Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
Inorg Chem. 2011 Jun 6;50(11):4764-71. doi: 10.1021/ic102319p. Epub 2011 May 11.
Treatment of a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, Ag{Ru(aet)(bpy)(2)}(2) (aet = 2-aminoethanthiolate; bpy = 2,2'-bipyridine), with NaI in aqueous ethanol under an aerobic condition afforded a mononuclear ruthenium(II) complex having an S-bonded sulfinato group, 1 (Ru(aesi-N, S)(bpy)(2) (aesi = 2-aminoethanesulfinate)). Similar treatment of optically active isomers of an analogous Ru(II)Ag(I)Ru(II) trinuclear complex, Δ(D)Δ(D)- and Λ(D)Λ(D)-Ag{Ru(d-Hpen-O,S)(bpy)(2)}(2) (d-pen = d-penicillaminate), with NaI also produced mononuclear ruthenium(II) isomers with an S-bonded sulfinato group, Δ(D)- and Λ(D)-2 (Ru(d-Hpsi-O,S)(bpy)(2) (d-psi = d-penicillaminesulfinate)), respectively, retaining the bidentate-O,S coordination mode of a d-Hpen ligand and the absolute configuration (Δ or Λ) about a Ru(II) center. On refluxing in water, the Δ(D) isomer of 2 underwent a linkage isomerization to form Δ(D)-[3] (+) (Ru(d-Hpsi-N,S)(bpy)(2)), in which a d-Hpsi ligand coordinates to a Ru(II) center in a bidentate-N,S mode. Complexes 1, Δ(D)- and Λ(D)-2, and Δ(D)-3 were fully characterized by electronic absorption, CD, NMR, and IR spectroscopies, together with single-crystal X-ray crystallography. The electrochemical properties of these complexes, which are highly dependent on the coordination mode of sulfinate ligands, are also described.
一种硫醇桥联的 Ru(II)Ag(I)Ru(II)三核配合物 Ag{Ru(aet)(bpy)(2)}(2)（aet = 2-氨基乙硫醇；bpy = 2,2'-联吡啶）在有氧条件下用 NaI 在水乙醇中处理，得到了一个具有 S 键合亚磺酰基的单核钌(II)配合物 1 (Ru(aesi-N, S)(bpy)(2)（aesi = 2-氨基乙磺酸盐）。类似地，用 NaI 处理具有光学活性的类似 Ru(II)Ag(I)Ru(II)三核配合物的对映异构体 Δ(D)Δ(D)-和 Λ(D)Λ(D)-Ag{Ru(d-Hpen-O,S)(bpy)(2)}(2)（d-pen = d-青霉素酸盐），也得到了具有 S 键合亚磺酰基的单核钌(II)异构体 Δ(D)-和 Λ(D)-2 (Ru(d-Hpsi-O,S)(bpy)(2)（d-psi = d-青霉素胺亚磺酸盐），分别保留了 d-Hpen 配体的双齿-O,S 配位模式和 Ru(II)中心的绝对构型（Δ 或 Λ）。在回流水中，2 的 Δ(D)异构体经历了键联异构化，形成 Δ(D)-[3] (+) (Ru(d-Hpsi-N,S)(bpy)(2))，其中一个 d-Hpsi 配体以双齿-N,S 模式与 Ru(II)中心配位。配合物 1、Δ(D)-和 Λ(D)-2 以及 Δ(D)-3 均通过电子吸收、CD、NMR 和 IR 光谱学以及单晶 X 射线晶体学进行了全面表征。这些配合物的电化学性质也与磺酸盐配体的配位模式高度相关。
