The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2'-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged RuIIAgIRuII trinuclear complex, [Ag{Ru(aet)(bpy)2}2]3+, in which two [RuII(aet)(bpy)2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged RuIIRuII dinuclear complex, [Ru2(cysta)(bpy)4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [Ru2(cysta)(bpy)4]4+ is reverted back to [Ag{Ru(aet)(bpy)2}2]3+ by treatment with Ag+ assisted by Zn reduction.

The reaction of [Ru(solvent)(2)(bpy)(2)](2+) (bpy = 2,2'-bipyridine) with D-H(2)pen (D-penicillamine) in ethanol/water in the presence of Ag(+) gave a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, [Ag{Ru(D-Hpen)(bpy)(2)}(2)](3+) ([1](3+)), in which two octahedral [Ru(II)(D-Hpen)(bpy)(2)](+) units are linked by a linear Ag(I) ion. Of three possible isomers (Delta(D)Delta(D), Delta(D)Lambda(D), and Lambda(D)Lambda(D)), [1](3+) formed the Delta(D)Delta(D) and Lambda(D)Lambda(D) isomers that were separately isolated by fractional crystallization with the use of [Sb(2)(R,R-tartrato)(2)](2-). In [1](3+), each D-Hpen ligand chelates to a Ru(II) center through thiolate and carboxylate groups, while an amine group of D-Hpen is protonated and does not participate in the coordination. On refluxing in ethanol/water, the Delta(D)Delta(D) isomer of [1](3+) was converted to Delta(D)Delta(D)-[2](3+), in which each D-Hpen ligand chelates to a Ru(II) center through thiolate and amine groups with a non-coordinating carboxyl group. On the other hand, a similar thermal linkage isomerization was not noticed for the Lambda(D)Lambda(D) isomer of [1](3+) under the same conditions. The isolated Delta(D)Delta(D)-[1](3+), Lambda(D)Lambda(D)-[1](3+), and Delta(D)Delta(D)-[2](3+) were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography for Lambda(D)Lambda(D)-[1](3+) and Delta(D)Delta(D)-[2](3+).

Treatment of a thiolato-bridged Ru(II)Ag(I)Ru(II) trinuclear complex, [Ag{Ru(aet)(bpy)(2)}(2)](3+) (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)](3+) (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.

Lanthanoid triisopropoxides are active catalysts for aldol reactions. Aldehydes give the corresponding β-hydroxyaldehydes at low temperatures in good yields, whereas ketones are less reactive, but form condensation products at high temperatures. Exceptionally, γ- or δ-diketones easily undergo condensation to give five- and six-membered unsaturated ketones in high yields. The lanthanoid propoxides, catalyzing the Michael addition of ketones to α,β-unsaturated ketones, which give δ-diketones, are also good catalysts for the Robinson-type annelation. In these reactions, the catalytic activity of the lanthanum propoxide is higher than those of the heavy lanthanoid propoxides, and is almost comparable to that of sodium isopropoxide. Since aluminum triisopropoxide shows poor activity, the lanthanoid propoxides are considerably basic for trivalent metal alkoxides.