The mixed-ligand complexes [Cp ∗ (CO) 2 Fe(CH 2 ) n M(CO) x Cp] (x=2, M=Fe or Ru; x=3, M=W, Cp ∗ =η 5 -C 5 (CH 3 ) 5 ; Cp=η 5 -C 5 H 5 ; n=3–6), type I, react with one equivalent of the hydride abstractor Ph 3 CPF 6 to give the transition metal-stabilized carbocation complexes [Cp ∗ (CO) 2 Fe{μ-(C n H 2n−1 )}M(CO) x Cp]PF 6 . Similarly the new heterobimetallic complexes [Cp(CO) 2 Ru{μ-(C n H 2n−1 )}W(CO) 3 Cp], type II, react with Ph 3 CPF 6 to give the carbocation complexes [Cp(CO) 2 Ru{μ-(C n H 2n−1 )}W(CO) 3 Cp]PF 6 . Spectroscopic data show that hydride abstraction selectively takes place from the methylene group β to the metal atom attached to the Cp ∗ ligand in type I complexes. In type II complexes, the reaction is totally metalloselective with hydride abstraction occurring at the CH 2 β to the ruthenium metal centre. All products have been characterized by IR, 1 H, 13 C NMR spectroscopy and elemental analysis. 1 H and 13 C NMR data clearly show that in the carbocation complexes one metal is σ-bonded to the alkanediyl carbocation while the other is bonded to the cationic end in a η 2 -fashion forming a chiral metallacylopropane type structure. The molecular structures of the cationic metallacyclic complexes [Cp ∗ (CO) 2 Fe{μ-(C 3 H 5 )}Fe(CO) 2 Cp]PF 6 [E.O. Changamu, H.B. Friedrich, M. Rademeyer, Acta Crystallogr., Sect. E 62 (2006) m442.] and [Cp ∗ (CO) 2 Fe(μ-C 3 H 5 )Ru-(CO) 2 Cp]PF 6 [H.B. Friedrich, E.O. Changamu, M. Rademeyer, Acta Crystallogr., Sect. E 62 (2006) m405.] have been confirmed by single crystal X-ray crystallography and reported elsewhere. The structures of the precursor complexes [Cp ∗ (CO) 2 Fe(CH 2 ) 3 Ru-(CO) 2 Cp] (1), [Cp ∗ (CO) 2 Fe(CH 2 ) 5 Ru-(CO) 2 Cp] (2), [Cp ∗ (CO) 2 Fe(CH 2 ) 5 W(CO) 3 Cp] (3), and [Cp(CO) 2 Ru (CH 2 ) 5 W(CO) 3 Cp] (4), have been confirmed by single crystal X-ray crystallography. The structure of [Cp ∗ (CO) 2 Fe(CH 2 ) 3 Ru(CO) 2 Cp] is compared with that of its corresponding cationic complex, [Cp ∗ (CO) 2 Fe{μ-(C 3 H 5 )}Ru(CO) 2 Cp]PF 6 .