Enantiospecific Synthesis of Δ and Λ [Ru(bpy)₂ppy]⁺ and [Ru(bpy)₂quo]⁺ (bpy = 2,2‘-Bipyridine, ppy = Phenylpyridine-H⁺, quo = 8-Hydroxyquinolate): ¹H and ¹³C NMR Studies and X-ray Structure Determination of <i>r</i><i>ac</i>-[Ru(bpy)₂quo]PF₆

In this paper, we describe the enantiospecific synthesis and the complete characterization of the two hexacoordinated ruthenium(II) monocations [Ru(bpy)2ppy]+ and [Ru(bpy)2quo]+ (bpy = 2,2‘-bipyridine, ppy = phenylpyridine-H+, quo = 8-hydroxyquinolate) in their enantiomeric Δ and Λ forms. The corresponding enantiomeric excesses (ee's) are determined by 1H NMR using pure Δ-Trisphat (tris(tetrachlorobenzenedialato)phosphate(V) anion) as a chiral 1H NMR shift reagent. A complete 1H and 13C NMR study has been carried out on rac-[Ru(bpy)2ppy]PF6 and rac-[Ru(bpy)2quo]PF6. Additionally, the X-ray molecular structure of rac-[Ru(bpy)2quo]PF6 is reported; this latter species crystallizes in the monoclinic C2/c space group (a = 22.079 Å, b = 16.874 Å, c = 17.533 Å, α = 90°, β = 109.08°, γ = 90°).本文报道了两种六配位二价钌单阳离子[Ru(bpy)₂ppy]⁺与[Ru(bpy)₂quo]⁺的对映专一性合成方法，以及其Δ和Λ对映异构体形式的完整表征结果，其中bpy=2,2'-联吡啶（2,2'-bipyridine）、ppy=苯基吡啶-H+（phenylpyridine-H+）、quo=8-羟基喹啉根（8-hydroxyquinolate）。 采用纯Δ-Trisphat（三(四氯苯二酰氧基)磷酸(V)阴离子，tris(tetrachlorobenzenedialato)phosphate(V) anion）作为手性¹H NMR位移试剂，通过¹H NMR测定了对应体系的对映体过量值（ee值）。 针对外消旋体rac-[Ru(bpy)₂ppy]PF₆与rac-[Ru(bpy)₂quo]PF₆开展了完整的¹H与¹³C NMR表征研究。 此外，本文还报道了rac-[Ru(bpy)₂quo]PF₆的X射线分子晶体结构：该化合物结晶于单斜晶系C2/c空间群，晶胞参数为a=22.079 Å、b=16.874 Å、c=17.533 Å，α=90°、β=109.08°、γ=90°。