The heterobimetallic complexes [Mn((PrNPPh2)-Pr-i)(3)Cu((PrNHPPh2)-Pr-i)] (1) and [Fe((PrNPPh2)-Pr-i)(3)Cu(iPrNHPPh(2))] (2) have been synthesized by the one pot reaction of (LiNPrPPh2)-Pr-i, MCl2 (M = Mn, Fe), and CuI in high yield. Addition of excess CuI into 2 or directly to the reaction mixture led to the formation of a heterotrimetallic [Fe((PrNPPh2)-Pr-i)(3)Cu-2((PrNPPh2)-Pr-i)] (3) in good yield. Complexes 1-3 have been characterized by means of elemental analysis, paramagnetic H-1 NMR, UV-vis spectroscopy, cyclic voltammetry, and single crystal X-ray analysis. In all three complexes, Mn or Fe are in the +2 oxidation state and have a high spin electron configuration, as evidenced by solution Evans' method. In addition, the oxidation state of Fe in complex 3 is confirmed by zero-field Fe-57 Mossbauer spectroscopy. X-ray crystallography reveals that the three coordinate Mn/Fe centers in the zwitterionic complexes 1-3 adopt an unusual trigonal planar geometry.