Chemistry of thiocarboxylates: syntheses and characterization of silver and copper thiocarboxylate complexes, and the structures of (Ph_4P)(M(SC{O}Me)_2)(M = Cu or Ag) and (Et_3NH)(Ag(SC{O}Ph)_2)

摘要

The bis(thiocarboxylate) complexes of silver (I) and copper (I) namely, [Ph_4P][M(SC{O}Me)_2], (M = Cu 1 or Ag 2) and [Et_3NH][M(SC{O}Ph)_2] (M = Cu 3 or Ag 4) were prepared from the appropriate metal salt, RC{O}S~- anions and the counter ion in the ratio 1:2:1. The structures of 1, 2 and 4 were determined by X-ray crystallography. The compounds 1 and 2 are isomorphous and isostructural. In both structures, the metal is bonded to sulfur atoms of two thioacetate ligands to give a near-linear geometry. A crystallographically imposed 2-fold rotational symmetry is present in the anions and the cations. The [Ag(SC{O}Ph)_2)~- anion in 4 also has an approximately-linear SAgS skeleton. One of the S atom interacts weakly with a second silver (I) ion to form a dimer. The N-H hydrogen atom of the Et_3NH~+ cation is involved in N-H...O hydrogen bonding to a carbonyl oxygen atom of the anion. There is a crystallographic center of symmetry present in this 'ion-pair dimer', having a rectangular arrangement of Ag_2S_2 with a T-shaped coordination geometry around the silver atoms. All the compounds decompose under a nitrogen atmosphere to the corresponding metal sulfides according to weight loss observed in TG.