Asymmetric Ruthenium(II) and Osmium(II) Complexes with New Bidentate Polyquinoline Ligands. Synthesis and NMR Characterization

摘要

A series of Ru(II) and Os(II) tris-chelate complexes with new bidentate 2-pyridylquinoline ligands have been synthesized and fully characterized by EA,1H-NMR and FAB-MS techniques. The new ligands are: L₁ = 4-p-methoxyphenyl-6-bromo-2-(2′- pyridyl)quinoline (mphbr-pq) and L₂ = 4-p-hydroxyphenyl-6-bromo-2-(2′-pyridyl)-quinoline (hphbr-pq). The complexes studied are: [Ru(bpy)₂L₁](PF₆)₂ (C₁), [Ru(bpy)₂L₂](PF₆)₂ (C₂), [Os(bpy)₂L₁](PF₆)₂ (C₃), [Os(bpy)₂L₂](PF₆)₂ (C₄) (bpy = 2,2′-bipyridine), [Ru(dmbpy)₂L₁](PF₆)₂ (C₅), [Ru(dmbpy)₂L₂](PF₆)₂ (C₆), [Os(dmbpy)₂L₁](PF₆)₂ (C₇), and [Os(dmbpy)₂L₂](PF₆)₂ (C₈) (dmbpy = 4,4′-dimethyl-2,2′-bipyridine). Moreover, new functionalized complexes C₉-C₁₂ were obtained by the basecatalyzed direct alkylation of C₂, C₄, C₆, and C₈ with 6-bromo-1-hexene. The complete assignment of the 1H-NMR spectra for the two new ligands (L₁ and L₂), and their Ru(II) or Os(II) complexes has been accomplished using a combination of one- and two-dimensional NMR techniques. The J_H,H values have been determined for the majority of the resonances.