Abstract
AbstractThe [μ2‐N2{CpRu(PPh3)2}2]2+ (12+) dication is a source of the formal 16‐electron [CpRu(PPh3)2]+ fragment, and it reacts with internal alkynes such as 1,3‐diphenylpropynone, 4‐phenyl‐3‐butyn‐2‐one, and 3‐cyclopropyl‐1‐phenylpropynone to yield η1‐vinylidene complexes 2a+–2c+ by C–C bond activation. In the case of 1,3‐diphenylpropynone, the η1‐ketone complex [CpRu(PPh3)2{PhC(η1‐O)C≡CPh}]+ (3a+) was isolated as its PF6– salt, and it is apparently an intermediate in the formation of the vinylidene complex. Complexes 2a+–2c+ were characterized as their BArF4– [ArF = 3,5‐bis(trifluoromethyl)phenyl] salts by NMR and IR spectroscopic methods, ESI‐MS, and EA. The single crystal X‐ray diffraction structure of 2aBArF4 is presented. These reactions represent the first examples where an internal alkyne undergoes C–C bond migration to form an η1‐vinylidene complex. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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