Fulvene-ruthenium and Cp-ruthenium complexes via [2 + 2 + 1] cyclotrimerization of phenylacetylene with [RuCl(Tp)(1,5-cod)]

Afsar Ali, Frederick P. Malan, Eric Singleton, Reinout Meijboom

Research output: Contribution to journalArticlepeer-review

14 Citations (Scopus)


The complex [RuCl(Tp)(1,5-cod)], which bears the labile 1,5-cod ligand, was prepared from a high-yielding route involving the reaction of [RuCl2(1,5-cod)(CH3CN)2] with KTp (Tp = HB(pz)3). The reaction of [RuCl(Tp)(1,5-cod)] with phenylacetylene in either ethanol or methanol gave anti-Markovnikov alkoxide-adduct complexes [Ru(Tp)(η6-C5H2Ph2-CH(Ph)R)] (R = OMe, OEt). These adducts were formed by [2 + 2 + 1] cyclotrimerization reactions of phenylacetylene mediated by the precursor complex, [RuCl(Tp)(1,5-cod)]. The ruthenium(II)-fulvene complex, [Ru(Tp)(η6-C5H2Ph2-CH(Ph))]+, involved in these transformations was successfully isolated in the presence of NH4PF6. These complexes were fully characterized by 1H NMR, 13C NMR, DEPT, HSQC, IR, and ESI-MS spectroscopy. The molecular structures of [Ru(Tp)(η6-C5H2Ph2-CH(Ph)R)] (R = OMe/OEt) and [Ru(Tp)(η6-C5H2Ph2-CH(Ph))]PF6 have been determined by X-ray single-crystal diffraction. These complexes have piano-stool structures around the ruthenium center where half of the coordination sites are occupied by the pyrazole ligand while the remaining sites are occupied by either the π-bonded cyclopentadiene (Cp) or fulvene ligand.

Original languageEnglish
Pages (from-to)5983-5989
Number of pages7
Issue number21
Publication statusPublished - 10 Nov 2014

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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