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)(NH₂NMe₂)₃}{BAr^F}] (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}{BAr^F}] with GaCp* leads to substitution of the hydrazine ligands by GaCp* and the formation of [{Ru(COD)(H)(GaCp*)₃}{BAr^F}] (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.