Heteroleptic ruthenium(II)/(III) 2,2′-bipyridine/1,10-phenanthroline complexes incorporating bidentate Schiff base N,O-ligands

Eight substituted bidentate Schiff base ligands HOC6H4CH = N-R (HL) (HL1: R = 4-ClC6H4, HL2: R = 2-ClC6H4, HL3: R = 4-NO2C6H4, HL4: R = 4-MeC6H4, HL5: R = 2,6-Me2C6H3, HL6: R = 2,46-Me3C6H2, HL7: R = CH2C6H5, and HL8: R = n-Pr) were synthesized by the typical condensation reaction. Interaction of cis-[Ru(bpy)(2)Cl-2]center dot 2H(2)O (bpy = 2,2-bipyridine) with one equivalent of HL ligand in the presence of KPF6 afforded the cationic ruthenium(II) complexes of the type [Ru(bpy)(2)(L)](PF6) (1-8). The reaction of cis-[Ru(phen)(2)Cl-2]2H(2)O (phen = 1,10-phenanthroline) and HL1 under similar condition gave complex [(phen)(2)Ru(L)](PF6) (1a). Treatment of cis-[Ru(phen)(2)Cl-2]center dot 2H(2)O with two equivalents of HL in the presence of KPF6 resulted in isolation of the cationic ruthenium(III) complexes of the type [Ru(phen)(L)(2)](PF6) (9-16). All complexes have been spectroscopically characterized. The structures of 1a center dot CH2Cl2, 2 center dot 1/2CH(2)Cl(2), 3 center dot CH3CN, 5 center dot 1/2H(2)O, 6,12 center dot 1/2HOCH(2)CH(2)OH, 13 center dot CH3CN, 15 center dot H2O, and 16 have been determined by single-crystal X-ray diffraction.