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 nuclear magnetic resonance and infrared 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.