Stoichiometric and Catalytic Degradation of SF6 with Cobaltocene

The controlled reduction of SF6 (25 °C, 1 bar) with cobaltocene results in the formation of the mixed salt [Cp2Co]2[SF5][F]. The salt can be characterized by solution and solid-state heteronuclear NMR and IR spectroscopies and demonstrates a degree of mineralization of the S and F atoms when reacted with borosilicate glass. Although [Cp2Co]2[SF5][F] is highly reactive, the structure of the corresponding [Cp2Co][F] is also reported herein, thus providing structural evidence for the naked fluoride anion. The mild activation of SF6 by cobaltocene also permits its catalytic degradation using phosphines as terminal reductants.