Formation of a Dinuclear Imido Complex from the Reaction of a Ruthenium(VI) Nitride with a Ruthenium(II) Hydride

The treatment of [Ru(L_OEt)(N)Cl₂] (1; L_OEt⁻ = [Co(η⁵-C₅H₅){P(O)(OEt)₂}₃]⁻) with Et₃SiH affords [Ru(L_OEt)Cl₂(NH₃)] (2), whereas that with [Ru(L_OEt)(H)(CO)(PPh₃)] (3) gives the dinuclear imido complex [(L_OEt)Cl₂Ru(μ-NH)Ru(CO)(PPh₃)(L_OEt)] (4). The imido group in 4 binds to the two ruthenium atoms unsymmetrically with Ru−N distances of 1.818(6) and 1.952(6) Å. The reaction between 1 and 3 at 25 °C in a toluene solution is first order in both complexes with a second-order rate constant determined to be (7.2 ± 0.4) × 10⁻⁵ M⁻¹ s⁻¹.