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

The treatment of [Ru(L<sub>OEt</sub>)(N)Cl<sub>2</sub>] (<b>1</b>; L<sub>OEt</sub><sup>−</sup> = [Co(η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>){P(O)(OEt)<sub>2</sub>}<sub>3</sub>]<sup>−</sup>) with Et<sub>3</sub>SiH affords [Ru(L<sub>OEt</sub>)Cl<sub>2</sub>(NH<sub>3</sub>)] (<b>2</b>), whereas that with [Ru(L<sub>OEt</sub>)(H)(CO)(PPh<sub>3</sub>)] (<b>3</b>) gives the dinuclear imido complex [(L<sub>OEt</sub>)Cl<sub>2</sub>Ru(μ-NH)Ru(CO)(PPh<sub>3</sub>)(L<sub>OEt</sub>)] (<b>4</b>). The imido group in <b>4</b> binds to the two ruthenium atoms unsymmetrically with Ru−N distances of 1.818(6) and 1.952(6) Å. The reaction between <b>1</b> and <b>3</b> 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<sup>−5</sup> M<sup>−1</sup> s<sup>−1</sup>.