STRUCTURAL CHARACTERIZATION OF RU-II [9]ANES(3) POLYPYRIDYL COMPLEXESBY NMR-SPECTROSCOPY AND SINGLE-CRYSTAL X-RAY-DIFFRACTION

The synthesis of a series of Ru-II complexes with the thioether ligand [9]aneS(3) and various polypyridyl ligands was carried out using [Ru( dmso)(4)Cl-2] as a starting material. The first synthetic step involve d the introduction of the thioether ligand and the isolation of the co mpound [Ru([9]aneS(3))(dmso)Cl-2]. The polypyridyl ligands were then e xchanged to give a series of complexes [Ru([9]aneS(3))(X)(Cl](+) (X = 1,10-phenanthroline (phen), 2,2'-bipyridyl (bpy), 4,4'-diphenyl-2,2',- bipyridyl (dbp) and 4,7'-diphenyl-1,10-phenanthroline (dip)). These co mplexes were characterised by NMR and UV spectra. The complexes with X = phen and bpy were crystallised and single crystal X-ray diffraction studies carried out. Distorted octahedral coordination geometry was o bserved for both complexes. The equatorial planes are formed by two ma crocyclic sulfur donor atoms and two nitrogen atoms from polypyridyl l igands (bpy or phen). The hexa-co-ordination is achieved via a chlorin e and the remaining sulfur, macrocyclic atom. The [9]aneS(3) macrocycl ic ligand adopts a [333] facial arrangement. The results from NMR stud ies for [Ru([9]aneS(3))(phen)Cl](+) and [Ru([9]aneS(3)) (bpy)Cl](+) in dicate that both complexes exist as two forms in solution with C-S sym metry consistent with a [333] facial arrangement. Copyright (C) 1996 E lsevier Science Ltd