Isolation, structure and spectroscopic properties of [Re2(C3S5)5]2– complexes and electrical conductivities of their oxidized species

Salts of the dianion [Re2(C3S5)5]2–[C3S52–= 4,5-disulfanyl-1,3-dithiole-2-thionate(2–)] with PPh4+1, NEt4+2 and NBun4+3 were prepared. A single-crystal X-ray analysis of 1 revealed that the dinuclear anion containing a Re–Re single bond and two Re–S–Re bridges involving the C3S5 ligands contains distorted-octahedral co-ordination geometries around both metal atoms and that the anions are associated into a dimeric form through sulfur–sulfur contacts, being further arranged into a chain through other such contacts. Redox potentials of the [Re2(C3S5)5]2– anion were determined by cyclic voltammetry. Complexes 1 and 2 were oxidized by iodine, [Fe(C5H5)2][PF6], and [ttf]3[BF4]2(ttf˙+= the tetrathiafulvalenium radical cation) or current-controlled electrolysis to yield species [ttf][Re2(C3S5)5], [PPh4]x- and [NEt4]y-[Re2(C3S5)5](x,y= 0.1–0.65). They behave as semiconductors with electrical conductivities of 2.0 × 10–3–4.9 × 10–2 S cm–1 for compacted pellets at room temperature. The electronic states of the oxidized complexes are discussed on the basis of electronic absorption, IR, ESR as well as X-ray photoelectron spectra.

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