The optically active mixed-ligand fac(S)-tris(thiolato)rhodium(III) complexes, Δ_L-fac(S)-[Rh(aet)₂(L-cys-N,S)]⁻ (aet = 2-aminoethanethiolate, L-cys = L-cysteinate) (1) and Δ_LL-fac(S)-[Rh(aet)(L-cys-N,S)₂]²⁻ were newly prepared by the equatorial preference of the carboxyl group in the coordinated L-cys ligand. The amide formation reaction of 1 with 1,10-diaminodecane and polyallylamine gave the diamine-bridged dinuclear Rh(III) complex and the single-chain polymer-supported Rh(III) complex with retention of the Δ_L configuration of 1, respectively. These Rh(III) complexes reacted with Co(III) or Co(II) to give the linear-type trinuclear structure with the S-bridged Co(III) center and the two Δ-Rh(III) terminal moieties. The polymer-supported Rh(III) complex was applied not only to the CD spectropolarimetric detection and determination of a trace of precious metal ions such as Au(III), Pt(II), and Pd(II) but also to concentration and extraction of these metal ions into the solid polymer phase. Chirality 28:85–91, 2016. © 2015 Wiley Periodicals, Inc.

Readily available L-tartaric acid, which is a bidentate ligand with two chiral centers forming a seven-membered chelate ring, was applied to the chiral ligand for the chiral nuclear magnetic resonance (NMR) shift reagent of samarium(III) formed in situ. This simple method does not cause serious signal broadening in the high magnetic field. Enantiomeric ¹³C and ¹H NMR signals and enantiotopic ¹H NMR signals of α-amino acids were successfully resolved at pH 8.0 and the 1:3 molar ratio of Sm(NO₃)₃:L-tartaric acid. It is elucidated that the enantiomeric signal resolution is attributed to the anisotropic magnetic environment for the enantiomers induced by the chiral L-tartarato samarium(III) complex rather than differences in stability of the diastereomeric substrate adducts. The present ¹³C NMR signal resolution was also effective for the practical simultaneous analysis of plural kinds of DL-amino acids. Chirality 27:353–357, 2015.© 2015 Wiley Periodicals, Inc.