Formation of the first heterobimetallic phosphido-bridged σ–π-acetylide complex [(C ₅ H ₅ ) ₂ Ti(µ–σ,η ² -CCPh)(µ-PPh ₂ )Ni(PPh ₃ )] by cleavage of the central C–C single bond in PhCC–CCSiMe ₃ and of the P–C bond in Ph ₃ P, and coupling of the fragments to PhCCSiMe ₃

An unexpected activation of the central C–C single bond of PhCC–CCSiMe3 and of one P–C bond in Ph3P and coupling of the fragments to PhCCSiMe3 was observed in the reaction of [Ni(PPh3)2(η2-PhCC–CCSiMe3)] with ‘(C5H5)2’ providing, via the tweezer-like titanocene nickel(0) triphenylphosphine bisacetylide complex [(C5H5)2Ti(µ–σ, η2-CCSiMe3)(CCPh)Ni(PPh3)]1, the phosphido-bridged σ–π-acetylide complex [(C5H5)2 Ti(µ–σ, η2-CCPh)(µ-PPh2)Ni(PPh3)]2.