Pd(thiosaccharinato)₂·H₂O, the first thiosaccharinato complex of a platinum-group metal

Abstract

A Pd(II) complex of the thiosaccharinato (tsac) anion, of stoichiometry Pd(tsac) 2 Á H 2 O was prepared by interaction of Na 2 PdCl 4 with thiosaccharin in methanol and characterized by infrared and 1 H and 13 C NMR spectroscopy. These spectral studies confirmed interaction of the metal center with the thiosaccharinate acting as a bidentate ligand through its thiol group and the N-atom. NMR measurements also confirmed that in solution thiosaccharin is mainly present in its thiolate tautomeric form.

Synthesis and Structural Analysis of New Palladium(II) Thiosaccharinates with Triphenylphosphane or Diphosphanes

“…Yield: 66 mg (76 %). It shows almost the same spectroscopic features of the hydrated product obtained by Vieytes et al 16. All the procedures performed to obtain good crystals of the substance were unsuccessful.…”

“…This behavior agrees with the NMR spectroscopic data in [D 6 ]DMSO. The thiocarbonilic carbon atoms (C1) show a unique 13 C NMR signal (189 ppm) low‐field shifted against to Htsac (161 ppm) and slightly shifted up‐field against the free thiosaccharinate anion (191 ppm) 16. In weak coordinating solvents like CH 2 Cl 2 , the poly‐nuclear structure of the solid complex 1 could be retained.…”

A comparative study of the coordination of saccharinate, thiosaccharinate and benzisothiozolinate ligands to cyclometalated [Pd(Me2NCH2C6H4-κN,C)(μ-Cl)]2: Molecular structures of [Pd(Me2NCH2C6H4-κN,C)(µ-X)]2 (X = sac, bit and tsac) and [Pd(Me2NCH2C6H4-κN,C)Cl(ampyH-κN)] (ampyH = 2-amino-3-methylpyridine)

“…The coordination chemistry of thiosaccharinate has also received recent attention [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18], but that of benzisothiozolinate (bit) remains virtually unexplored [19][20]…”

Activation of thiosaccharin at a polynuclear osmium cluster

“…The heterocyclic compound tsacH can, in principle, exist in two, principle tautomeric forms in solution (Chart 1) that parallel the wellknown lactam ⇌ lactim equilibria established for dione-containing heterocycles. In the case of tsacH, the pertinent equilibrium involves the heterocyclic thione (thioamide) and the thiol (thioimine) forms of the molecule [12,13], with the thiol contributor favored computationally [14] and confirmed experimentally by NMR measurements [15].…”