Some reactions of azides with diynyl-bis(phosphine)ruthenium-cyclopentadienyl complexes

Reactions of SiMe3(N3) with Ru(CCH)(PP)Cp’ [PP = (PPh3)2, Cp′ = Cp; PP = dppe, Cp′ = Cp*] afford Ru(N3)(PP)Cp′. Reactions of Ru(CCCCR)(dppe)Cp* with SiMe3(N3) give Ru{N3C(CN)CH2R}(dppe)Cp* (R = H 2, Ph 3). With RuCl(dppe)Cp* in the presence of [NH4]PF6, 2 gives binuclear [Cp*(dppe)Ru{N3C[{(CN)Ru(dppe)Cp*]CMe}]PF6 4. The reaction between TsN3 and Ru(CCCCH)(dppe)Cp* gives Ru{(NC)CNNTsCHC(NTs)}(dppe)Cp* 5, with a small amount of TsNPPh2CH2CH2PPh2NTs 6 being obtained from some reactions. X-ray determined structures of Ru(N3)(dppe)Cp* and 2–5 are reported, together with plausible routes to 2 and 3.