Fixation and spontaneous dehydrogenation of methanol on a triruthenium-iridium framework: synthesis and structure of the cluster anion [HRu3Ir(CO)(12)(OMe)](-)

The anionic mixed-metal cluster [Ru3Ir(CO)(13)](-) 1, found to be catalytic ally active in the carbonylation of methanol, reacts with methanol at 70 de grees C to give, with O-H activation of the substrate, the cluster anion [H Ru3Ir(CO)(12)(OMe)](-) 2, which upon prolonged reaction loses formaldehyde to give the cluster anion [H2Ru3Ir(CO)(12)](-) 3; both anions 2 and 3 cryst allise together as the double-salt [N(PPh3)(2)](2)[HRu3Ir(CO)(12)(OMe)][H2R u3Ir(CO)(12)] the single-crystal X-ray structure analysis of which reveals a butterfly Ru3Ir skeleton for 2 and a tetrahedral Ru3Ir skeleton for 3.