The reactions of the germylenes, [(Dipp)NCMeCHCORGeCl] (1a: R = Me, 1b: R = Ph) with [Ir₂Cl₂(μ-Cl)₂(η⁵-Cp*)₂] led to the formation of the adducts [(Dipp)NCMeCHCORGeClIrCl₂Cp*] (3a: R = Me and 3b: R = Ph). On the other hand, [Rh₂Cl₂(μ-Cl)₂(η⁵-Cp*)₂] does not react with the germylenes (1a and 1b). When the reactions of 1a and 1b are carried out with [Cp*TaCl₄], the reaction led to decomposition. The reaction of 1a or 1b with TaCl₅ yielded the transmetallated products [(Dipp)NCMeCHCORTaCl₄] (4a: R = Me, 4b: R = Ph) with the extrusion of GeCl₂. Our theoretical studies show that for, the insertion of TaCl₅ to 1a and the formation of 4a with concomitant elimination of GeCl₂ is energetically favourable. Extrusion of SnCl₂ is also observed when the corresponding stannylene, [(Dipp)NCMeCHCOMeSnCl] was reacted with TaCl₅. All these compounds have been characterized by ¹H and ¹³C NMR spectroscopy, elemental analysis and the constitution of compounds 1b, 3b, and 4a were confirmed by single-crystal X-ray crystallography.