Complexes of the type trans-[Re(PR₃)₂(Schiff base)]⁺ (R = ethyl and/or phenyl) 2–7 were prepared by the reaction of (nBu₄N)[ReOCl₄] with H₂sal₂en or H₂sal₂ibn followed by addition of a tertiary phosphine. The trans-[Re(PR₃)₂(sal₂en)]⁺ complexes 2–4 were stable in solution, whereas the trans-[Re(PR₃)₂(sal₂ibn)]⁺ complexes 6–7 were observed to convert to their corresponding cis-[ReO(PR₃)(sal₂ibn)]⁺ products through a process involving ligand dissociation, metal oxidation, and Schiff base ligand rearrangement. The conversion of the trans-[Re(PR₃)₂(sal₂ibn)]⁺ complexes is likely driven by steric interactions between the bulky backbone gem-dimethyl groups of the sal₂ibn ligand and the phosphine ligands. These complexes were isolated and characterized by ¹H and ¹³C NMR, FT-IR spectroscopy, cyclic voltammetry, and single crystal X-ray diffraction. The results reported herein provide insight into the factors that drive trans-[Re(PR₃)₂(Schiff base)]⁺ complex formation. This will aid in the development of novel ^186/188Re therapeutic agents and the design of novel bifunctional N₂O₂ Schiff base ligands.