing scheme of the form wꢁ
/
1/[s2(Fo)2ꢀ
/
(0.0848P)2ꢀ
/