Complexes of palladium(II) and platinum(II) with phenoxathiin and thianthrene

Abstract

Phenoxathiin interacts not only with Pdn but also with PtT1. Thianthrene undergoes closely parallel interactions with these metal ions. For each metal-ligand pair, l : l and 1: 2 complexes, [MCI,L] and [ML,]CI, have been identified by the method of continuous variation. The 1:2 complexes have, in addition, been characterized by microanalysis, i.r. and electronic spectra, and conductivity measurements. These complexes are believed to have approximate square-planar structures in which the heterocyclic compounds act as bidentate ligands. In nitrobenzene solutions, it appears that, in the 1: 2 complexes, one or both of the chloride ions may be weakly bonded to PdI1 or Ptn.

Synthesis and Characterization of Semiconductive Dichloridobis(thianthrene)gold(1+) Tetrachloridoaurate(1–)

“…Thermal activation is implicitly necessary for the electron transfer, and substantial conductivity is only achieved well above ambient temperature. 4 . Evaluated with the Kubelka-Munk function, the reflectance increases gradually up to the highest wavelength measured, 800 nm, with a steeper increment above 650 nm.…”

“…[2] The two sulfur atoms have thus in principle the possibility to bond simultaneously to one metal centre. The results from early attempts to prepare complexes of thianthrene with nickel, [3] palladium, platinum, [4] ruthenium, [5] silver, rhodium, iridium and gold, [6] the last mentioned with crystallographic support, [7] indicate that TA behaves preferably as a monodentate ligand. By means of Job's method of continuous variation and microanalysis, the metal/ligand ratios in the Pt II or Pd II complexes are known to vary with the solvent used.…”

“…Even at low laser power only strong fluorescence was observed. 4 ] is thermally stable up to 438 K. At this temperature the decomposition was detected visually. In the DSC (differential scanning calorimetry) measurements a very small endothermic effect around 350 K appeared, which, however, was only detected during the first heating and did not appear again in the subsequent heating/ cooling cycles (Figure 4).…”

“…By means of Job's method of continuous variation and microanalysis, the metal/ligand ratios in the Pt II or Pd II complexes are known to vary with the solvent used. [4] Whereas these two metals form complexes up to a 1:2 metal/ligand ratio, iridium is claimed to form complexes with a 1:3 metal/ligand ratio. [6] The reaction of AuCl 3 and TA in CHCl 3 is known to give a 1:1 complex, [AuCl 3 (TA)], with only one of the sulfur atoms attached to the square-planar coordinated Au atom (Figure 1, right).…”

Digold(I) Thianthrenyl Complexes. Effect of Diphosphine Ligands on Molecular Structures in the Solid State and in Solution

“…Thianthrene has been reported to form complexes with Ag(I), Au(I), and Pd(II) as neutral S-ligands. 10 − 12 Pd complexes containing a phosphine ligand bearing a thianthrenyl substituent have been reported to form a cyclic compound with a Pd–S bond. 13 An Fe complex with η 6 -coordinated thianthrene has also been prepared and reported to show electrochemical responses from the ligand and Fe centers.…”