Katalytische Carbonylierung von Aceton‐oxim an Bisoximato‐diruthenium‐Komplexen: Ein einfacher Zugang zu wasserfreiem Acetonin. Isolierung und Molekülstruktur von [Ru2(CO)5(Me2CNO)2(Me2CNOH)

Abstract

Catalytic Carbonylation of Acetone Oxime at Bisoximatodiruthenium Complexes: A Simple Access to Anhydrous Acetonine. Isolation and Molecular Structure of [Ru2(CO)5(Me2CNO)2(Me2CNOH)]In the presence of catalytic amounts of [Ru2(CO)4(Me2CNO)2(Me2CNOH)2] (1), acetone oxime reacts with carbon monoxide to give 2,3,4,5‐tetrahydro‐2,2,4,4,6‐pentamethylpyrimidine (‘acetonine’). CO2, and NH3. The reaction proceeds presumably via carbonylation of Me2CNOH to the unstable intermediate Me2CNOCHO which undergoes decarboxylation to give the corresponding imine Me2CNH. The final product is assumed to result from the cyclotrimerisation of Me2CNH with elimination of NH3. Evidence for the intermediacy of the imine comes from the analogous reaction of acetophenone oxime, PhMeCNOH, which gives the corresponding imine PhMeCNH as a stable product. The isolation of the complex [Ru2(CO)5(Me2CNO)2(Me2CNOH)] (2) suggests the carbonylation to take place at the bridging oximato ligand of 1.