Synthesis and structural characterisation of new Ru-II[12] aneS(4) complexes with polypyridylic and related ligands

The reaction between cis-[Ru(dmso)Cl-2] (dmso = dimethylsulfoxide) and the macrocycle 1,4,7,10-tetrathiacyclododecane ([12]aneS(4)) gives the complex cation [Ru([12]aneS(4))(dmso)Cl](+). A new series of Ru-II([12]aneS(4)) com plexes were obtained by replacing the dmso and the chlorine ligands with po lypyridylic or related monodentate ligands. Complexes with the general form ula [Ru([12]aneS(4))(L)](2+), where L = bidentate ligand: dipyridylamine (d ipa); 5-phenyl-1,10-phenanthroline (5-phen); 1,10-phenanthroline-5,6-dione (5,6-dione); o-phenylenediamine (pda) or 4,4'-diphenyl-2,2'-dipyridyl (dbp) have been synthesised. Related complexes containing monodentate ligands, [ Ru([12]aneS(4))(CH3CN)Cl](+), [Ru([12]aneS(4))(CH3CN)(2)](2+) and [Ru([12]a neS(4))(ind)Cl)](+) (ind = indazole) were also prepared. The complexes were characterised by NMR, UV/Vis and IR spectroscopy and their electrochemical behaviour was studied by cyclic voltammetry. The X-ray single crystal diff raction structures of the complexes [Ru([12]aneS(4))dmso)Cl]Cl, [Ru([12]ane S(4))(CH3CN)(2)][PF6](2), [Ru([12]aneS(4))(CH3CN)Cl]PF6, [Ru([12]aneS(4))(5 ,6-dione)][PF6](2). 2CH(3)CN, [Ru([12]aneS(4))(5-phen)] [PF6](2) and [Ru([1 2]aneS(4))(ind)Cl]PF6. CH3CN were determined. All complexes exhibit a disto rted cis-octahedral environment with the macrocycle adopting a folded confo rmation.