ja509364d_si_001.cif (92.47 kB)

A Diruthenium μ‑Carbido Complex That Shows Singlet-Carbene-like Reactivity

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posted on 12.11.2014, 00:00 by Shin Takemoto, Jun Ohata, Kento Umetani, Masahiro Yamaguchi, Hiroyuki Matsuzaka
Low-temperature deprotonation of the cationic μ-methylidyne complex [(Cp*Ru)2(μ-NPh)­(μ-CH)]­[BF4] (Cp* = η5-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 13C 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.