Reactions of Bifunctional Perfluoroarylsilanes with Activated C–F Bonds in Perfluorinated Arenes

Abstract

Reactions of bifunctional perfluoroarylsilanes, p- and m-C6F4(SiMe3)2 as well as o-BrC6F4SiMe3, with substituted perfluoroarenes having electron-withdrawing groups were investigated using NMR and density functional theory calculation techniques. The C–F bond in perfluoroarenes was activated by the para-position of an electron-withdrawing group, such as CF3, C6F5, CN, and NO2. The reaction of C6F4(SiMe3)2 mainly occurred at the para-position of the perfluoroarenes and also occurred at the ortho-position of C6F5CN and C6F5NO2. Two equivalent reactions of perfluoroarenes with bifunctional p- and m-C6F4(SiMe3)2 provided disubstituted perfluoroarenes, along with a small amount of protonated monosubstituted perfluoroarenes. The reaction of o-BrC6F4SiMe3 with the CF3- and CN-substituted pentafluorobenzenes provided unexpected coupling products between C–Br and C–F bonds, in addition to the coupling products between C–SiMe3 and C–F bonds.

Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

“…The yields were based on bromopentafluorobenzene. The identity and purity of the target compounds 2-4 were confirmed by 19 F NMR spectra (Bruker AV-300 (282.40 MHz) in CHCl 3 -CDCl 3 ), which were consistent with the literature data [147][148][149]. Compound 1 was also available from alternative sources (Decafluorobiphenyl 99%, Avocado Research Chemicals Ltd., London UK), and this was used in the study.…”