Herein, a copper‐catalyzed C−F bond defluorosilylation reaction of tetrafluoroethylene and other polyfluoroalkenes is described. Mechanistic studies, based on a series of stoichiometric reactions with copper complexes, revealed that the key steps of this defluorosilylation reaction are 1) the 1,2‐addition of a silylcopper intermediate to the polyfluoroalkene and 2) a subsequent selective β‐fluorine
An improved procedure for the preparation of trifluorovinylsilanes was established which involved addition of butyllithium to a mixture of chlorosilanes and commercially readily available chlorotrifluoroethylene at −78 to −130 °C, and the resulting monomer was polymerized with a catalyst such as CsF or (R2N)3S+ F2SiMe3− to give black metallic polymer which showed conductivity of 10−9 to 10−10 Ω−1cm−1