Abstract: | Molecular and Crystal Structure of Bis[chloro(μ‐phenylimido)(η5‐pentamethylcyclopentadienyl)tantalum(IV)](Ta–Ta), [{TaCl(μ‐NPh)Cp*}2] Despite the steric hindrance of the central atom in [TaCl2(NPh)Cp*] (Ph = C6H5, Cp* = η5‐C5(CH3)5), caused by the Cp* ligand, the imido‐ligand takes a change in bond structure when this educt is reduced to the binuclear complex [{TaCl(μ‐NPh)Cp*}2] in which tantalum is stabilized in the unusual oxidation state +4. |