Thiolato-Bridged Ru^IIAg^IRu^II Trinuclear Complex Composed of Bis(bipyridine)ruthenium(II) Units with Chelating 2-Aminoethanethiolate:  Conversion to a Disulfide-Bridged Ru^IIRu^II Dinuclear Complex

Abstract

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.

Ligand Noninnocence of Thiolate/Disulfide in Dinuclear Copper Complexes: Solvent-Dependent Redox Isomerization and Proton-Coupled Electron Transfer

“…Herein, we report that solvent-dependent redox isomerization of μ-thiolato Cu(II)Cu(II) to a μ-disulfido Cu(I)Cu(I) species is a phenomenon more general than previously recognized, and importantly that the Cu(II) thiolate/Cu(I) disulfide interconversion can be controlled completely by simple addition or removal of protons . This report provides the first evidence that the redox isomerization of Cu ligated by sulfur, a ubiquitous motif in bioinorganic chemistry, via proton-coupled electron transfer is a possible mechanism in the transport of Cu in living organisms .…”

(Acetato-κO){2-[(2-aminoethyl-κN)disulfanyl]ethanaminium}dichloridozinc(II)

“…Lead(II), bismuth(III), and copper(I) compounds with 2,2 0 -dithiobis(ethylamine) can show a variety of extended structural arrangements and are used as ionic conductive and non-linear optical materials (Louvain et al, 2007(Louvain et al, , 2014Tamura et al, 2007;Bi et al, 2008).…”

(2-Aminoethanethiolato-κ2N,S)bis[1,2-bis(diphenylphosphanyl)ethane-κ2P,P′]ruthenium(II) hexafluoridophosphate

“…For closely related structures, see: Tamura et al (2007); Matsuura et al (2006); Hanif et al (1999). For conformation descriptors of the chelate rings, see: Gispert (2008).…”

“…It has been recognized that the preparation of ruthenium complexes having non-bridging aliphatic thiolato group(s) is difficult because of the high reactivity of a thiolato group bound to a metal center. For example, the direct reaction of Ru II with 2-aminoethanethiol (Haet) led to the formation of thiolato-bridged trinuclear complex, [Ru{Ru(aet) 3 } 2 ] 2+ (Matsuura et al, 2006), and furthermore, the reaction of [Ag{Ru(aet)(bpy) 2 } 2 ] 3+ (bpy = 2,2′-bipyridine) with HCl did not give an expected mononuclear complex, [Ru(aet)(bpy) 2 ] + , but produced a dinuclear complex with a disulfide bond, [Ru 2 (cysta) (bpy) 4 ] 4+ (cysta = cystamine) (Tamura et al, 2007). Here, we report the synthesis and crystal structure of [Ru(aet) (dppe) 2 ]PF 6 , which is a quite rare example of a crystallographically characterized ruthenium(II) complex with an aliphatic thiolato donor.…”

“…1). The Ru-S [2.431 (2) Å] and Ru-N [2.212 (5) Å] bond distances are slightly longer than those of the related ruthenium(II) complexes with aet ligand(s) (Ru-S = 2.291-2.394 Å, Ru-N = 2.133-2.212 Å) (Tamura et al, 2007;Matsuura et al, 2006;Hanif et al, 1999). On the other hand, the Ru-P bond distances (average 2.380 Å) are similar to those of ruthenium(II) complexes with dppe ligands (av.…”