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

Abstract

A series of palladium(II) thiosaccharinates with triphenylphosphane (PPh3), bis(diphenylphosphanyl)methane (dppm), and bis(diphenylphosphanyl)ethane (dppe) have been prepared and characterized. From mixtures of thiosaccharin, Htsac, and palladium(II) acetylacetonate, Pd(acac)2, the palladium(II) thiosaccharinate, Pd(tsac)2 (tsac: thiosaccharinate anion) (1) was prepared. The reaction of 1 with PPh3, dppm, and dppe leads to the mononuclear species Pd(tsac)2(PPh3)2·MeCN (2), [Pd(tsac)2(dppm)] (3), Pd(tsac)2(dppm)2 (4), and [Pd(tsac)2(dppe)]·MeCN (5). Compounds 2, 4, and 5 have been prepared also by the reaction of Pd(acac)2 with the corresponding phosphane and Htsac. All the new complexes have been characterized by chemical analysis, UV/Vis, IR, and Raman spectroscopy. Some of them have been also characterized by NMR spectroscopy. The crystalline structures of complexes 3, and 5 have been studied by X‐ray diffraction techniques. Complex 3 crystallizes in the monoclinic space group P21/n with a = 16.3537(2), b = 13.3981(3), c = 35.2277(7) Å, β = 91.284(1)°, and Z = 8 molecules per unit cell, and complex 5 in P21/n with a = 10.6445(8), b = 26.412(3), c = 15.781(2) Å, β = 107.996(7)°, and Z = 4. In compounds 3 and 5, the palladium ions are in a distorted square planar environment. They are closely related, having two sulfur atoms of two thiosaccharinate anions, and two phosphorus atoms of one molecule of dppm or dppe, respectively, bonded to the PdII atom. The molecular structure of complex 3 is the first reported for a mononuclear PdII‐dppm‐thionate system.

Aurophilic interaction in gold(I) thiosaccharinates: Synthesis, characterization, crystal structures and DFT theoretical study

“…In the 1 H NMR the resonances of the thiosaccharinates appear as one doublet at 7.97 ppm (d, 2H, H6) and one multiplet at 7.85-7.70 ppm (m, 6H, H3/H4/H5), the last partially superimposed with a dppm multiplet. A similar spectra was obtained for a Pd(II) thiosaccharinate, [Pd(tsac) 2 (dppm)], with the anions tightly bonded to the metal center [21]. The presence of the ethanol molecule was also confirmed by its proton resonances Author's personal copy at 3.55 (q, 2H) and 1.06 (t, 3H) ppm.…”

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]…”

A comparative study of the coordination of saccharinate (sac), thiosaccharinate (tsac) and benzisothiazolinate (bit) ligands to trans-[PdCl2(H2NBz)2]: molecular structure of cis-[Pd(bit)2(H2NBz)2]

“…1) are versatile poly-functional ligands, shown to adopt a variety of coordination modes, and consequently their coordination chemistry has been widely studied [1,2]. Palladium(II) and platinum(II) complexes of these ligands have been detailed [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] with some showing promising biological properties [19][20][21][22][23][24]. In contrast, the coordination chemistry of the related benzisothiozolinate (bit) anion ( Fig.…”