No Fear of Perfluorinated Peroxides: Syntheses and Solid-State Structures of Surprisingly Inert Perfluoroalkyl Peroxides

摘要

We report on the solid-state structures of bis(nonafluoro-tert-butyl) peroxide [(F3C)(3)CO](2) and bis(undecafluoro-2-methyl-2-butyl) peroxide [(C2F5)(F3C)(2)CO](2). These peroxides were prepared from the corresponding hypofluorites and fluorinated silver wool. The solid-state structures obtained after in situ crystallisation show unusual COOC dihedral angles of 180 degrees, as well as elongated O-O bonds because of the bulky perfluorinated alkyl groups. The perfluorinated alkyl peroxides are insensitive to both impact (>40 J) and friction (>360 N), and resistant towards mineral acids (HX; X=F, Cl, Br) and elemental halogens (X-2). Ferrocene is oxidized by [(F3C)(3)CO](2) to [(FeCp2)-Cp-III][OC(CF3)(3)].