Reduction and oxidation reactions of the dirhenium(III) non-metal-metal-bonded edge-sharing complex, Re-2(mu -Cl)(2)Cl-4(PMe3)(4) (1), have been studied. Several new mono- and dinuclear rhenium compounds have been isolated and structurally characterized in the course of this study. Reductions of I with 1 and 2 equiv of KC8 result in an unusual face-sharing complex having an Re-2(5+) core, Re-2(mu -Cl)(3)Cl-2(PMe3)(4) (2), and a triply bonded Re-II compound, 1,2,7,8-Re2Cl4(PMe3)(4) (3), respectively. Two-electron reduction of 1 in the presence of tetrabutylammonium chloride affords a new triply bonded complex of the Re-2(4+) core, [(Bu4N)-N-n][1,2,7-Re2Cl5(PMe3)(3)] (4). Oxidation of 1 with NOBF4 yields a Re-IV mononuclear compound, trans-ReCl4(PMe3)(2) (5). Two isomers of the monomeric Re-III anion, [ReCl4(PMe3)(2)](-) (6, 7), have been isolated as side products. The crystal structures of compounds 2 and 4-7 have been determined by X-ray crystallography. The Re-Re distance in the face-sharing complex 2 of 2.686(1) Angstrom is relatively short. The metal-metal bond length in anion 4 of 2.2354 (7) Angstrom is consistent with the usual values for the triply bonded Re24+ core compounds, In addition, a cis arrangement of trimethylphosphine ligands in the starting material 1 is retained upon reduction in the dinuclear products 2-4.