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

We report on the solid‐state structures of bis(nonafluoro‐tert‐butyl) peroxide [(F 3 C) 3 CO] 2 and bis(undecafluoro‐2‐methyl‐2‐butyl) peroxide [(C 2 F 5 )(F 3 C) 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°, 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 [(F 3 C) 3 CO] 2 to [Fe III Cp 2 ][OC(CF 3 ) 3 ].