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

The treatment of [Ru(LOEt)(N)Cl2] (1; LOEt− = [Co(η5-C5H5){P(O)(OEt)2}3]−) with Et3SiH affords [Ru(LOEt)Cl2(NH3)] (2), whereas that with [Ru(LOEt)(H)(CO)(PPh3)] (3) gives the dinuclear imido complex [(LOEt)Cl2Ru(μ-NH)Ru(CO)(PPh3)(LOEt)] (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.