W. Uhlig, SILYL TRIFLATES - VALUABLE MATERIALS FOR THE SYNTHESIS OF ORGANOSILICON OLIGOMERS AND POLYMERS, Polymers for advanced technologies, 8(11), 1997, pp. 731-740
The highly reactive silyl triflates R4-nSi(OSO2CF3)(n) are valuable ma
terials in organosilicon chemistry. Numerous new triflate derivatives
of mono-, oligo- and polysilanes were prepared by stepwise substitutio
n of trifluoromethanesulfonyl groups for phenyl groups or other leavin
g groups. Conversions of silyl triflates with nucleophiles proceed reg
ioselectively and, in most cases, quantitatively at low temperatures w
ith short reaction times. Therefore, silyl triflates are suitable reag
ents for the synthesis and functionalization of linear and cyclic olig
osilanes. Novel polycarbosilanes, polysilylalkynes and polysilylphenyl
enes, which show a regular alternating arrangement of silylene groups
and organic units, were prepared from lpha,omega-bis[(trifluoromethyl)
sulfonyloxysilyl]- substituted compounds and dinucleophiles. Branched
polysilanes and polysilynes were obtained by reductive coupling of pol
ymeric silyl triflates with potassium-graphite. (C) 1997 by John Wiley
& Sons, Ltd.