Synthesis of Novel S‐Bridged Heterotrinuclear Complexes Containing Six‐Membered Chelate Rings: Structural, Spectroscopic, and Electrochemical Properties of [Co{Rh(apt)₃}₂]³⁺ (apt = 3‐Aminopropanethiolate)

Abstract

A bidentate ligand, 3-aminopropanethiolate (apt), was synthesized and treated with RhCl 3 ·3H 2 O in basic water to yield a novel mononuclear complex, fac(S)- [Rh(apt) 3+ (2b), which were characterized by stereochemical, spectrochemical, and electrochemical methods. 2a and 2b are stable and exhibit trivalency in water. X-ray crystallographic analysis of 2a and 2b showed that all of the bridging sulfur atoms are fixed in the R configuration for the ∆ unit and in the S configuration for the Λ unit, and each complex has six six-membered chelate rings, all of which are in the chair conformation. The crystal structure of the corresponding 2-aminoethanethiolate (aet) trinuclear complex ∆Λ-[Co{Rh(aet) 3 } 2 ] 3+ (4a) was also deter-

The prominent charge-transfer effects of trinuclear complexes with nominally high nickel valences

“…Sulfur-containing transition metal (TM) compounds possess a variety of fascinating properties such as metalinsulator transitions [1,2], thermoelectric effects [3,4], and superconductivity [5]. Among them, many sulfurcoordinating TM multinuclear complexes have been synthesized through stepwise synthesis, which have a potential for new physical properties [6][7][8][9]. For instance, the single-crystalline [M 2 {Au 2 (dppe)(D-pen) 2 } 2 ]X 2 [dppe denotes 1, 2-bis(diphenylphosphino)-ethane, M=Co, Ni, and X 2 stand for anions] of which M sites are unusually stabilized in an octahedral structure bonded by the coordinations with two aliphatic thiolato, two amine, and two carboxylate donors [10,11], shows catalyst-like reactions for M=Co [12].…”

3-[1-(4-Chlorophenyl)ethyl]-1,3-thiazinane-2-thione

“…For the biological activity of thiazole compounds, see: Amir et al (2006). For a related structure, see: Cunico et al (2007).…”

Comparative studies of S-bridged complexes of 99mTc with fac(S)-[M(aet)3] (M=RhIII, IrIII; aet=2-aminoethanethiolate)

“…Quality control, effect of reducing agents concentration, pH and time on labelling efficiency, electrophoresis, HPLC, biodistribution studies in rats and scintigraphy in rabbit were performed. The results were compared with those of fac(S)-[Rh(aet) 3 ] labelled with 99m Tc [26,27]. 3 ] (M = Rh III , Ir III ) were obtained from the Ken-ichi Okamoto Laboratory, Department of Chemistry, University of Tsukuba, Japan.…”