SYNTHESES, PROPERTIES, CRYSTAL AND MOLECULAR-STRUCTURE OF A NOVEL NEUTRAL PENTANUCLEAR COPPER(I) IODIDE SPECIES - COPPER(I) COMPLEXES WITH TETRAETHYLTHIURAM MONOSULFIDE

The reaction of copper(I) iodide with tetraethylthiuram monosulfide L- Et afforded the novel copper(I) pentanuclear neutral complex [(Cu5L2I5 )-I-Et]. EtOH . MeCN 1. Its crystal structure may be described as a ve ry distorted octahedral central Cu3I3 cage having two additional CuLEt (I) units fused to the central cage by means of two iodine and one sul fur bridging atom. All copper(I) atoms in 1 are tetrahedral and both s ulfur ligands are bidentate. The solvent molecules occupy intermolecul ar vacancies generated by the manner in which 1 is packed in space. In contrast, other copper(I) halides CuX (X = Cl or Br) with tetraethylt hiuram monosulfide afforded the copper(I) complexes [CULEt(X)] (X = Cl 2 or Br 3) which exist in the solid state as monomeric units featurin g three-co-ordinate copper(I). The ligands are bidentate and co-ordina tion is completed by the halogen atoms. The complexes were additionall y characterized by IR and H-1 NMR spectra as well as magnetic suscepti bility measurements. Complexes 2 and 3 can be alternatively prepared b y sulfur abstraction from the disulfides, using triphenylphosphine. Co pper(I) iodide and tetraethylthiuram monosulfide failed to yield a mon onuclear compound under a variety of experimental conditions.