Designed synthesis of mononuclear tris(heteroleptic) ruthenium complexes containing bidentate polypyridyl ligands

Abstract

A general synthetic methodology is reported for tris(bidentate)ruthenium(II) complexes containing three different polypyridyl ligands, based on the sequential addition of the ligands to the oligomer [Ru(CO)₂Cl₂](subscript n). The tris(heteroleptic) complexes were characterized by FAB mass spectrometry and NMR spectroscopy. An X-ray crystal structure determination was made for the complex, [Ru(Me₂bpy)(phen)(bpa)](PF₆)₂. C₆H₁₄·[C₄ₒH₄₃F₁₂N₇P₂Ru, M = 1062.8; Me(2)bpy = 4,4'-dimethyl-2,2'-bipyridine, phen = 1,10-phenanthroline, bpa = bis(2-pyridyl)amine]: triclinic, space group <P1, a = 14.57(3) Å, b = 13.50(3) Å, c = 12.73(3) Å, α = 68.6(2)°, β = 63.5(1)°, γ = 79.8(2)°, V = 2082 Å(3), Z = 2. Aspects of the electrochemistry, spectroscopy, and photophysics of the tris(heteroleptic) species are discussed.