The reactions of the quadruply bonded complexes (n-Bu 4 N) 2 Re 2 X 8 (X=Cl, Br) with excess 3,6-dithiaoctane (CH 3 CH 2 SCH 2 CH 2 SCH 2 CH 3 or dto) under forcing conditions lead to the compounds Re 2 Cl 5 (dto) 2 (1) and Re 2 Br 5 (dto) 2 (2) with Re-Re triple bonds. X-ray crystallographic studies of compounds 1 and 2 reveal a common staggered, unsymmetrical molecular geometry with both dto ligands chelated to the same metal atom. This Re atom is also bonded to a single axial halide ligand, while the other four halides surround the second Re atom. In contrast to the only previous example of this type of dirhenium compound, Re 2 Cl 5 (dithiahexane) 2 , there is no sharing of axial chloride ligands between molecules in the crystal lattices of 1 and 2. The Re-Re bond distances are 2.2772(8) and 2.2826(6) Å in 1 and 2, respectively. Magnetic measurements, cyclic voltammetry, and IR, Vis and ESR spectra of 1 and 2 are reported. Addition of dto to a solution of (n-Bu 4 N) 2 Re 2 (NCS) 8 leads to the formation of (n-Bu 4 N) 2 Re 2 (NCS) 8 .dto (3). Crystallographic studies show 3 to consist in the solid state of chains of [Re 2 (NCS) 8 ] 2 - units linked together by dto molecules with each dto sulfur atom weakly coordinated to axial sites on Re atoms of different anions. The Re-Re quadruple bond distance in 3 is 2.2854(3) Å.