Synthesis, functionalization, and cross-linking reactions of organosilicon polymers using silyl triflate intermediates

The design and synthesis of new materials are two key steps in the advancement of technology. One of the most promising approaches of development of new materials that combine advantages of organic polymers with those of inorganic solids is to devise polymers that have a backbone of inorganic atoms to which are attached organic side groups. Among the best developed examples of ‘inorganic–organic polymers’ are organosilicon polymers. The synthesis of new organosilicon polymers using silyl triflate intermediates is reviewed in this article. Protodephenylation of phenylated polysilanes as well as poly(silylenemethylenes) by triflic acid gave new functionalized compounds. Network polymers were obtained by reductive coupling of silyl triflates with potassium–graphite. Novel poly(silylenealkynes) and poly(silylenearylenes) containing a regular alternating arrangement of silylene groups and organic units were prepared from α,ω-bis[(trifluoromethyl)sulfonyloxysilyl]-substituted compounds and dinucleophiles. Some of the polymers are potential organic precursor for ceramic materials. The correlation between structure and thermolytic behavior is demonstrated on selected examples.