188580-38-3Relevant academic research and scientific papers
Novel structural rearrangements induced by metal-metal interactions in ruthenium(II) ruthenocenyl- and (pentamethylruthenocenyl)acetylide complexes, RcC≡CRuL2(η5-C5R5) and Rc′C≡CRuL2(η5-C5R5)
Sato, Masaru,Kawata, Yasushi,Shintate, Hitoshi,Habata, Yoichi,Akabori, Sadatoshi,Unoura, Kei
, p. 1693 - 1701 (2008/10/08)
The reaction of RcC≡CH [Rc = (η5-C5H5)Ru(η5-C 5H4)] with RuCIL2(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-C 5H4)], 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-C5H 5) afforded a kind of allenylidene complex, a cyclopentadienyl-idenethylidene complex, [(η5-C5H5)Ru{μ-η 6:η1-C5H4C=C}Ru(PPh 3)2(η5-C5H5)] 2+, in 90percent yield. The one-electron oxidation of Rc′C≡CRu(PPh3)2(η5-C 5H5) gave the vinylidene complex (Rc′CH=C)Ru(PPh3)2(η5-C 5H5) in 62percent yield, while the two-electron oxidation led to the fulvene-vinylidene complex [(η6-C5Me4CH2)Ru{μ-η 5:η1-C5H4CH=C}Ru(PPh 3)2(η5-C5R5)] 2+ by an intramolecular hydrogen transfer in 59percent yield.
