Structural characterisation of RuII [9]aneS3 polypyridyl complexes by NMR spectroscopy and single crystal X-ray diffraction

Article abstract of DOI:10.1016/0277-5387(96)00310-5

The synthesis of a series of Ru^II complexes with the thioether ligand [9]aneS₃ and various polypyridyl ligands was carried out using [Ru(dmso)₄Cl₂] as a starting material. The first synthetic step involved the introduction of the thioether ligand and the isolation of the compound [Ru([9]aneS₃)(dmso)Cl₂]. The polypyridyl ligands were then exchanged to give a series of complexes [Ru([9]aneS₃)(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 complexes 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 observed for both complexes. The equatorial planes are formed by two macrocyclic sulfur donor atoms and two nitrogen atoms from polypyridyl ligands (bpy or phen). The hexa-co-ordination is achieved via a chlorine and the remaining sulfur, macrocyclic atom. The [9]aneS₃ macrocyclic ligand adopts a [333] facial arrangement. The results from NMR studies for [Ru([9]aneS₃)(phen)Cl]⁺ and [Ru([9]aneS₃) (bpy)Cl]⁺ indicate that both complexes exist as two forms in solution with CS symmetry consistent with a [333] facial arrangement. Copyright 1996 Elsevier Science Ltd.