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 ...