No Fear of Perfluorinated Peroxides: Syntheses and Solid-State Structures of Surprisingly Inert Perfluoroalkyl Peroxides
Graphical Abstract
Stretched planar peroxides: [(F3C)3CO]2 and [(C2F5)(F3C)2CO]2 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° as well as elongated O−O bonds because of the bulky perfluorinated alkyl groups. In addition, they are insensitive to both impact (>40 J) and friction (>360 N).
Abstract
We report on the solid-state structures of bis(nonafluoro-tert-butyl) peroxide [(F3C)3CO]2 and bis(undecafluoro-2-methyl-2-butyl) peroxide [(C2F5)(F3C)2CO]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°, 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 (X2). Ferrocene is oxidized by [(F3C)3CO]2 to [FeIIICp2][OC(CF3)3].
