Structural and Spectroscopic Characterization of Two New Thallium(I)/Thiosaccharinate Complexes

Abstract

The crystal structures of [Tl(tsac)] (1) and [Tl(tsac)-(ophen)] (2) (tsac ϭ anion of thiosaccharin; ophen ϭ 1,10 phenanthroline) have been determined at 116 K by single crystal X-ray diffractometry. Complex 1 crystallizes in the monoclinic space group P2 1 /a with Z ϭ 4 and complex 2 in the monoclinic space group C2/c with Z ϭ 8.In both complexes T I is coordinated to a thiosaccharinate anion through its sulphur and nitrogen atoms. A distorted eight fold coordination sphere around the cation in complex 1 is completed with two other longer Tl-S bonds and four Kristallographische und spektroskopische Charakterisierung von zwei neuen Thallium(I)-Thiosaccharinat-KomplexenInhaltsübersicht. Die Kristallstrukturen von [Tl(tsac)] (1) und [Tl-(tsac)(ophen)] (2) (tsac ϭ Anion von Thiosaccharin; ophen ϭ 1,10 Phenanthrolin) wurden röntgenographisch, bei 116 K, an Einkristallen bestimmt. Komplex 1 kristallisiert in der monoklinen Raumgruppe P2 1 /a mit Z ϭ 4 und Komplex 2 in the monoklinen Raumgruppe C2/c mit Z ϭ 8. In beiden Komplexen ist Tl I an ein Thiosaccharinat-Anion über das Schwefel-und das Stickstoffatom koordiniert. Im Komplex 1 ist eine verzerrte achtfache Koordina-

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

“…Therefore, and as it has been found in previously investigated thiosaccharinato complexes [3][4][5][6], one may expect interaction of the Pd(II) cation with the S and N atoms of the deprotonated ligand. This expectation was clearly confirmed by the analysis of IR spectrum of Pd(tsac) 2 Á H 2 O.…”

“…As discussed in our previous papers on different thiosaccharinato complexes [3][4][5][6] the most important and interesting vibrational modes for structural analysis, correspond to vibrations of the five-membered ring localized between 1500 and 400 cm À1 and which involve, in particular, the (CN), (CS), (NS) and (SO 2 ) motions. In table 1 these and other characteristic vibrations of free thiosaccharin [3] and of the Pd(tsac) 2 The data presented in this table show the same trends for Pd(tsac) 2 Á H 2 O as those observed for the other two complexes.…”

“…Tetramethylsilane was used as the internal standard and the chemical shifts are reported in ppm. The stability of the complex in such medium was monitored by 1 H-NMR at 303 K in DMSO-d 6 during the NMR experiments, to examine possible ligand substitution by DMSO. Special attention was paid to the emergence of DMSO signals, that must appear if DMSO enters the coordination sphere of the metal atom (cf [9] and references therein), and the emergence of signals due to the free ligand.…”

“…We have begun a systematic study of thiosaccharinato complexes, preparing and performing detailed structural and spectroscopic studies of different Cd(II) and Tl(I) complexes containing this ligand alone or together with other coordinating molecules [3][4][5][6]. * In order to investigate the differences in chemical behavior between saccharin and thiosaccharin we have also performed a theoretical study, using density functional theory, of the electronic structures of these molecules and their anions [7].…”

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]…”