AbstractA dimeric tantalum‐zinc neophylidyne complex proposed to be [{{TaCl2(μ‐CCMe2Ph)(μ‐Cl)(THF)2}{Zn(μ‐Cl)}}2](5a), which can be prepared easily on a scale of 50 mmol, is an ideal starting material for the synthesis of mono‐ and bis(ortho)‐chelated arylamine alkylidyne species such as the red Ta‐Zn neophylidyne complexes [TaCl2(μ‐C6H4CH2NMe2−2)(μ‐CCMe2Ph)ZnCl(THF)] (6) and [TaCl2‐{μ‐C6H3(CH2NMe2)2−2,6}(μ‐CCMe2Ph)ZnCl] (7), which have been isolated in high yields. Reaction of 7 with tmeda affords the Tav alkylidene complex [TaCl(=CHCMe2Ph){C6H3(CH2N(Me)CH2)−2‐CH2NMe2)‐6}] (8), which shows catalytic activity in the ring‐opening metathesis polymerization of norbornene.