A mononuclear platinum(II) complex with two monodentate-S H(4)tg(-) ligands, [Pt(H(4)tg-kappa S)(2)(bPY)] (1), was newly synthesized by the reaction of [PtCl2(bpy)] (bpy = 2,2'-bipyridyl) with NaH(4)tg (NaH(4)tg =1-thio-beta-D-glucose sodium salt) in water. Complex 1 reacted with additional [PtCl2(bpy)] in water to give an S-bridged dinuclear complex, [Pt-2(mu(2)-H(4)tg-kappa S-1:kappa S-1)2(bPY)2](2+) ([2](2+)), in which a square-planar [Pt(H(4)tg)(2)(bPY)] unit binds to a [Pt(bpY)](2+) moiety through two thiolato groups. Treatments of 1 with Cu2+ and Ni2+ in water in the presence of bpy produced S-bridged dinuclear complexes [PtCu(mu(2)-H(4)tg-kappa S-1:kappa O-2,S)(2)(bpy)(2)](2+) ([3](2+)) and [PtNi(mu(2)-H(4)tg-kappa S-1:kappa O-2,S)(2)(bPY)(2)](2+) ([4](2+)), respectively, in which a square-planar [Pt(H(4)tg)(2)(bpy)] unit binds to a [M(bpy)](2+) (M = Cu-II, Ni-II) moiety through two thiolato and two hydroxyl groups to form a chiral [M(N)(2)(O)(2)(S)(2)] octahedron with the Delta configuration. On the other hand, similar treatment with Cd2+ in the presence of bpy resulted in the formation of an S-bridged trinuclear complex, [Cd{Pt(mu(2)-H(4)tg-kappa S-1:kappa O-2,S)(mu(2)-H(4)tg-kappa S-1:kappa S-1)(bpy)}(2)](2+) ([5](2+)), in which each of two square planar [Pt(H(4)tg)(2)(bpy)] units binds to a Cd-II ion through two thiolato groups and one hydroxyl group to form a chiral [Cd(O)(2)(S)(4)] octahedron with the A configuration. Of two geometrical configurations, syn and anti, which arise from the relative arrangement of two beta-D-pyranose moieties, [2](2+) adopts the syn configuration with symmetric bridging sulfur atoms, while [3](2+), [4](2+), and [5](2+) all have the anti configuration with R configurational bridging sulfur atoms. All of the complexes were fully characterized by electronic absorption, CD, and NMR spectroscopies, along with single-crystal X-ray crystallography.