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Synthesis and structure of electron rich ruthenium polyhydride complexes and clusters containing AlCp* and GaCp*

Abstract:

The reactions of the ruthenium hydride complexes [{Ru(COD)(H)(NH 2NMe2)3}{BArF}] (BAr F[B{C6H3(CF3)2} 4), [{Cp*Ru}2(μ-H)4] and [{Cp*Ru}3(μ-H)3(μ3-H)2] with GaCp* and AlCp* are investigated. The reaction of [{Ru(COD)(H)(NH2NMe2)3}{BArF}] with GaCp* leads to substitution of the hydrazine ligands by GaCp* and the formation of [{Ru(COD)(H)(GaCp*)3}{BArF}] (1), while the reactions of [{Cp*Ru}2(μ-H)4] and [{Cp*Ru}3(μ-H)3(μ3-H)2] with ECp* (E = Al, Ga) results in the formation of the polyhydride clusters [{Cp*Ru(μ-H)(H)(μ-ECp*)}2] (2, E = Ga; 3, E = Al) and [{Cp*Ru}3(μ-H)5(μ3- ECp*)] (4, E = Al; 5, E = Ga). All Ru complexes react upon coordination of the group 13 ligand without loss of H2 or reductive elimination of Cp*H and without insertion into the Ru-H bonds; some of the products, however, showing Ru-H-E bridging motifs. All compounds were characterized by NMR spectroscopy, elemental analysis and single crystal X-ray diffraction studies. © 2009 The Royal Society of Chemistry.