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Updated: Apr 21, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
A diruthenium μ-carbido complex that shows singlet-carbene-like reactivity
Shin Takemoto1, Jun Ohata, Kento Umetani
1Department of Chemistry, Graduate School of Science, Osaka Prefecture University , Sakai, Osaka 599-8531, Japan.
Abstract:
Low-temperature deprotonation of the cationic μ-methylidyne complex [(Cp*Ru)2(μ-NPh)(μ-CH)][BF4] (Cp* = η(5)-C5Me5) with KN(SiMe3)2 affords a thermally unstable μ-carbido complex [(Cp*Ru)2(μ-NPh)(μ-C)] (2), as evidenced by trapping experiments with elemental S or Se and (13)C NMR spectroscopic observation. The reactivity of 2 toward CO2, Ph2S(+)CH2(-), EtOH, and an intramolecular C-H bond indicates that the μ-carbido carbon in 2 has an ambiphilic (nucleophilic and electrophilic) nature consistent with the formulation of 2 as the first example of a transition-metal-substituted singlet carbene. DFT study suggests that the Ru substituents in 2 are stronger σ-donor and weaker π-donor to the carbene center than amino substituents in N-heterocyclic carbenes.
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