The highly reactive silyl triflates R(4-n)Si(OSO2CF3)(n) are valuable
materials in organosilicon chemistry. Numerous new triflate derivative
s of mono-, oligo-, and polysilanes were prepared by stepwise substitu
tion of trifluoromethylsulfonyl groups for phenyl groups or other leav
ing groups. Conversions of silyl triflates with nucleophiles proceed r
egioselectively and, in most cases, quantitatively at low temperatures
with short reaction times. Therefore, silyl triflates are suitable re
agents for the synthesis and functionalization of linear and cyclic ol
igosilanes. Novel polycarbosilanes, polysilylalkynes, and polysilylphe
nylenes, which show a regular alternating arrangement of silylene grou
ps and organic units, were prepared from lpha,omega-bis[(trifluorometh
ylsulfonyloxy)silyl]- substituted compounds and dinucleophiles. Branch
ed polysilanes and polysilynes were obtained by reductive coupling of
polymeric silyl triflates with potassium-graphite.