The synthesis and isolation of [Ru(Cp)(P Cy 2 N Ph 2 )(=C=CHPh]PF 6 and [Ru(Cp*)(P Cy 2 N Cy 2 )(=C=CHPh)]PF 6 was successfully accomplished. Use of these ruthenium vinylidene complexes for stoichiometric reactions with a variety of amines was performed. Upon reaction with alkyl amines, deprotonation of the C β hydrogen resulted in formation of acetylide complex [Ru(Cp*)(P Cy 2 N Ph 2 )(−C≡CPh)], and the species was confirmed through independent synthesis. In contrast, reaction of the less basic aryl amine aniline with [Ru(Cp)(P Cy 2 N Cy 2 )(=C=CHPh)]PF 6 resulted in outer sphere addition to give a Fischer carbene product.
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Beardall et al. (2024) studied this question.
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