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 Cα–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 β-fluoride. Additionally, hydrolysis
of the metallabicyclic product affords a single isomer of hexafluoro-1-butene.