The oxidation of [Re(eta(6)-C10F18)(2)](+) with Ag-I in acetonitrile yields [Re(NCCH3)(6)](2+). This fully solvated Re-II compound was characterized by spectroscopic methods and X-ray structure analyses. We show that [Re(NCCH3)(6)](2+) acts as a precursor complex for a variety of substitution reactions. Treatment with monodentate triphenylphosphine (PPh3) and bidentate 1,2-bis(diphenylphosphino)-ethane (dppe) yields the complexes [trans-Re(PPh3)(2)(NCCH3)(4)](2+) and [trans-Re(dppe)(2) (NCCH3)(2)](+), respectively. [trans-Re-(dppe)(2) (NCCH3)(2)](+) is oxidized under mild conditions by Ag-I to its Re-II analogue [trans-Re(dppe)(2) (NCCH3)(2)](2+). Reactions of [Re(NCCH3)(6)](2+) with a halide mixture consisting of NaX and AgX (X = Cl, I) result in the formation of the corresponding Re-III complexes [trans-ReX2 (NCCH3)(4)](+). [trans-ReBr2 (NCCH3)(4)](+) can be obtained directly from [Re(eta(6)-C10H8)(2)](+) by oxidation with FeBr3 in acetonitrile. The title compound is thus a convenient starting material for Re-II and Re-III complexes by simple solvent exchange, which are otherwise difficult to access.