Synthesis and Coordination Behavior of a Bipyridine Platinum(II) Complex with Thioglucose

Abstract

A mononuclear platinum(II) complex with two monodentate-S H4tg(-) ligands, [Pt(H4tg-κS)2(bpy)] (1), was newly synthesized by the reaction of [PtCl2(bpy)] (bpy = 2,2'-bipyridyl) with NaH4tg (NaH4tg =1-thio-β-d-glucose sodium salt) in water. Complex 1 reacted with additional [PtCl2(bpy)] in water to give an S-bridged dinuclear complex, [Pt2(μ2-H4tg-κ(1)S:κ(1)S)2(bpy)2](2+) ([2](2+)), in which a square-planar [Pt(H4tg)2(bpy)] unit binds to a [Pt(bpy)](2+) moiety through two thiolato groups. Treatments of 1 with Cu(2+) and Ni(2+) in water in the presence of bpy produced S-bridged dinuclear complexes [PtCu(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([3](2+)) and [PtNi(μ2-H4tg-κ(1)S:κ(2)O,S)2(bpy)2](2+) ([4](2+)), respectively, in which a square-planar [Pt(H4tg)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 Δ configuration. On the other hand, similar treatment with Cd(2+) in the presence of bpy resulted in the formation of an S-bridged trinuclear complex, [Cd{Pt(μ2-H4tg-κ(1)S:κ(2)O,S)(μ2-H4tg-κ(1)S:κ(1)S)(bpy)}2](2+) ([5](2+)), in which each of two square-planar [Pt(H4tg)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 Λ configuration. Of two geometrical configurations, syn and anti, which arise from the relative arrangement of two β-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.

Synthesis of Ultrastable Copper Sulfide Nanoclusters via Trapping the Reaction Intermediate: Potential Anticancer and Antibacterial Applications

“…Therefore, the use of this material to trap CuS NCs was not successful. Besides, glucose (Glu) was also tested since it has been frequently used to coat nanoparticles to improve their biocompatibility and increase the cellular uptake efficiency of these nanoparticles. − After the addition of NaS-Glu to the yellow solution, the color gradually changed from yellow to light green after a few days at room temperature (Figure a), implying that NaS-Glu also cannot prevent the conversion of CuS NCs to CuS NPs. Although cysteine (Cys) could initially stabilize the formed NCs and the yellow color of the solution did not change, several days after dialysis, some precipitates were observed at the bottom of the vial.…”

Water-Molecule-Driven Vapochromic Behavior of a Mononuclear Platinum(II) System with Mixed Bipyridine and Thioglucose

“…Complex 1a , which is orange, was synthesized as described previously . In the diffuse-reflection spectrum, a solid sample of 1a exhibits a visible band at 430 nm (Figure S1a in the Supporting Information, SI) .…”

“…6 As part of our continuing efforts to create polynuclear and supramolecular architectures with aliphatic thiolate ligands, 7 we recently synthesized a 2,2′-bipyridine platinum(II) complex with 1-thio-β-D-glucose (H 5 tg), [Pt(H 4 tg-S) 2 (bpy)]•2H 2 O (1a; bpy = 2,2′-bipyridine), which acts as a versatile multidentate metalloligand that binds via the thiolato and hydroxyl groups of H 4 tg − . 8 An important structural aspect of 1a is the presence of both hydrophobic bpy and hydrophilic H 4 tg − groups in one molecule, leading to the formation of both π−π and hydrogenbonding interactions. While investigating the properties of 1a, we noticed that this compound is photoluminescent in the solid state.…”

“…Complex 1a, which is orange, was synthesized as described previously. 8 In the diffuse-reflection spectrum, a solid sample of 1a exhibits a visible band at 430 nm (Figure S1a in the Supporting Information, SI). 9 While 1a is nonemissive in water, it is emissive with an intense orange emission in the solid state when irradiated with UV light (365 nm) at room temperature (Figure 1b).…”

Metallosupramolecular Structures Derived from a Series of Diphosphine-bridged Digold(I) Metalloligands with Terminald-Penicillamine

“…It has been recognized that a thiolate group (RS – ) coordinated to a metal center (M) possesses a relatively high nucleophilicity to form M′–S bonds by reacting with thiophilic transition‐metal ions (M′) (Figure ) 4,5. We focused on the reactivity of the coordinated thiolato group and began to employ thiolato metal complexes as metalloligands for the stepwise construction of S‐bridged heterometallic multinuclear complexes in 1984 5–13. Currently, the metalloligand approach is being established for the rational construction of S‐bridged heterometallic multinuclear complexes 4,14.…”