Formation of perfluorinated polyphenylenes by multiple pentafluorophenylation using C6F5Si(CH3)3

Pentafluorophenylation of perfluoroarenes with C6F5Si(CH3)3 was investigated by using NMR and MALDI–TOF–MS techniques. Successive multiple pentafluorophenylation easily occurred not only on the para-position but also on the ortho-positions to provide perfluorinated p-phenylene and m-phenylene compounds. The perfluoroarenes having electron-withdrawing substituents provided oligo- to poly-(phenylene)s depending on the added amounts of C6F5Si(CH3)3, while the perfluoroarenes having electron-donor substituents gave H(C6F4)nF polymers produced from C6F5H, which was the decomposed product of C6F5Si(CH3)3.