Synthesis and Properties of Linear-Type S-Bridged RhIIINiIIRhIII Trinuclear Complexes with 2-Aminoethanethiolate (aet) or l-Cysteinate (l-cys). Crystal Structure of [Ni{Rh(aet)3}2](NO3)2
- 1 February 1995
- journal article
- research article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 68 (2) , 610-615
- https://doi.org/10.1246/bcsj.68.610
Abstract
The reaction of fac(S)-[Rh(aet)3] with Ni2+ at room temperature gave a linear-type S-bridged RhIIINiIIRhIII trinuclear complex, [Ni{Rh(aet)3}2]2+ (1). A similar reaction of ΔLLL-fac(S)-[Rh(L-cys-N,S)3]3− with Ni2+ produced the corresponding trinuclear complex with L-cys ligands, ΔLLLΔLLL-[Ni{Rh(L-cys-N,S)3}2]4− (ΔLLLΔLLL-2), retaining the ΔLLL configuration of the starting complex. The crystal structure of 1(NO3)2 was determined by X-ray diffraction. [Ni{Rh(aet)3}2](NO3)2·2H2O, chemical formula C12H40N8S6O8NiRh2, crystallizes in the triclinic space group with a = 12.249(3), b = 13.366(4), c = 10.260(2) Å, α = 108.76(1), β = 102.46(1), γ = 101.21(1)°, V = 1488.7(7) Å3, Z = 2, and R = 0.024. In 1 the central NiII atom is situated in a distorted octahedral geometry, coordinated by six thiolato sulfur atoms from the two octahedral fac(S)-[Rh(aet)3] units. The two fac(S)-[Rh(aet)3] units have the same absolute configuration to form the racemic (ΔΔ/ΛΛ) isomer. The optically active ΔΔ and ΛΛ isomers of 1 were derived from ΔΔΔΔ- and ΛΛΛΛ-[{Rh(aet)3}4Zn3(HO)]5+ respectively, by adding excess Ni2+. The electronic absorption spectral behavior of 1 indicated that the intermolecular exchange of the fac(S)-[Rh(aet)3] units occurs in solution, which results in the formation of the ΔΛ (meso) isomer from a 1 : 1 mixture of the ΔΔ and ΛΛ isomers. The chemical properties of the present RhIIINiIIRhIII complexes are discussed in comparison with those of the corresponding CoIIINiIICoIII and RhIIICoIIIRhIII complexes.Keywords
This publication has 21 references indexed in Scilit:
- Preparation and Some Properties of Linear-Type S-Bridged IrIIICoIIIIrIII Trinuclear Complexes with 2-Aminoethanethiolate (aet) or l-Cysteinate (l-cys). Crystal Structure of ΔΛ-[Co{Ir(aet)3}2](NO3)3Bulletin of the Chemical Society of Japan, 1993
- Preparation and Some Properties of [CoIIorIII{RhIII(aet or l-cys-N,S)3}2]-Type S-Bridged Trinuclear ComplexesBulletin of the Chemical Society of Japan, 1990
- The Formation and Stereochemistry of [CoIII3(l-cys-N,S)n(aet)6−n]3−n Type S-Bridged Complexes (n=0–6, l-cys=l-cysteinate, and aet=2-aminoethanethiolate)Bulletin of the Chemical Society of Japan, 1989
- Preparation and Resolution of Bis[tris(2-aminoethaneselenolato)cobalt(III)-μ-Se, μ-Se′, μ-Se″]cobalt(III) ComplexBulletin of the Chemical Society of Japan, 1988
- S-Bridged Polynuclear Complexes. II. Formation and Some Properties of [M{Co(l-cys-N,S)3}2]-Type Complexes (M=Fe(III), Co(III), and Ni(II); l-cys=l-cysteinate)Bulletin of the Chemical Society of Japan, 1988
- S-Bridged Polynuclear Complexes. I. Selective Formation and Crystal Structure of (+)600CD-Bis[tris(l-cysteinato-N,S)cobaltate(III)-μ-S,μ-S′,μ-S″]cobalt(III) Nitrate PentahydrateBulletin of the Chemical Society of Japan, 1986
- Synthesis of [Co(CoL3)2]3+ by nitric acid oxidation of CoL3 (L = -SCH2CH2NH2) and induced electron transfer. Crystal structure of [Co(CoL3)2]2(SO4)Cl4Inorganic Chemistry, 1985
- Electron spin resonance study of iron(III) and ruthenium(III) in a trinuclear complex of tris(2-mercaptoethylamine)cobalt(III)Inorganic Chemistry, 1975
- Electronic and circular dichroism spectra of polynuclear 2-aminoethanethiol complexesInorganic Chemistry, 1967
- Complexes Derived from Strong Field Ligands. XV. The Formation of Trinuclear Complexes by Coördination of Tris(β-mercaptoethylamine)-cobalt(III) to Metal IonsInorganic Chemistry, 1962