ИСТИНА

Over the last decade, we are systematically studying the reactivity of a,b-unsaturated ketones in thermal reactions with ruthenium carbonyls.[1-2] The reactions of Ru3(CO)12 yield ruthenium complexes of various nuclearities containing fivemembered oxaruthenacycles, which are formed by σ-coordination of the metal atom with carbon atom in β-position of the organic ligand. In this work, thermal reaction of Ru3(CO)12 with 4-dimethylaminobut-3-en-2-on, Me2NCH=CHCOMe, was studied. Among the reaction products two unusual compounds 1 and 2 (Scheme) were characterized by NMR and single crystal X-ray diffraction. Each of these ionic products contain polynuclear organoruthenium cation, and hexanuclear hydride anion cluster [НRu6(CO)18]-. In the cationic complexes 1 and 2, charge redistribution along organic moiety lead to formation of the imine group; as a consequence, the carbon atoms in α- and β-positions of the organic ligand are σ-bonded to ruthenium atoms. The coordination to metal atoms facilitates double bonds migration in the aminovinylketone fragment.