Chemistry of thiocarboxylates: syntheses and characterization of silver and copper thiocarboxylate complexes, and the structures of [Ph4P][M(SC{O}Me)(2)] (M = Cu or Ag) and [Et3NH][Ag(SC{O}Ph)(2)]

The bis(thiocarboxylate) complexes of silver(I) and copper(I) namely, [Ph4P ][M(SC{O}Me)(2)], (M = Cu 1 or Ag 2) and [Et3NH][M(SC{O}Ph)(2)] (M = Cu 3 o r Ag 4) were prepared from the appropriate metal salt, RC{O}S- anions and t he counter ion in the ratio 1 : 2 : 1. The structures of 1, 2 and 4 were de termined by X-ray crystallography. The compounds 1 and 2 are isomorphous an d isostructural. In both structures, the metal is bonded to sulfur atoms of two thioacetate ligands to give a near-linear geometry. A crystallographic ally imposed 2-fold rotational symmetry is present in the anions and the ca tions. 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) i on to form a dimer. The N-H hydrogen atom of the Et3NH+ 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 Ag2S2 with a T-shaped coordination geo metry around the silver atoms. All the compounds decompose under a nitrogen atmosphere to the corresponding metal sulfides according to weight loss ob served in TG.