Some reactions of co-ordinated cycloheptatriene and cyclo-octa-1,5-diene in ruthenium (d6) complexes

Abstract

The complex of empirical formula Ru(cht)Cl₂ has been shown to be dimeric with the cycloheptatriene (cht) bonding as a tridentate ligand. This complex reacts with Group 5B Lewis bases (L) to give monomers [Ru(cht)Cl₂L]. Reaction of the dimer with halide-abstracting thallium salts gives the complexes [Ru(cht)ClL₂]⁺[L₂=(MeCN)₂ or 2,2′-bipyridyl(bipy)]. The complexes [Ru(cht)Cl₂L][L = PPh₃ or AsPh₃] react with thallium β-diketonates (L″) to give the complexes [Ru(C⁷H⁸L″)L″L], in which the olefin is bonded as a dienyl. The temperature-dependent n.m.r. spectrum of the 4-phenylbutane-2,4-dione derivative is discussed. The polymer [{Ru(cod)Cl₂}_n](cod = cyclo-octa-1,5-diene) undergoes bridge-cleavage reactions with acetonitrile givjng the monomer [Ru(cod)-Cl₂(NCMe)₂] which reacts with bipy to give [Ru(cod)Cl₂(bipy)].