The construction of fluorocarbene ligands within the coordination sphere of transition metal complexes using sequential nucleophilic and electrophilic addition to a vinylidene complex is described. Reaction of [Ru(η⁵-C₅H₅)(dppe)(CCPhF)][N(SO₂Ph)₂] with [NMe₄]F results in nucleophilic attack of fluoride at the metal-bound carbon of the vinylidene ligand to give alkenyl complex [Ru(η⁵-C₅H₅)(dppe)(–CFCFPh)]. Subsequent eletrophilic fluorination with N-fluorobenzenesulfonimide (NFSI) results in the formation of the fluorinated carbene complex [Ru(η⁵-C₅H₅)(dppe)(CF–CHFPh)][N(SO₂Ph)₂]. The fluorocarbene complexes undergo rearrangement to liberate free fluorinated alkenes, a process governed by the choice of solvent and anion, representing a new metal-mediated route to fluorinated alkenes from alkynes.