Activation of C-F and Ni-C Bonds of [P,S]-Ligated Nickel Perfluorometallacycles

The first example of a [P,S]-ligated metal perfluorocyclopentane is reported. The new metallacycle undergoes C-alpha-F activation in the presence of a Lewis acid, followed by chemoselective ligand migration, affording a fused metallabicyclic product. Reactivity of this product includes an unprecedented nucleophile-induced ring-opening reaction, involving loss of a beta-fluoride. Additionally, hydrolysis of the metallabicyclic product affords a single isomer of hexafluoro-1-butene.