688 Yoshimura et al.
(sodium benzophenone ketyl) DME (2 mL) under
a nitrogen atmosphere. The mixture was stirred at
ambient temperature for 1.5 h, resulting in the for-
mation of a dark blue solution of SmI2. After adding
the substrate (0.5 mmol) to the solution, the flask
was placed in an oil bath maintained at 90°C and
the reaction mixture was refluxed for 3–7 h. For pho-
toirradiation, a Xe lamp was used through Pyrex or
a UV filter. After the resulting mixture was cooled
to room temperature, the mixture was treated with
HCl (1 mol/L, 20 mL) and the product was extracted
with ether (10 mL × 3). The combined organic layer
was washed with the saturated NaHCO3 solution and
brine, dried over anhydrous MgSO4, and filtered. The
solvent was removed under reduced pressure to af-
ford the corresponding disilanes, which did not re-
quire further purification. The disilanes were identi-
fied by comparison with their authentic compounds:
2a [1172-76-5], 2b [1145-98-8], 2c [18410-59-8], and
2d, see [7d].
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Representative Procedure for Polymerization of
Dichloromethylphenylsilanes
Sm powder (4 mmol) was placed in a 20-mL three-
necked flask equipped with a reflux condenser and
a dropping funnel with 1,2-diiodoethane (1 mmol)
and freshly distilled (sodium-benzophenone ketyl)
DME (10 mL) under nitrogen atmosphere. The mix-
ture was stirred at ambient temperature for 1.5 h,
resulting in the formation of a dark blue solution of
SmI2. After dropwise adding dichloromethylphenyl-
silane (1 mmol) to the solution, the reaction mixture
was stirred for 6 h and photoirradiated through a
glass filter (Asahi Glass). The reaction mixture was
treated with EtOH (1 mL), poured into hydrochlo-
ric acid (1 mol/L, 20 mL), and extracted with ether
(50 mL × 3). The combined organic layer was
washed with the saturated NaHCO3 solution and
brine, dried over anhydrous MgSO4, and filtered.
The solvent was removed under reduced pressure,
affording polysilane as a white solid. Yield: 0.130 g
1
(68%, hν > 435 nm). H NMR spectra: δ (CDCl3):
–0.85 to 0.86 (m, 3H), 6.40–7.46 (m, 5H). IR (KBr)
νmax: 3056, 2956, 1427, 1250, and 1105 cm−1. The
molecular weight of the polymer was determined by
GPC calibrated by polystyrene standards with THF
as the eluent.
ACKNOWLEDGMENTS
This research was supported by the Industry-
University Cooperation Program of Sakai
City.
Heteroatom Chemistry DOI 10.1002/hc