A mononuclear complex acting as a novel chiral ligand, [Ni(1-Meaet)(2)] (1-Meaet = 1-amino-2-propanethiolate; 1b) was synthesized. Using this mononuclear complex, the S-bridged trinuclear complex [Ni{Ni(1-Meaet)(2)}(2)](2+) (2b), hexanuclear complex [Pd-2{Ni0.6Pd0.4(1-Meaet)(2)}(4)](4+) (3b), and dinuclear complexes [Pt(bpy){Ni(1-Meaet)(2)(H2O)(2)}](2+) (bpy = 2,2'-bypyridine; 4b) and [Pt(bpy) {Ni(1-Meaet)(bpy)}](2+) (5b) were synthesized. Molecular structures for 3b and 5b were determined by X-ray diffraction. In the crystal structure of 3b, two Pd(II) ions are bridged by four metalloligands, cis(S)-[Ni(1-Meaet)(2)] and/or cis(S)-[Pd(1-Meaet)(2)] units, forming a C-4h symmetrical S-bridged hexanuclear structure with high optical selectivity of the ligand, in which all [M(1-MeaCt)(2)] units have the absolute cis(S)-R,S configuration. In the crystal structure of 5b, the Ni(II) ions are surrounded by two 1-Meaet and one bpy to have an approximately octahedral geometry with 50% ligand diastereoselectivity of the mixed crystals Of Delta(RR)/Delta(ss) and Delta(RS)/Delta(RS) configuration. Moreover, the lowering of the nucleophilicity of the sulfur atom was observed by the introduction of the methyl group. The properties of 1b-5b were discussed in comparison with the corresponding act (2-aminoethanethiolate) complexes 1a-5a using X-ray absorption, UV/Vis, IR, far-IR, Raman and NMR spectra, as well as structural analysis. (c) 2005 Elsevier Ltd. All rights reserved.