Complex (PNP)TiCH^tBu(CH₂^tBu) (PNP⁻ = N[2-P(CHMe₂)₂-4-methylphenyl]₂) eliminates H₃C^tBu to form transient (PNP)TiC^tBu, which activates the C–F bond of ortho-difluoropyridine and ortho-fluoropyridine to form the alkylidene–fluoride complexes, (PNP)TiC[^tBu(NC₅H₃F)](F) (1) and (PNP)TiC[^tBu(NC₅H₄)](F) (2), respectively. When (PNP)TiCH^tBu(CH₂^tBu) is treated with meta-fluoropyridine, the ring-opened product (PNP)Ti(C(^tBu)CC₄H₃-3-FNH) (3) is the only recognizable titanium metal complex formed. Theoretical studies reveal that pyridine binding disfavors 1,2-CF bond addition across the alkylidyne ligand in the case of ortho-fluoride pyridines, while sequential [2 + 2]-cycloaddition/β-fluoride elimination is a lower energy pathway. In the case of meta-fluoropyridine, [2 + 2]-cycloaddition and subsequent ring-opening metathesis is favored as opposed to C–H bond addition or sequential [2 + 2]-cycloaddition/β-hydride elimination. In all cases, C–H bond addition of ortho-fluoropyridines or meta-fluoropyridine is discouraged because such substrate must bind to titanium via its C–H bond, which is rather weak compared to the titanium–pyridine binding.