The asymmetric pi basic metal fragment {TpRe(CO)(Melm)} (Tp = hydridotris(pyrazolyl)borate, Melm = 1-methylimidazole) forms thermally stable complexes with ethyl acetate, acetic anhydride, N-methylsuccinimide, N-acetylpyrrole, and N-methylmaleimide in which the metal binds a carbonyl group in a g fashion. In all cases a single diastereomer is observed, indicating that one enantioface of the carbonyl is selectively coordinated. X-ray and NMR data for the compound TpRe(CO)(Melm)(eta(2)-N-methylsuccinimide) indicate that metal coordination effectively removes the T interaction between the bound carbonyl and the nitrogen of the succinimide ring.