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

Abstract

The anionic mixed-metal cluster [Ru₃Ir(CO)₁₃]^– 1, found to be catalytically active in the carbonylation of methanol, reacts with methanol at 70 °C to give, with O–H activation of the substrate, the cluster anion [HRu₃Ir(CO)₁₂(OMe)]^– 2, which upon prolonged reaction loses formaldehyde to give the cluster anion [H₂Ru₃Ir(CO)₁₂]^– 3; both anions 2 and 3 crystallise together as the double-salt [N(PPh₃)₂]₂[HRu₃Ir(CO)₁₂(OMe)][H₂Ru₃Ir(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.