Reaction of [Fe(Cp*)(dppe)Cl] [1, Cp* = eta(5)-C(5)Me(5), dppe = eta(2)-ethylenebis(diphenylphosphine)] and NH4-PF6 in methanol with equiv of Me(3)SiC=CH produced the vinylidene complex [Fe(Cp*)(dppe)(=C=CH2)][PF6] (2) isolated in 89% yield. The complex 2 was readily deprotonated by KOBu(t) in tetrahydrofuran (THF), giving the ethynyl iron complex Fe(Cp*)(dppe)(-C=CH) (3) isolated after workup as a thermally stable orange solid in 98% yield. The addition of 0.95 equiv of [Cp(2)Fe][PF6] to a -80 degrees C solution of 3 gave the low-spin Fe(III) intermediate 3[PF6] characterized by ESR spectroscopy. Upon stirring for 5 h, 3[PF6] produced a brown solution from which the bis(vinylidene) complex [Fe(Cp*)(dppe)](=C=CH-HC=C=)[(dppe)(Cp*)Fe][PF6](2) was isolated (4, 87 %) as a stable compound.