Two rhenium compounds, α-Re 2Cl 4(dppe) 2 and trans-ReCl 2(dppe) 2, were isolated during the study of the reactivity of Re 2Cl 6-(P(n-Bu) 3) 2 with the bidentate phosphine 1,2-bis(diphenylphosphino)ethane (dppe) in the presence of acetonitrile, and a high yield synthetic route was developed for α-Re 2Cl 4(dppe) 2. The structures of α-Re 2Cl 4(dppe) 2 · (C 6H 6) 4, α-Re 2Cl 4(dppe) 2 · (dppe), and trans-ReCl 2(dppe) 2 · ((CH 3) 2CO) 2 were determined by X-ray crystallography and the following data obtained: α-Re 2Cl 2(dppe) 2 · (C 6H 6) 4, monoclinic P2 1/ c, with a = 14.841(3), b = 12.161(4), c = 18.628(7) A ̊ , β = 95.33(3)°, V = 33348(2) A ̊ 3, Z = 2, R1 = 0.0418 , and wR2 = 0.1046; α-Re 2Cl 4(dppe) 2 · (dppe), monoclinic P2 1/ c, with a = 10.695(3), b = 16.858(7), c = 19.710(7) A ̊ , β = 101.78(1)° , V = 3479(2) A ̊ 3 , Z = 2, R1 = 0.0450 and wR2 = 0.1023; trans-ReCl 2(dppe) 2 · ((CH 3) 2CO) 2, monoclonic P2 1./ c , with a = 11.507(3), b - 13.519(3), c = 17.243(4) A ̊ , β = 96.08(2)°, V = 2667.3(11) A ̊ 3, Z = 2, R1 = 0.0369, wR2 = 0.0887 . Additional characterizations of α-Re 2Cl 4(dppe) 2 were performed with 31P NMR and UV-Vis spectroscopy.