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The reaction of RcC⋮CH [Rc = (η5-C5H5)Ru(η5-C5H4)] with RuClL2(η5-C5R5) [R = H or Me; L2 = 2PPh3 or Ph2PCH2CH2PPh2 (dppe)] in the presence of NH4PF6 and subsequent treatment with base gave Ru(II) ruthenocenylacetylide complexes RcC⋮CRuL2(η5-C5R5) in good yields. In a similar manner, the pentamethylruthenocene analogues, Rc‘C⋮CRuL2(η5-C5R5) [Rc‘ = (η5-C5Me5)Ru(η5-C5H4)], were also prepared. Cyclic voltammograms of the complexes showed two reversible one-electron-oxidation processes, consisting of the processes [Ru(II)Ru‘(II)] to [Ru(III)Ru‘(II)] and then to [Ru(III)Ru‘(III)]. Chemical oxidation of the complexes induced novel structural rearrangement. The two-electron oxidation of complex RcC⋮CRu(PPh3)2(η5-C5H5) afforded a kind of allenylidene complex, a cyclopentadienylidenethylidene complex, [(η5-C5H5)Ru{μ-η6:η1-C5H4CC}Ru(PPh3)2(η5-C5H5)]2+, in 90% yield. The one-electron oxidation of Rc‘C⋮CRu(PPh3)2(η5-C5H5) gave the vinylidene complex (Rc‘CHC)Ru(PPh3)2(η5-C5H5) in 62% yield, while the two-electron oxidation led to the fulvene−vinylidene complex [(η6-C5Me4CH2)Ru{μ-η5:η1-C5H4CHC}Ru(PPh3)2(η5-C5R5)]2+ by an intramolecular hydrogen transfer in 59% yield.

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