Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh3, NCMe, NCPh, imines, ketones, Et2O, THF, MeOH, and Mel affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(-)(4) salts. The new complexes have been characterized spectroscopically and, for [Re(eta1-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH3, 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Cequivalent toCR)(CO)(3)(bipy)] (R = Ph, 12; R SiMe3, 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate.